JPS63502285A - Olefin chlorosilane and olefin halide functional group-containing polymer and method for producing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Olefin chlorosilane and olefin halide functional group-containing polymers and their manufacturing method Background of the invention 1. Cross-reference of related applications This application is a part of U.S. Patent Application No. 1113.511 filed December 16, 1985. Continuation application No. 813,511 is a U.S. patent filed on December 14, 1984. This is a partial continuation of Application No. 881,950, and S8g1.950 is No. 4,540,753, issued September 10, 1985 (hereinafter referred to as CO). This is a partial continuation application of the patent of Cozevlth et al. The disclosure of is incorporated herein by reference.

2. Field of invention The present invention provides a novel alpha olefin copolymer, its production method, and a copolymer. Contains methods for joining polymer chains and cross-linking to form cross-linked copolymers with special applications. It is something to do.

More specifically, the present invention relates to ethylene and α-olefins other than ethylene. , olefinic chlorosilanes and olefinic hydrocarbon halides. Low 1 halogen-containing monomer and optionally at least one non-conjugated diene The present invention relates to copolymers of the same standard.

These copolymers may be statistical (random) polymers or A continuous or discontinuous first segment and an alpha olefin consisting of A chain consisting of a monomer containing μ, 1, α-olefin and at least one halogen-containing monomer. It may be segmented into continuous or discontinuous segments.

In particular, the present invention utilizes the method of making these copolymers and optionally uses a crosslinking agent to It is about how to bridge.

Where the copolymer is segmented, the crosslinked copolymer has a nodular shape (no duralforll). In this nodular form, the crosslinking agent itself improves dispersibility. may contain functional groups.

The invention further provides that the at least one halogen-containing monomer is an olefinic chlorosilane or Grafted polymer chains formed from copolymer chains that are olefinic or olefinic hydrocarbon It is related to the manufacturing method of remurft polymer.

Preferably, the copolymers of the invention exhibit a narrow molecular weight distribution. set of copolymer chains Sei can be “tailored” (tai 1or). Controllable composition Among the factors are the sequence of the monomers, their relative proportions in the chain, the portion of cross-linking and Frequency, composition and placement of additional substitutions in and from the chain (this (all of which follow the method of invention). For example, olefin chlorosilane and and olefinic hydrocarbon/X rides can be restricted to specific parts of the chain.

When using a tubular reactor in the method of the invention, such "tailoring" An important means to achieve this is to introduce the reactants along the adhesive The composition, proportions, and flow rates of the reactants are varied.

The non-crosslinked random and segmented copolymers of the present invention are useful for coating inorganic substrates. They are used in glass fiber and filled rubber compositions. Non-shelf Bridge random and segmented - olefin chlorosilanes or olefin halides Copolymers are linked to form unusual branched structures; they can be grafted or used as an intermediate for the formation of block polymers and thermoplastic elastomers and compatibilizer-like compositions.

The crosslinked random copolymers of the present invention can be used in numerous elastomeric applications, such as sealing. Sheeting caulks, sealants, gaskets, etc. used in the production of Nodular copolymers can be used in lubricating oil compositions like oil additives. used for things.

3. Background explanation of related materials For convenience, some terms used repeatedly throughout this specification are defined below. Attach: (a) Inter-CD is a composition variation with respect to ethylene content between polymer chains. Define the movement. It consists in removing equal weight fractions from both ends of the distribution. The total copolymer sample thus obtained contains the weight percent required to From the average ethylene composition in terms of ethylene weight percent of the copolymer samples prepared occurs as the minimum deviation (similar to standard deviation) of deviations need to be symmetrical do not have. When it appears as a single number, for example 15% Inter-CDs It means the greater of the positive or negative deviations. For example, Gaussian set If the standard deviation of the composition distribution is 10%, then 95.5% of the polymer is 20% ethylene by weight. is the average value within the range. In such a sample, 95.5% by weight of the polymer Int er-CD is 20% ethylene by weight.

(b) Intra-CD is a compositional variation with respect to ethylene within the copolymer chain. be. It is the weight (vt%) of ethylene present between the two parts of one copolymer chain. , with each portion comprising a minimum of 5% by weight of the chain.

(C) Molecular weight distribution (MWD) is a measure of the range of molecular weights within a given copolymer sample. It is. It is the ratio My/Mn of weight average molecular weight to number average molecular weight and 2 Characterized by at least one ratio of average molecular weight to weight average molecular weight Mz/My Here, My-ΣNj old 2/ΣN1 old Here N1 is the number of molecules in the weight old (d) Viscosity index (V, 1.) indicates that the lubricating oil exhibits a minimum decrease in viscosity as the temperature increases. It is the ability to adapt. The larger this ability is, the more v,1. is expensive.

Ethylene-propylene copolymers, particularly elastomers, are important stopper market products.

Two basic types of ethylene propylene copolymers are on the market. ethylene ・Propylene copolymer (EPM) is produced by free radical generators such as organic peroxides. It is a saturated compound that requires vulcanization. Ethylene-propylene terpolymer (EP D) l) contains a small amount of a non-abrasive diolefin, such as dicycloveztagene; ．． 4-hexadiene or ethylidene norbornene.

These provide sufficient unsaturation to allow sulfur vulcanization. at least two Such polymers containing monomers, namely EPM and EPDM, are hereinafter referred to as are collectively called copolymers.

These copolymers are low cost compounds that are particularly suitable for very good weather resistance and good heat aging resistance. It is a thing. Typical automotive uses are tire sidewalls, internal tubes, radiators and heater hoses, vacuum tubing, weather stripping and sponges. Used as a door seal and viscosity coefficient (V, 1.) improver for lubricating oil compositions. be exposed. Typical applications for machines include household appliances, industrial hoses and garden Hoses, molded and extruded sponge sections, gaskets and seals, conveyors It's a belt cover. These copolymers are used in adhesives, parts of household appliances, and wire and cable insulation and plastics Also used for bending.

As mentioned above, EPM and EPDM are based on their respective characteristics. , has many different uses. Adapting such copolymers to specific applications The properties are known to be determined in turn by the composition and structure of this copolymer. It's been done. For example, the ultimate properties of EPM or EPDM copolymers are Depending on factors such as composition distribution, sequence distribution, molecular weight and molecular weight distribution (IWD) Determined.

The efficiency of peroxide curing is composition dependent. increased ethylene levels It is shown that the chemical cross-linking per peroxide/molecule increases as . Ethylene content also influences rheological and processing properties, leading to crystallization. This inhibits processability, and at temperatures below the effective crystal melting point of rubber, the cured product becomes soft. Too “hard<°too hard” EPM or EPDM: The kneading behavior of the polymer (will llngbehavior) changes rapidly depending on Mi. Narrow MvD copolymer is crumbled into crumbs on a roll machine, while broad MVD material is used in regular processing. It is rolled into a band under the following conditions. At the shear rate encountered in processing equipment, , a copolymer with a wider MVD has a narrower M[) of the same weight average molecular weight. It has a substantially lower viscosity than other polymers with There is always a need to discover polymers that have properties. This is the lubricant's v, 1° change. Easily exemplified in the area of stimulants.

Motor oil avoids significant friction losses and facilitates cold starting However, in order to ensure proper and free oil circulation from the time the engine starts up, It should not be too viscous at low temperatures. On the other hand, excessive engine wear and excessive In order to avoid oil consumption, the viscosity should not be too small. Due to temperature changes It is most preferred to use a lubricating oil that exhibits minimal viscosity changes.

The ability of a lubricating oil to resist temperature increases with minimal decreases in viscosity is determined by its viscosity index (V, 1.). Therefore, it is shown. The larger this ability is, the more v,1. is expensive.

Polymeric additives are widely used in lubricating oil compositions and provide favorable viscosity-temperature properties to the compositions. give. For example, V,+, EPM or EPDM as improving agent or more. Lubricating oils that typically use ethylene-(C3-C,8) alpha-olefin copolymers Compositions are known. These additives prevent viscosity changes that occur with temperature changes. It is designed to produce a lubricating oil composition that packs as little weight as possible. this Lubricating oils containing polymer additives such as and maintains favorable low viscosity fluidity at engine start temperature during unidirectional operation. Ru.

Two important properties of these additives (although the only necessary properties) relate to low temperature performance and shear stability. Low temperature performance is It is related to maintaining low viscosity at very low temperatures, while shear stability It relates to the resistance of an excipient to being broken down into smaller chains.

Ideally, preferred ■, 1. The modifier is a polymer with good shear stability.

These polymers generally have low thickening efficiency and low molecular weight. But generally Therefore, low molecular weight polymers have low bulk viscosities and exhibit cold flow. They are one Difficult to handle in general rubber processing factories.

When operated carefully, a reactor consisting of polymerization to enhance its various properties on a selective basis depending on the intended use. It turns out that it is possible to do this. The most suitable actor within the scope of the invention is m1x ( ree tubular and batch reactor.

Typical prior art techniques for producing copolymers by processing in a tubular reactor are as follows. These are: Junghans (E, Junghans), Gunvolt (A, G) umboldt) and beer (G, Bier;) Lido and alkyl aluminum halide catalyzed ethylene and proble Polymerizatis of ethy lene and propylene t.

amorphous copolymers with catalysts or vanadiumoxychloride and alkyl alu ainum halldes)”;MakroIio’1.Chew,, Volume 58 (12/12/62); pages 18-42, Discloses the use of a tubular reactor to produce lopyrene copolymers , where the composition varies along the length of the chain. To explain in more detail , this reference example shows how vanadium compounds and aluminum are used in tubular reactors. Amorphous ethylene-propylene using Ziegler catalyst made from nitrogen alkyl Discloses the production of ren copolymers. Ethylene predominates in the first part of the tube. If the monomer mixture is previously polymerized and the monomer mixture is made-up during the polymerization, If this is not done, the monomer concentration will favor propylene along the tube. It has been disclosed that there is a change in These concentration changes occur during the chain growth reaction. However, it has also been disclosed and shown that copolymer chains containing more ethylene at one end than at the other end are formed. It is done. The copolymer formed in the tube is chemically non-uniform, but the molecular It is also disclosed that the amount distribution is uniform. made in a tube Using the data reported in their Figure 17 for a copolymer of The My/M/n ratio of Limer is 1.6, and from their Figure 18, this copolymer The intermolecular compositional dispersion (Inter-CD, explained in detail below) of It is estimated that the

Vehner, J.P., “Laminar Flow Polymerization of EPDM Polymers” lnar Flow Polymerization or EPDM Pol ymer” ;^cs Symposium Series 65 (1978); 140 (52 The page provides data on the polymerization of tubular reactor solution polymerization using one catalyst. A computer simulation was carried out to determine the effect on the molecular weight distribution of the mer products. Disclose the results of the study. The special polymer imitated is ethylene - It was an elastomeric terpolymer of propylene-1,4-hexadiene.

On page 149, it says that because monomers have different reactivities, monomers run out. It is stated that polymers with different compositions can be obtained depending on the method. But its composition It is not possible to tell whether changes occur between molecules or within molecules. 148 pages m table predicts various polymers with about 1.3(7) Mν/in. Ru. Section 3 on page 144 states that as the tube diameter increases, the polymer molecular weight decreases. If it becomes too low, there will be no practical interest in it. And that reactor It is expected to be a plug. Section 1 on page 149 states that It is implied that the resulting compositional dispersion is unfavorable for product quality.

Wehner, U.S. Pat. No. 3,681,306, discloses the Ethylene/higher α-olefin copolymer with good processability through polymerization This is an example disclosing a method for producing mer. According to this reference example, this 21 step method is cold flow, which contributes to predetermined properties, especially processability in commercial applications. properties such as high green strength and rollability (a+1llablllty) 1119 polymerization method to create custom ethylene/α-olefin copolymers with I will provide a. According to this reference example, the process of the invention is a synergistic compound useful in the production of EPDM. Ethylene/problene such as 15-ethylindene-2-1rubornene using a catalyst It is particularly suited for producing elastomeric copolymers.

The preferred method uses one tubular reactor followed by one bot-reactor. . However, using one tubular reactor and simulating two stages It is also disclosed that different reaction conditions can be used. Column 2, lines 14-20 As can be seen, the inventive method is more versatile than that produced in a single-stage reactor. Create polymers with high MVD. Middle of the first (piperine) reactor The product polymer is in column 5, ! Approximately 2 My as disclosed in lines +4-57 /Mn ratio, but the final porous produced by the method of the invention is The remer has a My/Mn of 2.4-5.

Closon, U.S. Pat. No. 3,825,858, discloses that the reactants are With reference to a closed-circuit tubular reactor that recirculates at a The hinge support (lO) for limb 1 of the This can prevent harmful deformations caused by straining, especially during cleaning of the reactor. Ru.

U.S. Pat. No. 4.065.520 to Bayley et al. Batch reactor for making ethylene copolymers, including elastomers, with Discloses the use of A bedding supply tank for the reactor is placed; The feed to each tank is varied to produce polymer. The product made is It has crystalline to semicrystalline to amorphous regions, with gradients varying between them. touch The medium system uses vanadium compounds alone or in combination with titanium compounds. Vanadium oxy-trichloride and diisobutyl aluminum chloride An example is Nium. Titanium compounds are used in all examples. go In some examples hydrogen and diethyl lead (known as a transfer agent) are used. It will be done. The resulting polymer chains have a compositionally dispersed first length and a uniform second length. have Subsequent lengths have various other compositional distributions.

Mick (Y, former Tsuda) Schrag (J, Schrag) and Ferry (J, Ferry) “Ethylene-propylene terpolymer from infinite dilution viscoelasticity” Estimation of long-chain branching in Long-Cha in Branchlng in Ethylene-Propylene T erpolymers from Infinite-DilntionVis coelastlc Properties)' J, Appl, Po1. Sc i, Vol. 18, p. 193 (1974) describes narrow MVD ethylene-propylene Ren copolymers are disclosed. For example, in the ■ table on page 198, 1.19 ~1.32 ilv/in) EPDI4 copolymers are disclosed.

"C, ni, 5hih" "molecular weight and molecular weight fraction of ethylene-propylene" Effect on the non-Newtonian behavior of diene polymers”1lj (The Er rector　Mo1ecular　Weightand　Mo1ecular Weight Distribution on the Non-New tonlan Behavior of Ethylene-Propylene e-DlenePolymers)” Trans, Soc, Rheol, 1 Volume 4, page 83 (1970), gives a complete series of compositionally homogeneous fractions. disclosed. For example, the data in Table 1 is based on a highly homogeneous polymer “sample.” Based on the reported data, the MWD of this sample is also very narrow. stomach. However, it does not disclose polymers having intramolecular dispersibility.

We handle ethylene-α-olefin copolymer as a lubricant additive. The apparent prior art is as follows: U.S. Pat. No. 3,697,429 to Engel et al. Ethylene-propylene copolymers with a content of 40-83% by weight 9 6 ethylene and a difference in ethylene content from that of the second copolymer of up to about 4 mers. Discloses a mixture that is a minimum of 4 vt% ethylene. These mixtures are lubricating oils. V,+, when used as a improver, oil pour point depressant and ethylene-propylene co Minimizes adverse interactions with the polymer to provide suitable low temperature viscosity properties.

40.000, with a propylene content of 20 to 70 mol%, ethylene-propylene v of the copolymer in lubricating oil, 1. It is disclosed as an improving agent. These copolymers The preferred My/Mn is less than about 4.0.

Johnston et al., U.S. Patent No. 3. l19L, No. 078 is 2 Contains 5-55 wt% ethylene, has a Benpunto index of 1it-33, and has an average Benpunto index of 1it-33. ethylene-propylekene copolymer with a particle size not exceeding 20 carbon atoms. Discloses use as a lubricating oil additive. My/Mn is less than about 8.

These additives can improve the viscosity without adversely affecting the rheological depressants. gives the oil good low-temperature properties.

U.S. Patent No. 3,551.338 to Jacobson '4 Contains less than 1.3 vt% of polymer flanks that are insoluble in n-decane at 5°C , using ethylene copolymer of Go-80a+ole% ethylene as oil additive Discloses that. This decane-insoluble flank John in the polymer Reducing the tendency of the polymer to form haze in oil, this haze This is probably evidence of low temperature instability caused by unfavorable interactions with pour point depressants. Ru.

The 'S4v/Mn' of these copolymers is "surprisingly narrow, less than about 4.0, more Preferably it is 2.6 or less, for example 2.2.

In the viscosity index improver, it is necessary to improve the desired properties rather than the required properties of randomly cross-linked polymers. It's not even a characteristic. Unsaturated branched ethylene terpolymers and tetrapolymers An example of a related patent is US Pat. No. 3,790,480. Ethylene, C5-0 Polymers of 18 higher α-olefins and two dienes are taught; have the same or different polymerizable double bonds. By 1.4-hexadiene In a group of dienes represented by Another group, represented by 2,5-norbornadiene, which polymerizes rapidly, has a patent Both double bonds can be copolymerized using the polymerization process of Favorable viscosity index improvement The agent is an ethylene tetrapolymer in which both groups of double bonds are used. A port like this Rimers contain dienes along the entire length of the chain and are nodularly branched. He hasn't done it. For a given TE, the random branch looks like a 1-Jular branch. No efficient method improves shear stability.

The superior properties are probably due to the use of a diene with two active double bonds. Long chain branching occurs, and at the same time the bulk viscosity of the polymer increases, but originally This is probably because it does not significantly increase the viscosity or thickening efficiency of. increased bar The thick viscosity facilitates the manufacture and storage of the polymer. The catalyst used for polymerization is chi - It is a Glar type catalyst. Both double bonds of 2.5-norbornadiene are Ziegler - Can be polymerized with a catalyst. However, other dienes, 1,4-hexane Dienes have only one double bond that polymerizes with Ziegler's catalyst. therefore The polymer contains a small amount of unsaturation.

Summary of the invention The purpose of the invention is l) ethylene; 2) α-olefin; and 3) a) an olefinic chlorosilane having the structural formula 5IRR' x, where i) x is in the range 0-2 1i) R is a Ziegler copolymerizable olefin; 1i) R' is a saturated or is selected from the group consisting of unsaturated and branched and polycyclic hydrocarbons; a hydrocarbon having 30 carbon atoms, b) an olefin of the structural formula RR' hydrocarbon halide, where i) R is A Ziegler copolymerizable olefin, 1i) R' is saturated or unsaturated and branched or unbranched aliphatic, aromatic, cyclic and polycyclic a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of hydrocarbons; , 1i) X is halogen at least one halogen-containing monomer selected from the group consisting of a) and b); This is achieved by the present invention which provides copolymers of mer.

R Ziegler copolymerizable olefins include norbornenyl, dicyclopentenyl, and and l-hexenyl.

The olefinic chlorosilane utilized in the copolymer of the present invention has the structural formula: %formula% :) X is in the range 0-2: 1i) n is greater than or equal to 0; 1i) R and R' are the same or different; Each of R and R' can be saturated or unsaturated and branched or unbranched. selected from the group consisting of aliphatic, aromatic, cyclic and polycyclic hydrocarbons It is a hydrocarbon containing 1-30 carbon atoms.

There are olefin chlorosilanes. A specific olefin chlorosilane with this structural formula to vinyldimethylchlorosilane, vinylethyldichlorosilane, 5-1- Xenyl = 6-dimethylchlorosilane, l-hekymonyl-6-trichloraryl dichlorosilane, 5-trichlorosilyl-2-norbornene, and 5-methyl It is dichlorosilyl-2-norbornene.

Olefinic hydrocarbon halides are chlorides and bromides. Copolymers of the invention The specific olefin halide used is 5-chloromethyl-2-norbornene and 2-parachloromethylphenyl-5-norbornene.

The copolymers of the invention additionally contain at least one non-conjugated diene. preferred diene Examples include 5-ethylidene-2-norbornene, 4-hexadiene, and di- There are cyclopentadiene and mixtures thereof.

An important aspect of the invention is that a primary polymer comprising a copolymer of ethylene and an alpha-olefin one segment and at least one halogen-containing segment of ethylene, α-olefin and the above. towards a copolymer chain with a second segment consisting of a copolymer of monomers the scheme and the second segment are contigu ous) segment or multiple forms of discontinuous segments, and the second segment make up less than 50% of the copolymer chains. In addition, at least one halogen The containing monomer is crosslinked under conditions that do not substantially crosslink the first segment. obtain.

In one embodiment of this segmented copolymer of the invention, the first segment is The second segment comprises two segments, one at each end of the chain, forming the center of the copolymer chain. configure the components.

The present invention further provides a minimum of My/Mn of 2 or less and Hzl'\4v of 1.8 or less. For compositions consisting essentially of a plurality of the above segmented copolymers representing one I'm being kicked.

The invention further provides for forming a copolymer chain consisting of said first and second segments. Directed to the method. The method consists of a reaction mixture of polyolefins and α-olefins. , the weight of the ethylene-α-olefin copolymer produced is the expected polymer at the completion of polymerization. Form the first segment by polymerizing to the point where it reaches 50% of the weight, and the final segment. Reaction of monomers containing one halogen to form the second segment forming a second segment by introducing it into the mixture.

In one embodiment, substantially one first segment and substantially one second segment The copolymer chains consisting of the The second segment is produced by performing the second segment manufacturing step until the end of the segment.

In another embodiment, the second segment has almost complete reaction of the mer. and the resulting ethylene-α-olefin-halogen-containing monomer copolymer. Polymerize to the point where the weight is less than 50% of the expected polymer weight at the completion of polymerization; is formed by continuing the reaction to form the first segment; this implementation In the method of embodiments, the resulting copolymer chain consists essentially of one first segment. and substantially one second segment.

To make the copolymer chains of the present invention, at least one non-conjugated diene is present in the reaction mixture. added to.

The production method involves adding additional ethylene, α-olefin, non-conjugated diene and halide after initiation of polymerization. further comprising inserting at least one logen-containing monomer into the reaction mixture. You can also do it.

In a preferred embodiment of the process of the invention, ethylene, α-olefin and The halogen-containing monomer reaction mixture is essentially one type of catalyst and at least one halogen-containing monomer reaction mixture. +oix (in the ree reactor, the growth reactions of almost all copolymer chains are the same) Occasionally occurs in such a way that multiple polymer chains are formed, and therefore sufficient these copolymer chains contain almost no transfer agent. dispersed within the reaction mixture.

Preferably, the at least one 1x-f'ree reactor is a tubular reactor. In addition, ethylene, other alpha-olefin monomers, non-collaborative dienes and and at least one halogen-containing monomer. It is injected at at least one point along the reactor.

In other cases, a batch reactor is used.

The preferred α-olefin used in the reaction is propylene.

A front consisting of a first segment as the center of the chain and second strand segments at each end of the chain. By this method, the copolymer chains described above can be made of ethylene propylene and at least one A reaction mixture of monomers containing /-logen is introduced into the inlet of the reactor and its From there, a reaction mixture containing at least one of ethylene and propylene is added along the reactor. a monomer containing at least one halogen. created by introducing the vector into a second location after the first location. this At least one halogen-containing monomer used in the manufacturing process forms an olefin chloride. can be achieved.

If at least one halogen-containing monomer is an olefinic hydrocarbon halide, The resulting copolymer chains can be used in reactions to produce graft and block polymers. It will be done.

Such graft and block polymers are reacted with the prepared tallating agent and their This is then reacted with a monomer that is polymerized by anions to form a graft polymer. do. The metalating agent consists of branched alkyllithium and n-butyllithium. selected from at least one of the following groups.

In another embodiment, the copolymer chains are first reacted with Lewis acid; This is then reacted with a cationically polymerizable polymer to form a graft polymer. Ru.

Lewis acid is ethylaluminum dichloride, boron trichloride, and aluminum trichloride. selected from at least one of the following programs.

Isobutylene is used as the cationically polymerizable monomer. butadiene , isoprene and styrene are both anionically and cationically polymerizable.

Another important aspect of the invention is that essentially ethylene alpha-olefin and at least Directed to one halogen-containing monomer. The chain has both of these properties because preferable.

One or more non-conjugated dienes may be present. Suitable dienes include 5-ethylidene- These include 2-norbornene, 1,4-hexadiene and dicyclopentadiene.

Intra-co has an average weight percent composition of 95 wt% of the copolymer chains. having an ethylene composition that differs by no more than 15%, more preferably no more than 10%. It is something.

Inter-CD consists of a minimum of 2 parts of 6 strands - each part consisting of a minimum of 5vt% of the strands. have a composition of at least 5 vt% ethylene, more preferably at least 10 vt% ethylene. , most preferably differing by at least 2° vt% ethylene.

The invention further comprises a plurality of copolymer chains of the invention consisting essentially of a copolymer chain of the invention; The present invention is directed to compositions in which the mer chains are random copolymer chains.

Copolymers of the invention with olefinic chlorosilanes as halogen-containing monomers - Chains are used in glass fiber compositions consisting of glass fibers and plastic substrates. I can stay. Such copolymer chains of the present invention combine glass fibers with polymer chains. and then inserted into these compositions with this coating composition. Alternatively, A reaction mixture consisting of glass fibers, plastic matrix and copolymer chains is The glass fiber composition is first formed and then reacted to form the glass fiber composition.

In another important aspect of the invention, the copolymer chains are hardened.

When the halogen-containing monomer in the copolymer chain is an olefinic chlorosilane, , the crosslinking agent used is selected from the group consisting of water and a polyfunctional proton donor at least one composition.

Polyfunctional nucleophiles in which the halogen-containing monomer is an olefinic hydrocarbon halide are amines, polyamines other than diamines, and thioureas.

Cross-linking of the segmented copolymer chains of the present invention includes substantially cross-linking of the second segment. a substantially uncrosslinked first segment extending therefrom. can be used to produce nodular copolymers containing Ru. Each of the first and second segments of this nodular copolymer is substantially connected. present in the form of a continuous segment or multiple discontinuous segments; Each of the components constitutes substantially less than 50 vt% of the polymer chain.

The nodular regions of the Noginylar copolymers of the present invention also have functional properties with dispersive properties. It may also include a region containing a functional group. Such nodular copolymers are -Inserting agents with dispersible functional groups during the copolymer formation process Therefore, it is created. These agents include amides, pyridines, polycaprolact The lowest of polycaprolactam, pyrrolidone and imidazole.

It has one dispersing group. These agents, due to their dispersive groups, and attaches to the polyfunctional crosslinker in the nodule.

Such nodular copolymers are utilized in lubricating oil compositions. They are generally , about 1 to about 15 o of the total lubricating oil composition. ovt% amounts are used as additives.

Detailed description of the invention The present invention relates to ethylene, an alpha-olefin, and at least one olefinic chlorosilane. and at least one olefinic hydrocarbon halide and optionally a non-conjugated diene. The present invention relates to novel copolymers comprising compounds selected from the group consisting of:

The present invention relates to random and segmented copolymer chains comprising the above components. It is something that The segmented chain consists of the first segment of ethylene and alpha-olefins. and ethylene, alpha-olefin and olefinic chlorosilanes or olefins. a second and seventh segment of a hydrocarbon halide; Each of the second segments is one segment or more discrete segments within one limit. It can exist in the form of ment.

The present invention further provides cured compositions of the random and segmented copolymers described above. Involved. The curing step consists of crosslinking the copolymer chains with a crosslinking agent. Ko If the halogen-containing monomer in the polymer is an olefinic chlorosilane, use The crosslinking agent selected from the group consisting of water and a polyfunctional proton donor selected from one composition. The halogen-containing monomer in the copolymer is an olefin. In the case of a hydrocarbon halide, the crosslinking agent consists of ZnO and a polyfunctional nucleophile. at least one composition selected from the group consisting of:

The invention further provides olefin chloride as a monomer containing at least one halogen. Randoms and cells of the invention containing rosilanes or olefinic hydrocarbon halides It relates to graft polymers formed with segmented copolymers. Halide-containing co The polymer is a cation like Lewis acid.

reaction product with a cationically polymerizable monomer; to form a graft polymer. Alternatively, the copolymer is a metalating agent. The product of this reaction reacts with an anionically polymerizable monomer and the graph form a toppolymer.

Copolymers of the invention comprising an olefinic chlorosilane as at least one third compound reacts with hydroxy-terminated polymers, such as polyester, to form thermoplastic elastomers. Tomer can be formed.

Crosslinking of the segmented copolymers of the invention can produce nodular copolymers. child Nodular copolymer products such as the second segment are substantially cross-linked. comprising a nodular region with a substantially uncrosslinked first segment extending therefrom; . Additionally, the crosslinking agent itself may contain functional groups that exhibit dispersibility.

Suitable α-olefins include those containing 3-18i1 carbon atoms, e.g. Examples include lopyrene, butene-1, pentene-1, etc. 3-8 carbon α-olefin is Preferred from economic considerations. The most preferred α-olefin according to the invention is It is pyrene.

The olefin chlorosilane of the present invention has a structural formula X in the range of θ to 2, and R in the Ziegler - A copolymerizable olefin, where R' is saturated or unsaturated, as well as and ° is a group consisting of unbranched aliphatic, aromatic, cyclic and polycyclic hydrocarbons. A hydrocarbon of 1-30 carbon atoms selected from R is also norborneni 1-hexenyl, dicyclopentenyl, and 1-hexenyl. nine Rorosilane further has a structural formula of 0% selected from , where X ranges from θ to 2 and n is greater than or equal to 0. R and R′ are the same or different, each of which is saturated or unsaturated; Branched or unbranched aliphatic, aromatic, cyclic and polycyclic hydrocarbons A hydrocarbon having 1-30 carbon atoms selected from the group consisting of. favorable fruit In the examples, chlorosilane is vinyldimethylchlorosilane, vinylethyldichlorosilane, Chlorosilane, 5-hexenyldimethylchlorosilane, 5-hexenyltrichloro Rosilane, 7-octenyltrichlorosilane and phenylallyldichlorosilane selected from the group consisting of:

In other embodiments, the at least one third compound is an olefin halide. The preferred olefin halide is the 5-para-lambda halide. Chloromethyl phenyl-2-norbornene and 5-chloromethyl-2-nor Bornen.

Typical non-component dienes are as follows: (a) linear acyclic dienes; For example, 1,4-hexadiene; 1,6-octadiene; (b) a branched acyclic diene, such as 5-methyl-1,4-hexadiene; 3, 7-cymethyl-1. Tooctadiene; 3,7-dimethyl 1,7-octadiene and mixed isomers of dihydromircene and dihydrocimene; (C) Monocyclic-alicyclic dienes, such as 1,4-cyclohexadiene, 1,5-cyclohexadiene, Clooctadiene; 1,5-cyclododecadiene; (d) polycyclic-alicyclic, fused- and bridged ring dienes, such as tetrahydroin; methino C tetrahydroindene; dicyclopentadiene; bicyclo(2, 2,1)-pelator 265-diene; alkenyl, alkylidene, cycloalke Example 5-methylene-2-nor Bornene (MNB), 5-ethylidene-2-norbornene (ENB), 5- (4-cyclopentenyl-2-norbornene; 5-cyclohexylidene-2-norbornene Bornene is among the non-common dienes commonly used to make these copolymers. A diene containing at least one double bond in the tension ring is preferred. commercially used The diene is 5-ethylindene-2-norbornene (ENB), 1,4-hexadiene. Polyfunctional proton donation with ene, dicyclopentadiene, and mixtures thereof The bodies are polyfunctional alcohols, amines, polycarboxylic acids and polythiols .

Suitable polyfunctional nucleophiles are diamines, polyamines below diamines and 1,000 ureas. It is.

The particular Lewis acids used are ethylaluminum dichloride, boron trichloride, and and aluminum trichloride.

In the grafting reaction, styrene is a model that can be polymerized both cationically and anionically. Used as a nomer (cloudy).

Another feature of the polymers made according to the present invention is that they are grafted or cross-linked. Molecular weight distribution (MWD) force in front of the bridge (for cytostatic segments, My less than 2 /in ratio and Hz/My ratio of less than 1.8. . Particularly when used as an oil additive, preferred uncoupled )) Preferably, the polymer has a )1w/Mn of less than about 1.6 and less than about 1.4. Full is most preferred. The preferred Mz/my is less than about 1.5, most preferably less than about 1.3. Good meng.

It is known that the advantageous properties of the copolymers according to the invention are related to these ratios. ing. Small (weight) fractions of materials affect these ratios in a disproportionate manner , while not significantly altering the excellent properties that depend on these ratios. For example, low molecular weight The presence of a small fraction (e.g. 2%) of the copolymer reduces Mn and its This increases Mv/Hn above 2 while keeping jz/My below 1.8. hold Therefore, the polymers according to the invention to be linked should have a πv/M of less than 2 n and Hz/My of less than 1.8.

A copolymer according to one embodiment of the invention is made in a tubular reactor. It is preferable to When this process is performed with a tubular or actor, the tube In the first part of the reactor, ethylene is preferentially loaded due to its high reactivity. match. However, as the ethylene runs out, the monomer concentration decreases in the tube. Along the line, the amount of propylene increases. As a result, the copolymer chains Ethylene concentration is higher in chain segments grown near the vector population (polymerization reaction (measured at the point where the Ren concentration increases. An illustrative copolymer chain of ethylene-propylene is shown schematically below. where E represents the ethylene component and P represents the propylene component within the chain. : As can be seen from this illustrative diagrammatic chain, the left-most segment (1) of this is The chain moieties formed in the reactor population, here the reaction mixture has a reactive Ethylene, the larger constituent of , is exceptionally abundant. This segment is a 4-engine It consists of one molecule of lene and one molecule of propylene. However, later segments are As the more reactive ethylene is formed towards the right, the more reactive ethylene disappears and the reaction The mixture has a proportionally increasing concentration of propylene, with subsequent chain segments containing propylene. Ren concentration becomes higher. The resulting chains are intramolecularly heterogeneous.

Halogen-containing monomers, i.e. olefin chlorosilane or olefin carbonization When describing the invention using hydrogen halides, all aspects of homogeneity and heterogeneity are The properties of ethylene are related to the relative proportions of ethylene to other monomers in the chain. It will be done. Regarding the intramolecular composition dispersion (intra-chain composition variation) of the copolymers discussed here, properties are associated with Intra-CD.

In the copolymer chains according to the invention, the composition can vary both optically and along the length of the chain. . In one embodiment aspect, the objective of the invention is to minimize the amount of aperture change. I ter-CD is the composition between the fraction of the copolymer and the average composition. The difference between copolymer fractions containing the highest amount of ethylene and those containing the lowest amount It is also characterized by an overall difference in composition between the copolymer fractions. Ji Measuring the width of Inter-CD as shown by Ju'nghanns et al. Techniques for determining this are known. Here p-xylene-dimethylformamide solvent /nonsolvent was used to fractionate the copolymer into fractions of different intermolecular composition.

Other solvent/non-solvent systems such as hexane-2-propanol can be used. This is discussed in more detail below.

The Inter-CD of the copolymer according to one embodiment of the invention is as follows: 95vt% of the polymer chains are 15vt% or differ by less than that. The preferred Inter-CD is about 13% or less, and the most preferred The difference is about 10% or less. In contrast, Jangan et al. It was found that the Acta copolymer had an Intra-CD of 15 vt% or more. .

In general, the Inter-CD of the copolymer according to one embodiment of the invention is as follows: at least two parts of each intramolecularly heterogeneous chain - each part consisting of a minimum of 5vt% of the chain; - differ from each other in composition by 5vtX ethylene. Unless otherwise specified, This property of Intra-CD, as referred to herein, has a minimum amount of copolymer chains. Based on a 5vt% portion of. Intra-CD of the copolymer according to the invention such that at least two parts of the remer chain differ by at least 10 vt% ethylene. be. Both the minimum 20 vt% ethylene difference and the minimum 40 vt% ethylene difference are applicable to the present invention. It is thought that it follows.

An experimental method for determining Intra-CD is described below. First of all, I Determine the inter-CD as below, then break the polymer chain along its shape. into fragments, and determine the Inter-CD of the fragments. Under As seen in the illustrative example, the difference between the two results is due to Intra-CD.

Consider a heterogeneous sample polymer containing 30 monomer units. That's ASB, C. It consists of three molecules.

A　EEEEPEEEEPEEEEPPEEEPPEPPPEPPPPPPPB　EE EEEPEEεPEEEP・PEEEPPPEPPPEEEPPPCEEEPEEE PEEEPEEEEPEEEEPPEIEPPPEEPPP Molecule A is 3B, 8vt% Ethylene, B is 46.6% and C is 50% ethylene. Average ethylene of mixture The content is 44,396. In this sample, Inter-CD is the highest Contains 5.7% more ethylene than average, with the lowest ethylene-containing polymer This means that the remer contains 7.5% less ethylene than average. paraphrase If 100 vt% of polymer has an average of 44.3% surrounding +5.7% ethylene and -7,526 ethylene. Therefore, a given weight percent of polymer is When it is 100%, Inter-CD is 7,596. The distribution is It is shown graphically as per song k1 in Figure 3 by Cozewith et al. Ru.

When a chain breaks down into fragments, new Inter-CDs are created. easy , only molecule A decomposes into fragments as shown by the diagonal line below. It is considered that El:EEP/EEEPE/EEPPE/EPPEP/PPEPP /PPPPPP72.7%-172,t%-150%-130,8%-114,3 %- and 0%-! +Len part is obtained. Molecules B and C are similarly broken; When divided into weight fractions with different compositions, this is shown by curve 2 in Figure 3. Inter-CD is obtained. The difference between the two numerical curves is due to Inter-CD .

Considering such data, especially data near the final point region, this sample The maximum (L5%) of the chain profile produced by the additive weight % range (a) is between the two curves. The difference is only a minimum of 15% ethylene, shown as (b), and the other part (sec The composition may be different from that of tion). The difference in composition shown by (b) is This cannot be due to differences between children. If so.

If this were the case, the separation process of the original polymer would be seen only in the degraded chains. would have produced a higher ethylene content.

Seen in numbers between original and fragmented strands, shown by (b) and (d) The compositional difference given gives the lowest value of Intra-co. Intra=less CDs The great part of both is that it has been separated from the original polymer. a chain segment having a composition difference (b) or (d) with the highest or lowest composition polymer; This is because they have been separated. In this example, the original polymer deposited in (b) has a 72.7% ethylene moiety and a 0% ethylene moiety in the same chain. Karu. Due to the inefficiency of the fragmentation process, a practical study of Intra-C The resulting polymer is less, or or a section where more ethylene binds along its contour. It is very possible that Therefore, this method has a lower Intra-C Determine the D range. To improve detection, the entire original polymer was fractionated. For example, in a hypothetical example, molecule A is separated from molecule B and from molecule C), these fractions until they no longer show Inter-CD (or smaller Inter-CD). refractionate (until it shows r-CD). This molecularly homogeneous fraction is then fragmented Then, once the entire A has been separated, fragmented, fractionated, and analyzed, the chain breaks A piece of Intra-CD fractionated the entire mixture of molecules ASBSC, 72.7%-0 %-72.7%.

Polymers that are intramolecularly heterogeneous in polymer mixtures coalesced from several sources – To measure fractions, the mixture must be fractionated to show further heterogeneity. must be divided into different fractions.

The fragments that result from the breakage of the original polymer are normal statistical separation of segments across a given monomer conversion range in a given monomer conversion range. It must be large enough so that a cloth is formed. Approximately 5% by weight of the polymer The spacing is convenient. For example, if the average polymer molecular weight is about 105, then the molecular weight is about 5 000 fragments are suitable. Plug flow or battery Detailed mathematical analysis of chain polymerization shows that the rate of change in composition along the polymer chain contour is the most drastic. This indicates that there is a high ethylene conversion near the polymerization end. low pressure The shortest fragment is needed here to indicate the lopyrene content portion.

The most commonly used method for determining the compositional dispersity of nonpolar polymers is phase separation. Solvent/non-solvent fractionation is based on the thermodynamics of This method uses Kando (M , Cantov) “Polymer Fractionation (Polymer Fraetlona- tion)’, Academlc 1967.341 ff page and image Nagaki ()1. T, Tanaku's "Polymer" Development in Polymer Chara cterlzation)-Volume 3, Page 1 (19112). child They are inserted here by reference.

For amorphous copolymers of ethylene and propylene, molecular weight is more important than composition. Governing insolubility in solvent/non-solvent solutions. High molecular weight polymers are given Does not dissolve very well in solvent formulations. There is also a relationship described here. ethylene polymerizes much faster than propylene, so high ethylene polymers also have large molecular weights. There is a tendency to Moreover, ethylene-rich chains are more carbonized than propylene-rich chains. It tends to be poorly soluble in hydrogen/polar non-solvent mixtures. Thus, high molecular weight, high Ren chains are easily separated on a thermodynamic basis.

The fractionation method is as follows: Dissolve the unfragmented polymer in n-hexane at 23 °C to form an approximately 1% solution ( l polymer/100cc hexane). If the isopropyl alcohol becomes cloudy, drop into the solution until the mixture is mixed and allow the precipitate to settle. Remove the supernatant and remove the precipitate. Pass through MylarR (polyethylene terphthalate) film at 50°C Dry by drying. Start the titration again and collect subsequent fractions, which was analyzed and repeated until 100% of the polymer was collected.

With ideal titration control, especially at terminal compositions, 5-10v of the original polymer t% fraction is generated.

To indicate the breadth of the distribution, % ethylene versus 1/2 the weight % of a fraction of that composition. and the total weight percent of the fractions collected so far. Fragment another part of the polymer of cumulative light. A suitable way to do this is to This is a method of pyrolysis: the polymer is placed in a sealed container in a nitrogen burgee oven. Heat a 2-inch thick layer at 330°C for 60 minutes. This is a 105 molecular weight polymer should be sufficient to fragment the polymer into approximately 5000 molecular weight polymers. This way The decomposition does not change the average ethylene content of the polymer. This polymer has a high molecular weight It is fractionated by the same method as the precursor. Ethylene content in selected fractions Both quantity and molecular weight are measured.

Ethylene content is 35-85 vt. Ethylene-propylene containing 96 ethylene. as measured by ASTM-03900 for copolymers. 8526 and above In the above case, ASTM-D223g can be used to obtain the methyl group concentration.

This methyl group concentration of ethylene-propylene copolymers in a distinct manner: L Chi 17'7 ++ It is related to the percent. Como other than propylene If a polymer is used, ASTM tests covering a wide range of ethylene contents There are no The composition of the mer can be revealed. These are all nuclei equal to the spectrum. It is an absolute method that does not require calibration when operated in a manner that contributes to the Echi Ranges not covered by the STM test for ren-propylene copolymers These nuclear magnetic resonance methods are also used in

Molecular weight and molecular weight distribution were determined using a Chromatics KWX-8 perchromatograph. measured. The device was heated to 135°C with 1.2.4-)lichlorobenzene as the mobile phase. used as

Showadesis (Showa Denko America) Polystyrene Gel Column 802.80 3.804 and 805 are used. This method is used to “liquify polymers and related substances Liquid chromatography or Polymers and Related Material m’, J, Cazes W, Marcel Dekker, 1981, page 207 (see (Inserted herein by reference). Don't make corrections for column expansion. Yes; but data on generally accepted standards, such as the National Bureau of Standards. Polyethene 1484 and anionically produced hydrogenated polyisoprene (ethylene (alternatives to lene-propylene copolymers) with respect to My/Mn or Hz/My. It has been demonstrated that such a correction is less than 0.05 units. My is L Commercially available product sold by DC/formerly 1ton (Roy Riviera Beach, Florida) Can be performed using computer software - GPC2, MOLVT2 .

The amount of halogen-containing monomer present is determined by the conventional method used to determine the halogen content of polymers. Easily measured by analytical methods.

The average amount of ethylene in the polymer may be only about 10% by weight. preferable The minimum value is about 25%. A more preferred minimum value is about 3096. maximum etile The content can be about 90% by weight. The preferred maximum value is about 85%, with the most Preferred is about 80%. Ethylene content of the two segments that make up the polymer may be the same or different. If different, the preferred The composition range is the same as stated above for the overall polymer.

, the molecular weight of the copolymers made according to the present invention can vary over a wide range. , heavy It is believed that the weight average molecular weight is only about 2,000. preferred minimum value is approximately 10,000. The most preferred minimum value is about 20,000. maximum weight It is believed that the weight average molecular weight can be as high as about 12,000,000. preferred The maximum value is approximately 1,000,000. The most preferred maximum value is about 750, It is 000. Preferred minimum content of ethylene propylene copolymer chain segments The molecular weight is 2×IQ'. Ethylene/propylene-non-conjunctive diene chain segmentation The preferred minimum MW is 2 x 103 for this client.

Solution polymerization is the preferred medium for the polymerization process of the present invention, and any medium can be utilized. example For example, suitable solvents include carbonated solvents such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents. Hydrogen solvents or halogenated substitutes of such solvents. The preferred solvent is 0 1□ or less, straight chain or branched chain - saturated hydrocarbon, C-09 saturated aliphatic or aromatic It is a hydrocarbon or a C-C6 halogenated hydrocarbon. The most preferable is 01□ or below. lower straight-chain or branched-chain hydrocarbons, especially hexane. Non-limiting, illustrative of solvents Examples are butane, pentane, hexane, heptane, cyclopenkune, cyclohexane cyclohexane, cyclohebutane, methylcyclopentane, methylcyclohexane, isooct Tan, benzene, toluene, xylene, chloroform, chlorobenzene, tetra These are chloroethylene, dichloroethane, and trichloroethane.

Preferably, the polymerization process is carried out in a m1x-tree reactor apparatus, which There is little mixing between parts of the reaction mixture containing polymer chains starting at different times. This is one of the devices that does not cause this problem. Suitable actors are continuous flow tubular or stirred It is a stirred batch reactor. Tubularia lids are well known and It is designed to minimize mixing of reactants in both directions. As a result, the reactant The concentration varies along the length of the actor. In contrast, continuous flow stirred tank reactors The reaction mixture in the reactor (CFSTR) is mixed with the incoming feed and A solution with a substantially homogeneous composition is produced throughout the reactor. Therefore the reaction mixture The growing chains in the part of the CF are of different ages, so that one CF STR is not suitable for the method of the invention. However, all catalysts are - If three or more stirring tanks are used as a series, the tubular rear It is known that it is possible to approach the performance of a vector. Therefore, this series of Such a tank is considered to be in accordance with the present invention and is a functional example of a tubular reactor. It is an alternative.

A batch reactor is a suitable vessel, preferably with suitable stirring equipment, To this, catalyst, solvent and monomer are added at the beginning of polymerization. The reactants are then and allowed to polymerize for a sufficient time to obtain the desired product. Is it for economic reasons? Therefore, a tubular reactor is better than a batch reactor to carry out the process of the present invention. More preferred.

In addition to the importance of the glue-actor system for making copolymers according to the invention, the polymerization Preferably it is done as follows: a, the catalyst system produces essentially one type of active catalyst, b0 the reaction mixture undergoes chain transfer Containing few agents, the polymer chains start almost all at the same time, which means that the In a tach reactor it is the same time and in a tubular reactor it is the length of the tube. at the same point along.

Solvents and reactants (e.g., -, ethylene, alpha-olefins, non-component dienes and and olefinic chlorosilanes or olefinic hydrocarbons. one or more feeds of 1) along the length of the tubular reactor.

when added at least one point during the polymerization in a batch reactor, The desired polymer is obtained.

This method of operation is used to control the rate of polymerization of polymer compositions. is preferred. However, most of the time, all the catalyst is placed at the inlet of the tube or In addition to at the start of actor operation, almost all polymer chains start at the same time. It is necessary to meet the requirements of

The process according to the invention therefore comprises: (a) in at least one rAis-tree reactor; (b) substantially one type of activity; Using a catalyst system to produce a catalyst, (c) using at least one reaction mixture substantially free of transfer agent; (d) is a method in which the growth reactions of almost all polymer chains start at the same time; It is most preferable to carry out the test under the following conditions.

Tubular reactors are preferred °reactors for carrying out the process according to the invention. - system, the following illustrative description and examples relate to this system; ``As will be readily apparent to those skilled in the art who have the benefit of this disclosure, there are other can also be applied.

When carrying out the process according to the invention, at least one tube reactor is used It is preferable to do so. Therefore, in its simplest form, such a process uses only one glue actor. However, skilled persons who would benefit from this disclosure As can be easily seen, one or more glue actors are also used, and they are be used in parallel depending on the reason, or supply multiple monomers to change the intramolecular composition. Used as a continuous series with mouths.

For example, by adding additional monomer(s) during the polymerization, various A structure is created. This is illustrated in Figure 4 of Kozewith et al. monomer during polymerization of ethylene-propylene copolymer chain segment. - Plotted against position along the length of the chain shape for multiple additions. song Intra-co of line 1 transfers all monomers to tubular reactor population or Alternatively, it can be obtained by feeding it to the starting point of a batch reaction. In contrast, songs Line 2 Intra-CD is along the tube or in the batch reactor. by adding additional ethylene at the point where the chain reaches about half its final length. It can be made by Curve 3 Intra-CD requires multiple additions of feed Ru. Curve 4, Intra-CD, has additional comonomers other than ethylene added. formed when This structure allows the entire ethylene composition range to be removed from the chain. Noh. In each case, a second ride is added. The segment distribution looks like this and can be controlled.

The composition of the catalyst used in the production of alpha-olefin copolymers is such that the copolymer product properties such as compositional dispersibility and MVD. According to the present invention The catalyst used in carrying out the process has substantially one active type in the reaction mixture. It must be something that provides a sexual catalyst. To be more specific, it is must provide one main active catalyst that drives almost all polymerization reactions. No. If the copolymer product is according to the invention, for example a narrow MWD and an In In cases where tra-CD is indicated, additional types of active catalysts may also be present. like that Additional active catalyst is added to the total copolymer at 35%. We believe that we can provide copolymers as high as vt%. I'm being teased. Preferably, they contribute no more than about 10% of the copolymer. That is. Therefore, essentially the active catalyst of Class 18 accounts for the entire copolymer produced. It should provide at least 85%, and more preferably at least 90%. Growth The contribution of each type of catalyst to polymerization depends on the number of active catalyst types. Characterize the catalyst. It can be easily measured using the method described below.

How to characterize a catalyst by the number of active catalyst types is within the skill of those skilled in the art. Yes, C, Cozewith and G, Ve rstrate)'s "ethylene-propylene copolymer. Reactivity ratio, evaluation and Its meaning (Ethylene-Propylene Copolymers.

Reactivity Ratlons, Evaluatton and 5 1gn1f1cance)', Marcosolecules, This is clarified by Volume 4, page 482 (1971). This is by reference will be inserted here.

According to these authors, the copolymers produced in continuous flow stirred reactors are of one kind. If active catalysts of the same type are present, the MWD and It is disclosed that it should have a narrower Inter-CD. Fractionation and The combined composition of gel permeation chromatography (GPC) is around the average. The MvD (number average molecular weight to weight average molecular weight) of these samples changed by 3%. It is shown that the ratio (to 2) approaches 2. To confirm a single type of active catalyst It is this latter property (My/Mn - about 2) that appears to be more important. other On the other hand, other °catalysts have an Inter-CD greater than ±10% around the average. , giving a copolymer with a multi-mode MVD with a My/Mn value of 2 or more. . These other catalysts appear to have more than one type of active catalyst.

The catalyst system used to carry out the process according to the invention is a Ziegler copolymerization catalyst. , it generally refers to (a) transition metals, i.e. I-B, II[-0 of the periodic table , IVB.

VB, VIB, ■B and compounds of group 1 metals, and (b) I-A of the periodic table , n-A, ll-8 and m-A group metal organometallic compounds including.

A preferred catalyst system for carrying out the process according to the invention has a vanadium valence of 3. Comprising a hydrocarbon-soluble vanadium compound of ~5 and an organoaluminum compound. The catalyst system is expected to provide essentially one active catalyst type as described above. I'm reading. At least one of the selected vanadium compound/organoaluminum pair is a raw material. Regarding the valence structure, xQ-3, R -Hydrocarbon group: where AcAc-acetylacetonate; V(AcAC)3; vocx <AcAc) 3-,, (2) where x=1 or 2: and ■04・nB Here, a hydrocarbon-soluble complex compound can be created with n-2-3, B=VCJ a. Lewis bases, such as tetrahydrofuran, 2-methyl-tetrahydrofuran , dimethylpyridine.

In Structural Formula 1 above, R is preferably aliphatic, cycloaliphatic or aromatic from 01 to 010. Aromatic hydrocarbon groups, such as ethyl (Et), phenyl, isobutyl, propyl n-butyl, 1-butyl, t-butyl, hexyl, cyclohexyl, octyl and naphthyl. A non-limiting, illustrative example of a compound of structural formula (1) is vanadyl. Trihalides, alkoxy halides, and alkoxides such as VOCA3, VOCA 2 (OBu) (here Bu-butyl) and ■0 (OC2H5) It is 3. The most preferred vanadium compounds are vex%vocz3 and VOC A2 (OR) There is.

As mentioned above, the promoter is preferably an organoaluminum compound. Regarding chemical formulas These compounds can be: Here, R and R' are carbon as described above regarding the structural formula of the vanadium compound. Hydrogen groups may be the same or different. Most preferred organoaluminization The compound is an aluminum alkyl sesquichloride, such as M2Et3CJ! 3 ma or M, (iBu) 3cA3.

A catalyst system consisting of R is preferably ethyl has been found to be particularly effective.

For best catalytic performance, the molar amounts of catalyst components added to the reaction mixture must yield an aluminum/vanadium molar ratio (Al/V) of at least about 2. Must be. The preferred minimum M/V is about 4. The maximum M is mainly due to catalyst cost. considerations and where chain transfer caused by organo-aluminum compounds is minimized. Based on your wishes (as detailed below). As is known, organoaluminization of species consisting of The compound acts as a chain transfer agent, so if there is too much in the reaction mixture, The 14v/Mn of the polymer is greater than 2. Considering these, At! /V's highest The maximum value may be about 25; however, a maximum amount of 17 is more preferred. most preferred The maximum value is approximately 15.

The following types of transfer agents for the Ziegler-catalyzed polymerization of α-olefins are well known: In accordance with the examples, hydrogen or diethyl chloride for the production of EPM and EPDM is shown. aluminum, or diethyl lead. Such agents are Control of molecular weight of EPM and EPDM produced in a flow stirred reactor very commonly used to Substantially one type used by the present invention In the active Ziegler catalyst system of ゛, the addition of chain transfer agent to CFSTR is – Reduces molecular weight but does not affect molecular weight distribution. On the other hand, the tube according to the present invention The chain transfer reaction during the blister reactor reaction broadens the polymer molecular weight distribution.

The chain that terminates before the addition of a heptamine containing at least one halogen is a monomer. Does not include. The presence of chain transfer agent in the reaction mixture is then minimized or should be completely ignored. Difficult to generalize about all possible reactions However, the amount of chain transfer agent used will depend on the desired MwD and compositional dispersion. should be limited to such an amount as to provide a copolymer product in accordance with the range of . The maximum amount of chain transfer agent present in the reaction mixture is approximately 0.2 mol/αO1 transition It may also be a metal (e.g. vanadium), but again the resulting copolymer - the product must comply with the desired constraints on MVD and compositional dispersion; stomach. Chain transfer reactions can occur even if no chain transfer agent is added, because the This is because pyrene and organoaluminium cocatalysts also act as chain transfer agents.

In general, organic alkaline compounds that combine with vanadium compounds to provide only one active species. Provides the highest copolymer molecular weight with acceptable catalytic activity among minium compounds Organic aluminum should be chosen. Furthermore, Ai! /V ratio is the copolymer product Again, give the maximum molecular weight with acceptable catalytic activity. Ru Ai! /V should be used. Chain transfer by propylene is often limited by be done.

Molecular weight distribution and Inter-CD are the catalysts that lead to chain growth termination during the polymerization process. It also spreads through inactivation. Vanadium paper used according to the invention The Ziegler catalysts of the It is known that it is accepted. The relationship between active catalyst lifetime and catalyst system composition is currently unknown. Although it is not known, the catalyst consists of Deactivation can be reduced by using short residence times and minimal temperatures. Wear.

If catalyst deactivation has occurred, the halogen-containing monomer feed is It is preferably added to the reactor when 50% of the catalyst in it is still active. . The polymerization according to the invention initiates the growth of almost all comonomer chains at the same time. It must be carried out in an adequate manner and under sufficient conditions. This is the process step described below. This is realized using floors and conditions.

The catalyst components are premixed, i.e. to form an active catalyst outside the reactor, and It is preferable to ensure that rapid chain initiation occurs. pre-mixed Aging of the catalyst system, i.e. aging of catalyst components (e.g. vanadium) outside the reactor The amount of time that compounds (aluminium and aluminum) coexist with each other remains within limits. It is preferable to If aging is not done for a sufficient period of time, the components will become active catalysts. The species may not have interacted with each other enough to provide adequate amounts, resulting in Chain initiation does not occur simultaneously. Because the activity of that type of catalyst decreases with time, It is also known that sizing should be kept within maximum limits. minimal aging The time depends on factors such as concentration of catalyst components, temperature and mixing equipment. It is believed that it can be as short as a second.

The preferred minimum aging time is approximately 0.5 seconds, and the most preferred minimum aging time is approximately 0.5 seconds. The time is approximately 1 second. Vanadium is preferred, although the maximum aging time is infinitely long. / For organoaluminum catalyst systems, the preferred maximum value is at least 500 seconds, approximately 5000 seconds. Good too. More preferably, the maximum value is about 200 seconds. most preferred maximum age The programming time is about 100 seconds. Preliminary mixing can be carried out at low temperatures, such as below 40°C. can. Preferably, the preliminary mixing is carried out at a temperature of 25" or less, most preferably 15" or less. Yes.

The temperature of the reaction mixture should also be kept within the following ranges. The temperature of the reactor population is At the start of the reaction, it must be high enough to ensure complete and rapid chain initiation. No. The length of time that the reaction mixture is kept at elevated temperature limits the possibility of undesirable chain transfer and catalysis. It must be short enough to minimize the amount of media inactivation reactions.

Temperature control of the reaction mixture takes into account the fact that polymerization reactions generate large amounts of heat. For 1. It's somewhat complicated. This problem can be solved by rearranging the pre-chilled feed. It is preferred to treat by absorbing the heat of polymerization in addition to the vector. this In the process the reactor is operated adiabatically and the polymerization The temperature may increase throughout the process. Instead of pre-chilling supplies, for example by a heat converter surrounding at least part of the reactor, or by a batch Known automatic cooling technology in the case of reactors or multiple stirred reactor series Heat can be removed from the reaction mixture by .

When operating an adiabatic reactor, the reactor inlet temperature is approximately -50℃. The temperature may be between 140°C and 140°C. The exit temperature of the reaction mixture can be as high as about 150°C. It is believed that. The preferred maximum outlet temperature is about 70°C. most preferred highest The value is approximately 50°C. The actuator acts like a cooling jacket to remove the heat of polymerization. If there is no means of cooling the reactor, the temperature of the reaction mixture may be increased. - toward the exit, the heat of polymerization, the heat specific to the reaction mixture, and the copolymer in the reaction mixture; It rises by an amount that depends on the weight percent of the rimmer. Ethylene in hexane solvent - in the case of propylene copolymerization, about 10 per weight percent of the resulting copolymer The temperature increases by ℃.

It will be appreciated by those skilled in the art with the benefit of the above disclosure how to make copolymers according to the present invention. It is well within the skill of the art to determine the appropriate operating temperature conditions. For example, adiabatic Assuming an actor, the reaction mixture containing 5% copolymer has an exit temperature of 35°C. Desired. The temperature of the reaction mixture is approximately 10° C. per 1 weight percent of copolymer. , or increase by 5 wt% Pre-chilled feed to 35℃-50℃-15℃ is required to maintain be. If external cooling is used to absorb the heat of polymerization, the inlet temperature should be The temperature limit may be higher than the above temperature limit applied elsewhere.

Preferred maximum copoly of reactor outlet for heat removal and reactor temperature limitation Mer concentration is 25vt/100vt, diluent. The most preferred maximum concentration is 1 5vt, /100vt. There is no lower concentration limit depending on the operating capacity of the reactor. , for economic reasons, the copolymer concentration should be at least 2vt,/LOOvt. preferable. Most preferably, a minimum of 3vt/reaction mixture passes through the reactor. The flow rate is chosen to improve mixing of the reactants in the radial direction and to minimize mixing in the axial direction. must be large enough for Sufficient radial mixing ensures that the copolymer chains Not only is it advantageous for both Intra-CD, but also generated by the polymerization reaction. It is also advantageous to minimize thermal radial temperature gradients.

The radial temperature gradient increases the polymerization rate in the temperature gradient region that broadens the molecular weight distribution of the copolymer. This is because it becomes Experts will note that these objectives are difficult to achieve with very viscous solutions. I know something strange. This problem can be solved by using a static mixer (static mixer). ) For the use of radial mixing equipment such as C example: manufactured by Keessys be overcome to a certain extent.

The residence time of the reaction mixture in the alx-tree reactor can vary over a wide range. Conceivable. The minimum value is believed to be only about 1 second. The preferred minimum value is approximately It is 10 seconds.

The most preferred minimum value is about 15 seconds. I believe the maximum value is about 3600 seconds. It is. A preferred maximum value is about 1800 seconds. The most preferred maximum value is about 90 It is 0 seconds.

As previously mentioned, the composition of the inventive copolymer chains can be modified by adding various reactants to the reactor. It depends on what you do. In tubular reactors, halogen-containing monomers react If inserted into the reactor population and along almost the entire length of the reactor, the random Polymer is produced. Halogen-containing monomer is present at one or more locations along the reactor. with additional ethylene and α-olefins supplied appropriately. A segmented copolymer is produced. The copolymer chain contains α - where the olefinic chlorosilane or olefinic hydrocarbon halide is added; The second segment grows accordingly.

Can be crosslinked with olefin halide functional groups. The third component of the copolymer is an olefin. chlorosilane, the crosslinking agent is a polyfunctional proton donor as indicated above. Water is one of the The halogen-containing monomer is an olefin hydrocarbon halide. In some cases, the crosslinking agent is zinc oxide or a polyfunctional nucleophile as described above.

The structure of the resulting crosslinked comonomer also depends on the arrangement of the monomers along the copolymer chain. Ru. Olefinic chlorosilane or olefinic hydrocarbon halide reactor population The olefinic chlorosilane or olefinic hydrocarbon halide is introduced into the entire chain. When present in the body, cross-linking occurs throughout the chain. olefin chloro silane or olefinic hydrocarbon halide at one or more locations along the reactor to produce copolymer chains with adjacent first and second segments of sufficient length. When introduced at an addition rate such that crosslinking results in nodular regions of the second segment. A first segment extends from a second segment. additional functional groups This can be achieved by adding a polyfunctional proton donor or a polyfunctional nucleophile containing Variants of such nodular copolymer products can be made. Like that Examples of functional groups include amide, pyridine, polycaprolactone, pyrrolidone, and imidazole. sol, polycaprolactam, etc. Such groups are suitable for dispersion in lubricating oil compositions. Acts as an agent.

Glass fiber compositions, at the current state of technology, glass fibers and glass fiber compositions are It is difficult to achieve sufficient adhesion with the plastic substrate containing the material. Copo of the present invention Rimer chains can be inserted into glass fiber compositions to improve the bonding of the compositions. Wear. This improvement is achieved by attaching glass fibers to the chlorosilane functional groups in the chain. This is achieved through a reaction.

The chlorosilyl-containing copolymer chains are prepared by converting lath fibers into copolymer chains by conventional means. The copolymer chains are modified by coating and reacting the coating composition with an adhesive. You can get it. Alternatively, the copolymer chains can be used to make glass fiber compositions. can be cured with non-common agents, e.g. water. .

The copolymer chains of the present invention can similarly be used for silicates and carbon blacks. It can be used in rubber compositions containing fillers. The copolymer chain The filler is used to improve bonding in the composition by bonding the filler to the rubber. (.

The copolymers of the present invention can be used in combination with a compatibilizer and a thermoplastic elastomer. and graft polymers.

In one embodiment of this process of the invention, the copolymer chains are React with a metalating agent such as aluminum. Then, anionically polymerizable monomers is added, which polymerizes anionically to form an ethylene-α-olefin copolymer. give a monomer chain grafted onto the mer chain.

In another embodiment of the invention, a cationic catalyst such as Lewis acid is copolymerized. hydrocarbon on the remer mirror)) react with the rogene functional group, then cationically The monomers that can be combined are added and grafted onto the copolymer chains.

When chlorosilyl is inserted at each end of the ethylene-α-olefin copolymer chain The copolymer chains of the invention are reacted with a hydroxy-terminated thermoplastic resin to form a thermoplastic resin. Elastomers can also be formed.

The lubricating oil product according to the invention comprises ethylene as detailed above and at least one other α-ol. Lubricating viscosity containing an effective amount of a viscosity index improver, which is a nodular copolymer with lefins. The base stock consists of a large amount of lubricating oil. In more detail, the combination The chains forming the nodular copolymer have a gv/in ratio of less than 2 and a gv/in ratio of less than 1. have an MVD characterized by at least one Hz/My ratio less than 8; preferred is most preferred.

In one embodiment of the invention, the Intra-CD of the copolymer is: i.e. at least two parts of each intramolecularly heterogeneous chain (each part consists of at least 5vt of the chain) %) differ from each other by a minimum of 5 vt% ethylene. Intra-C D may be such that at least two portions of the copolymer chains contain at least 10 vt% ethylene. Only Ren is different. A minimum of 20 wt% ethylene difference, and a minimum of 40 vt% ethylene It is considered that the difference is also in accordance with the present invention.

In another embodiment of the invention, the Inter-CD of the copolymer is : 95vt% of the copolymer chains are copolymer average 'rIl amount percent ethylene The composition differs by less than 15 vt%. A preferred Inter-CD is about 13% or more. The most preferred is about 10% or less.

In special embodiments, the copolymer may be used in lubricating oil or oil additive concentrate compositions. When inserted into a composition, the copolymer has the above-mentioned MWD, Intra-CD, It has all the characteristics of Inter-CD. In current practice, ethylene-propylene Most preferred are pyrene copolymers. Preferences for copolymers for use as lubricant additives Preferred ethylene contents are from about 30% to 75% by weight.

When used as a lubricating oil additive, the weight average molecular weight of the copolymer is typically only 2, It is thought that 000 is sufficient.

The preferred minimum value is about 15,000, with about 5.000 being the most preferred minimum value. . It is believed that the maximum weight average molecular weight can be as high as about 12,000,000. . The preferred maximum is about aoo, ooo, with about 250.000 being the most preferred maximum. It is a value.

The preferred ethylene content is between 30% and 75%.

The nodular copolymers of the present invention can be used in lubricating oils as viscosity index improvers or as viscosity index improvers. As modifier, widely varying amounts are used from about 0.001 to 49 vt%. . The ratio that gives the best results depends on the nature of the lubricant base stock and The purpose for which a lubricant is used varies slightly depending on the specific purpose. Waru. As a lubricant for diesel or gasoline engine crank chamber lubricants If used, the polymer concentration ranges from about 0.1 to 15.0 wt% of the total composition. , which is an effective amount that results in improved viscosity index. Generally, such ports Rimmer additives are sold as oil additive concentrates, and here they are is about 5 to 50 vt% based on the total amount of hydrocarbon mineral oil diluent for the additive, More preferably it is present in an amount of 6 to 25 vt%. Polymers of the invention typically contain 9 Hydrocarbon water with a viscosity of approximately 2-40 centistokes (ASTMD-445) at 9°C Used in lubricating oils based on mineral oils: but up to about 25vt% with hydrocarbon mineral oils. Synthetic lubricants such as esters of tribasic acids and monobasic acids, polyglycyl mixture with complex esters derived from cole, tribasic acids and alcohols The novel compositions of the present invention are based on all-nodular polymers. from about 0.05% to about 25% a+o1% of a halogen-containing monomer; Preferably about 0.1 to about 15ao1%, even more preferably +! Approximately 0.15 to approximately 10 It comprises i+o1% halogen-containing monomer. Manufacturing method of nodular copolymer in which the halogen-containing monomer is added in an amount of about 0.1 to about 80 v based on total monomer. t% is preferably used in the reaction mixture, with about 0.5 to about 50 vt% being more preferred. It is even more preferable. The most preferred range is from 2% to 20%.

See the following examples for a novel method of forming the nodular polymers of the present invention. more easily understood by

This example shows ethylene, propylene and 5-trichloro with narrow MWD. The formation of a random terpolymer of silyl-2-norbornene will be described. polymerization rear The catalytic converter is a 1 inch (2,54 J) diameter pipe with monomer and catalyst at one end. , cocatalyst and hexane solvent are continuously fed. Monomers are prepared in a standard manner before use. It is purified by a method to remove polar impurities.

The catalyst solution is LL5g of VCZ4 at 5.0! by dissolving in purified hexane. It is adjusted accordingly. The co-catalyst is 142gAj! 2EtCI13 to 5. low purification n-heki It is dissolved in San. These two solutions were prepared at a temperature of θ℃ and a residence time of 6 seconds, as shown in Table 1. The flow rate shown is fed through the catalyst premixer. Premixed catalyst beam a In the vector population, the monomers dissolved in hexane are combined. All flow velocities are It is shown in Table 1. . The supply temperature is 0°C, and the reactor is operated to bring the outlet temperature to 20°C. I will make it happen. Reactor residence time is 30 seconds. Pyridine is released from the reactor. Add to the mouth to calm down the polymerization reaction. Vacuum evaporate at 60°C on a thin film evaporator. This removes solvent and unreacted monomers from the reaction product. of volatile substances Final traces are removed by devolatilization extrusion and the product is recovered in dry air.

The product has a narrow MWD, My/Mn-1,4, 3.5vt% 5-trichloro Contains rosilyru-2-norbornene.

Example 2 The olefin chlorosilane used is 5-methyldichlorosilyl-2-norbornene. except that it was fed into the reactor at a flow rate of 0.026 kg/hr. Repeat the method of Example 1. The final product contains 2.2vt% olefin chlorosilane. Including, My/Mn values are i, e.

Example 3.

The halogen-containing monomer is 5-chloromethyl-2-norbornene by repeating the polymerization method of Example 1. return. The polymerization reaction is quenched with water and solvent, and the unreacted monomer is steamed. Remove by stripping. Steam stripping precipitates the polymer in water let After recovering the wet polymer by sieving, it is dried on a hot rubber roll machine. do.

The product contains 2.4% halogen-containing monomer and has a Mv/Mnlia of 1.4. be.

Example 4 Describes the production of nodular copolymers with chlorosilyl-2-norbornene. Ru. Repeat the polymerization procedure of Example 1, except that no olefinic chlorosilane is present in the feed. do not have. Dissolved in hexane at points along the length of the reactor corresponding to a residence time of 20 seconds. A second feeder consisting of ethylene and silant monomer is injected. second The polymer produced after feeding contains 0.5 yt% silane termonomer. reactor The polymer exiting - exhibits a narrow )1vO of My/)In-1,4.

Polymerization was quenched by adding water to the reactor outlet and as described in Example 3. The polymer is recovered by sea urchin steam stripping. Polymer during product recovery When brought into contact with water, the chains are bonded together by the functional groups of trichlorosilane, forming a nodule. lar copolymer is produced.

Example 5 This example illustrates the formation of a ni-segment polymer.

The third component is 5-parachloromethylphenyl-2-norbornene (PCPN). The polymerization procedure described in Example 1 is repeated except for the following. Polymerization is carried out for 1 second, then Expo to hexane A second feed of decomposed ethylene is added to the reactor to increase the polymerization rate and increase the rate of the third component. Increase conversion. After a residence time of 6 seconds, the conversion was almost complete and the ethyl alcohol dissolved in hexane A second monomer consisting of ethylene and propylene is added to the reactor and Forms an ethylene-propylene copolymer segment. Set the reactor conditions to m Shown in the table. 49% of the polymer is formed before introducing the third monomer feed stream.

The polymerization beam is quenched by water at the exit of the actor, and the solution is extracted with water to remove the catalyst residue. remove things Polymer is recovered by steam stripping and rolling machine for rubber Dry with The polymer exhibits a narrow )lvD with a My/in value of 1.7.

Example 6 Repeat the polymerization of Example 5, but deash the polymer solution. After removing the catalyst residue, add 1,5-diaminohene to a stirred tank container. A hexane solution of xane was supplied at a rate of 1.211 o1/mol third component. stirring The stirring tank was kept at 150℃ and 200 psig (14 kg/cd). maintain phase. Residence time is 10 minutes. Under these conditions the chains are functionalized with a third component. groups to form a nodular copolymer. steam stripper this Collect by drying and drying.

Example 7 The polymer prepared in Example 5 was dissolved in dry hexane and the solution was sparged with dry nitrogen. Fog to remove traces of water. 1.1 sol/hexane solution of butyllithium Add in the proportion of functional terpolymer in mol jEI. Butyl lithium is poly replaces the chloride functionality in the polymer to produce a lithiated polymer. Then such Ren is added to the solution at a ratio of 0.3 vt/vt copolymer. Styrene is anio This gives polystyryl chains that are stacked together.

Example 8 The polymerization procedure of Example 5 was repeated, except that the monomer feed was changed several times as shown in the table. Inject along the length of the reactor and add 5-parachloromethylphenyl- Contains 2-norbornene, with essentially only ethylene and propylene at the center of the chain form a narrow 3MvD copolymer chain containing segments consisting of . center segment The ment constitutes approximately 70v1% of the chain. The two terminal segments are approximately IVt% P Includes CPN. The polymer was recovered as in Example 5 and recycled as in Example 7. It is oxidized. Styrene was added to the solution at a ratio of 0.4 vt/vt copolymer. Ethylene that is anionically polymerized and grafted with polystyrene at both ends of the chain. -Provides a propylene copolymer.

Below 0 (at the time of adding supplies) 2. Rear, lid - Addition to population - Reaction time has not completely elapsed.

At the time of adding the following supplies: Ethylene 0.65 0.25 Propylene 5.5- Halogen-containing monomer 0.12 2. Addition in the reactor population - reaction time is less than the total heat elapsed when adding the feed at the point Residence time 0216 Hexane 30.0 2.0 30.0 Ethylene 0.2 0.1 0.4 Propylene 3.0-4.0 Addition of halogen-containing monomer 0.0L5--26 to the reactor population - during reaction The interval is 0 after the complete fever has passed.

Hexane 20 5 25 1G Ethylene 0.1 0', 050.5 0.1 Propylene 1.0 - 3.0 0 Halogen-containing monomer o, ooe--o, oe2, added to reactor population - anti- Full fever has not yet passed during this time.

Procedural amendment October 9, 1986 International Application No. PCT/US86102707 Polymer and its manufacturing method 3 Person making the amendment Relationship to the incident: Patent applicant Name: Exxon Research and Engineering Company 4 agents Address: 1-11-28 Nagatacho, Chiyoda-ku, Tokyo. Translation of the written description and claims, international search report

Claims (69)

[Claims] 1. A. one contiguous segment or multiple consisting of a copolymer of ethylene and α-olefin in the form of discrete segments of a first segment; B. Ethylene and α-olefin and (a) has the structural formula SiRR'xCl3-x, where i) x is in the range 0-2; ii) R is a Ziegler copolymerizable olefin; iii) R' is a saturated or unsaturated olefin; Saturated and branched or unbranched aliphatic, aromatic, cyclic and polycyclic carbons a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of Olefin chlorosilane, (b) has the structural formula RR'x where i) R is a Ziegler copolymerizable olefin; ii) R' is saturated or unsaturated; Saturated and branched or unbranched aliphatic, aromatic, cyclic and polycyclic carbons A hydrocarbon containing 1-30 carbon atoms selected from the group consisting of iii) an olefinic hydrocarbon halide where x is a halogen a copolymer with at least one halogen-containing monomer selected from the group consisting of a second segment consisting of; a copolymer chain consisting of; The second segment constitutes 50 weight percent of the copolymer chain and is The second segment is one contiguous segment or in the form of multiple discrete segments; The at least one halogen-containing monomer does not crosslink the first segment to a substantial degree. copolymer chains that can be crosslinked under harsh conditions. 2. the group in which R is norbornenyl, dicyclopentenyl and 1-hexenyl; The copolymer according to claim 1, which is a Ziegler copolymerizable olefin selected from Rimmer chain. 3. The claimed at least one halogen-containing monomer is an olefinic chlorosilane. A copolymer chain according to range 1. 4. Olefin chlorosilane has the structural formula CH2=CH-(CRR')n-SiRxCl3-x, where i) x is in the range 0-2, ii) n is greater than or equal to 0; iii) R and R' are the same or different; and each of R and R' is saturated or unsaturated and branched or branched. Claims selected from the group consisting of aliphatic, aromatic, cyclic and polycyclic hydrocarbons A copolymer chain according to item 3. 5. A claim in which at least one halogen-containing monomer is an olefinic hydrocarbon halide A copolymer chain according to claim 1. 6. The copolymer chain of claim 1 further comprising a non-conjugated diene. 7. Non-conjugated diene is 5-ethylidene-2-norporene, 1,4-hexadiene , dicyclopentadiene and mixtures thereof. A copolymer region according to range 1. 8. Surface Mw/Mn with copolymer chains less than 2 and Mz/Mw less than 1.8 substantially consisting of a plurality of copolymer chains according to claim 1, each having one composition. 9. The first segment has a low Mw/Mn of less than 2 and an Mz/Mw of less than 1.8. consisting essentially of a plurality of copolymer chains according to claim 1, in which at least one composition. 10. Glass fiber, plastic matrix, claim 1~ consisting of a copolymer chain described in any of Section 7, and the glass fiber is a copolymer chain. A glass fiber composition having a portion of a polymer attached thereto. 11. Glass fiber, plastic matrix, claim 1~ Forming a glass fiber composition comprising a copolymer chain according to any of paragraph 7. A method of a) coating the glass fiber with copolymer chains; b) applying the coating composition to the plastic A method consisting of the steps of inserting into a matrix. 12. Glass fiber, plastic matrix, claim 1~ 8. A method of forming a glass fiber composition comprising a copolymer chain according to claim 7, , a) consisting of glass fibers, a plastic matrix and copolymer chains. b) reacting the reaction mixture to form a composition; How to become. 13. A. One segment or copolymer of ethylene and α-olefin within the same limits a first segment consisting of a plurality of discontinuous segments of the rimmer; B. Ethylene and α-olefin and a) has the structural formula SiRR'xCl3-x, where i) x is in the range 0-2; ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated- or unsaturated - and branched or unbranched aliphatic, aromatic, cyclic and polycyclic hydrocarbons a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of Olefin chlorosilane, b) has the structural formula RR'x, where i) R is a Ziegler copolymerizable olefin; ii) R' is a plurality of carbon atoms; alkyl, saturated - or unsaturated - and branched or unbranched 1-30 selected from the group consisting of aliphatic, aromatic, cyclic and polycyclic hydrocarbons A hydrocarbon containing carbon atoms, iii) X is halogen Olefin hydrocarbon halide a copolymer with at least one halogen-containing monomer selected from the group consisting of a second segment consisting of; The second segment comprises less than 50 weight percent of the copolymer chain and has the same in the form of one or more discrete segments within the field; The at least one halogen-containing monomer crosslinks the first segment to a substantial degree. It is a polymerization method for producing copolymer chains that can be crosslinked under Te, I. A reaction mixture of ethylene and α-olefin is produced by ethylene-α - Olefin copolymer weight is determined at the completion of polymerization for first segment formation. The first polymer is polymerized to the point where it reaches a minimum of 50% of the weight of the desired polymer. forming a segment; II. At least one halogen-containing monomer is added to the second Form the second segment by inserting it into the reaction mixture for segment formation. to do, Polymerization method consisting of. 14. Formation of a second segment is performed after completion of formation of the first segment, and Therefore, a component consisting of substantially one first segment and substantially one second segment. 14. The method of claim 13, wherein polymer chains are formed. 15. 14. The method of claim 13 comprising adding a non-conjugated diene to the reaction mixture. Method. 16. A. One segment or copolymer of ethylene and α-olefin within the same limits a first segment consisting of a plurality of discontinuous segments of the rimmer; B. Ethylene and α-olefin and a) has the structural formula SiRR'xCl3-x, where i) x is in the range 0-2; ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated or unsaturated; Sum- and branched- or unbranched aliphatic, aromatic, cyclic and polycyclic carbonization a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of hydrogen; Olefin chlorosilane, b) has the structural formula RR'x, where i) R is a Ziegler copolymerizable olefin; ii) R' is saturated or unsaturated; Saturated and branched or unbranched aliphatic, aromatic, cyclic and polycyclic carbons a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of iii) X is halogen; olefin hydrocarbon halide a copolymer with at least one halogen-containing monomer selected from the group consisting of a second segment consisting of; The second segment comprises less than 50 weight percent of the copolymer chain and has the same in the form of one or more discrete segments within the field; The at least one halogen-containing monomer crosslinks the first segment to a substantial degree. can be crosslinked under conditions that do not A polymerization method for producing a copolymer chain comprising: 1. Ethylene, α-ole The reaction mixture of fins and at least one halogen-containing monomer is combined with at least one halogen-containing monomer. The reaction of the gen-containing monomer is substantially completed and the resulting ethylene-α-olefin - the weight of the halogen-containing monomer copolymer to form the second segment Allowing the polymerization to occur to the point where less than 50% of the expected polymer weight is present upon completion of the polymerization. forming a second segment by II. Continue the reaction to form the first segment. to form a first segment, thereby substantially forming one first segment. forming a copolymer chain consisting of a segment and substantially one second segment. A method consisting of steps. 17. Additional ethylene, alpha-olefins, non-conjugated dienes and halogen-containing monomers Inserting at least one of the polymers into the reaction mixture after initiation of polymerization. The method according to paragraph 13. 18. Reaction of ethylene, alpha-olefin and at least one halogen-containing monomer The mixture is prepared using substantially one type of catalyst and at least one min-free b) In the reactor, growth of essentially all copolymer chains begins at the same time. polymerizing in a manner and under conditions sufficient to form a large number of copolymer chains. The copolymer chains are dispersed within the reaction mixture, and the reaction mixture is treated with a transfer agent (tranfer). 14. The method of claim 13, wherein the method is substantially free of sfer-agent. 19. Claim 18 comprising carrying out the polymerization in a tubular reactor. The method described in section. 20. Ethylene, other α-olefin monomers, nonconjugated dienes, and the above an additional reaction mixture comprising at least one of at least one halogen-containing monomer; Claim 19 further comprising injecting at at least one location along the reactor. Method described. 21. 21. The method of claim 20, wherein the α-olefin is propylene. 22. The first segment constitutes the center of the copolymer chain and the second segment A copolymer chain consisting of two segments, one at each end of the polymer chain, a) Reaction mixture of ethylene, propylene and at least one halogen-containing monomer is introduced at the reactor inlet and at least one halogen-containing monomer is introduced along the reactor. b) ethylene and propylene at a second site to create a second segment; A reaction mixture containing a compound selected from the group consisting of at least one of introducing the first segment at the first section between the inlet and the second section along the form, 21. The method of claim 20, comprising forming by forming. 23. At least one halogen-containing monomer is an olefinic chlorosilane, The process further reacts the copolymer chains with a hydroxy-terminated thermoplastic to form a thermoplastic resin. 23. The method of claim 22, comprising forming a lastomer. 24. at least one halogen-containing monomer is an olefinic hydrocarbon halide, More ways a) reacting the copolymer chains with a metalating agent; b) reacting the anionically polymerizable monomer with reacting with the copolymer chains reacted in step a) to form a graft polymer; 14. The method of claim 13, comprising the steps of: 25. The metalating agent is composed of branched alkyllithium and ropechillithium. the anionically polymerizable monomer is styrene; The method according to scope item 24. 26. at least one halogen-containing monomer is an olefinic hydrocarbon halide, The process further comprises a) reacting the copolymer chains with Lewis acid, and b) cationic polymerization. a graft polymer by reacting the monomers with the copolymer chains reacted in step a). form a 14. The method of claim 13, comprising the steps of: 27. Lewis acid reacts with ethylaluminum dichloride, boron trichloride, and amine trichloride. selected from at least one of aluminum, and the cationically polymerizable monomer is styrene. A method according to claim 26. 28. At least one halogen-containing monomer is an olefinic chlorosilane and the reaction mixture If the object contains multiple polymer chains, the above method may further include a second segment of the copolymer chain. at least one composition selected from the group consisting of water, and a polyfunctional proton donor. 14. The method of claim 13, comprising crosslinking with a compound. 29. At least one halogen-containing monomer is an olefinic hydrocarbon If the mixture contains a large number of copolymer chains, the above method further comprises a second segment of copolymer chains. ment with at least one compound selected from the group consisting of ZnO and a polyfunctional nucleophile. 14. The method according to claim 13, which comprises crosslinking with a compound. 30. A. a second section of the copolymer chain substantially crosslinked by at least one crosslinking agent; a nodule region of substantial cross-linking of the segment, said Each of the second segments comprises substantially ethylene and an alpha-olefin and a) has the formula SiRR'xCl3-x, where i) x is in the range 0-2; ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated or unsaturated; Sum- and branched- or unbranched aliphatic, aromatic, cyclic and polycyclic carbonization a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of hydrogen; Olefin chlorosilane, b) has the structural formula RR'x, where Here i) R is a Ziegler copolymerizable olefin, and ii) R' is a saturated or Unsaturated and branched or unbranched aliphatic, aromatic, cyclic and polycyclic a hydrocarbon having 1-30 carbon atoms selected from the group consisting of hydrocarbons, iii) x is halogen olefin hydrocarbon halide a copolymer with at least one halogen-containing monomer selected from the group consisting of a nodule region comprising; B. a substantially uncrosslinked material from which the first segment extends; a copolymer chain, each of said first segments comprising substantially ethylene and A substantially uncrosslinked copolymer chain consisting of a copolymer of α-olefin and α-olefin. Consisting of Conditions in which the first segment of the halogen-containing monomer is not crosslinked to a substantial degree. A nodular copolymer product of copolymer chains that can be crosslinked under A product. 31. at least one halogen-containing monomer is an olefinic chlorosilane; Claims wherein the two crosslinking agents are selected from the group consisting of water and a multifunctional proton donor. 31. A nodular copolymer product according to paragraph 30. 32. Each of the first and second segments of the chain are substantially the same. in the form of one or more discrete segments within one limit, with a second segment Each of the members comprises substantially less than 50 weight percent of the copolymer chains. 32. The nodular copolymer of claim 31, comprising: 33. at least one halogen-containing monomer is an olefinic hydrocarbon halide; one crosslinker is selected from at least one of the group consisting of ZnO and a polyfunctional nucleophile; 31. The nodular copolymer product of claim 30. 34. Substantially each of the chain first and second segments have the same limits. in the form of one or more discontinuous segments within the in a claim in which each segment comprises less than 50 weight percent of the copolymer chain. A nodular copolymer according to Range 32. 35. I. A. a substantially uncrosslinked first segment, each of which is substantially identical; in the form of one or more discrete segments within a limit, each substantially is a substantially cross-linked first segment consisting of a copolymer of ethylene and an alpha-olefin. Mento and B. a second segment, substantially each of which comprises ethylene and an alpha-olefin; and (a) has the structural formula SiRR'xCl3-x, where i) X is in the range 0-2; ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated or unsaturated; - and branched or unbranched aliphatic, aromatic, cyclic and polycyclic hydrocarbons a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of Olefin chlorosilane, (b) has the structural formula RR'x, where i) R is a Ziegler copolymerizable olefin, and ii) R' is saturated or unsaturated. Saturated and branched or unbranched aliphatic, aromatic, cyclic and polycyclic carbons a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of iii) x is halogen; olefin hydrocarbon halide a copolymer with at least one halogen-containing monomer selected from the group consisting of a second segment consisting of; The second segments of the copolymer chains are joined by at least one crosslinker and cross-linked to each other. to form a nodular region, with a substantially uncrosslinked first segment a copolymer chain extending from the nodule region; II. Nodular copolymer consisting of nodular regions containing dispersible functional groups -Product. 36. Amide, pyridine, polycaprolactone, polycaprolactam, pyrrolide a dispersible group comprising at least one composition from the group consisting of The nodular copolymer of claim 35, wherein the nodular copolymer is attached to the crosslinking agent within the nodules. . 37. I. copolymer chains, each of which has an A. 1 segment within the same limit or in the form of multiple segments, made from copolymers of ethylene and α-olefins. a first segment consisting of; B. ethylene and an α-olefin, and a) having the structural formula SiRR′xCl3-x; , where i) X is in the range 0-2 ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated or unsaturated; Sum- and branched- or unbranched aliphatic, aromatic, cyclic and polycyclic carbonization a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of hydrogen; Olefin chlorosilane, b) has the structural formula RR'x, where i) R is a copolymerizable olefin, ii) R' is saturated or unsaturated and branched or unbranched aliphatic, aromatic; carbon containing 1-30 selected from the group consisting of aromatic, cyclic and polycyclic hydrocarbons; With hydrogen chloride, iii) x is halogen; olefin hydrocarbon halide a copolymer of at least one halogen-containing monomer selected from the group consisting of a second segment consisting of; Substantially each of the second segments accounts for 50 weight percent of its copolymer chains. and each of said second segments has one or more segments within the same limits. in the form of discontinuous segments, Said at least one halogen-containing monomer substantially comprises said first segment. Can be crosslinked under non-crosslinking conditions; the second segment of the copolymer chain has at least 1 bonded by two crosslinkers copolymer chains; II. Nodular copolymer consisting of nodular regions containing dispersible functional groups A. The reaction mixture of ethylene and α-olefin was The weight of the tyrene-α-olefin-copolymer to form the first segment is B. Polymerize until a minimum of 50% of the expected polymer weight is reached upon completion of the polymerization; inserting at least one halogen-containing monomer to form a second segment; C. Cross-linking the second segment by inserting a multifunctional coupling agent containing a dispersive functional group A method including steps of bridging to form a nodule. 38. According to any of claims 30-36 or claim 3 comprising an effective amount of a nodular copolymer additive prepared by the method described in paragraph 7. A lubricating oil composition. 39. Nodular copolymer additive according to claim 27 or 35 A lubricating oil composition comprising from about 0.1 to about 15.0% by weight of the total composition. 40. Substantially at least Mw/Mn less than 2 and Mz/Mw less than 1,8 The copolymer consists of a plurality of polymer chains having one olefin, and a) has the structural formula SiRR'xCl3-x, where i) x is 0 -2 range, ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated or unsaturated; Sum- and branched- or unbranched aliphatic, aromatic, cyclic and polycyclic carbonization a hydrocarbon containing 1-30 carbon atoms selected from the group consisting of hydrogen; Olefin chlorosilane, b) has the structural formula RR′x, where: i) R is a Ziegler copolymerizable diene; ii) R' is a saturated or unsaturated group; From branched or unbranched aliphatic, aromatic, cyclic and polycyclic hydrocarbons a hydrocarbon having 1-30 carbon atoms selected from the group consisting of iii) x is halogen; olefin hydrocarbon halide and at least one halogen-containing monomer selected from the group consisting of Composition. 41. 41. The composition of claim 40 further comprising a non-conjugated diene. 42. Non-conjugated diene is 5-ethylidene-2-norporene, 1,4-hexadiene Claims selected from the group consisting of The composition according to item 41. 43. Is the average weight percent ethylene composition 95 percent by weight of the copolymer chains? have an ethylene composition that differs by no more than 15% by weight from each copolymer chain; at least two portions (each portion consisting of at least about 5% by weight of the chain) are at least about 5% of each other. The composition of claim 40, which differs in composition by weight percent ethylene. thing. 44. Is the average weight percent ethylene composition 95 percent by weight of the copolymer chains? have an ethylene composition that differs by no more than 15 weight percent from the At least two portions of the remer chain (each portion comprising a minimum of about 5 weight percent of the chain) Claims differing in composition from each other by at least about 10 weight percent ethylene. Composition according to item 40. 45. 95 weight percent of the copolymer chains have an average weight percent ethylene composition having an ethylene composition that differs by no more than 15% by weight from substantially each copolymer. At least two portions of the chain (each portion consisting of a minimum of about 5% by weight of the chain) are at least a Claim 40 which differs in composition by about 20 weight percent ethylene. Composition of. A claim having at least one of Mw/Mn of less than 46.2 and Mz/Mw of less than 1.8. The composition according to claim 40. 47. R consists of norbornenyl, dicyclopentenyl, and 1-hexenyl; Claim 40 is a Ziegler copolymerizable olefin selected from the group consisting of: composition. 48. Claim 40, wherein said plurality of copolymer chains are random copolymer chains. Compositions as described in Section. 49. The claimed at least one halogen-containing monomer is an olefinic chlorosilane. A composition according to range item 40. 50. at least one set selected from the group consisting of water and a polyfunctional proton donor; comprising a composition according to claim 49 crosslinked by reaction with a composition. Cured copolymer composition. 51. The copolymer chains are polyfunctional alcohols, amines, polycarboxylic acids, upon reaction with at least one polyfunctional proton donor selected from the group consisting of 51. The composition of claim 50, which is thus crosslinked. 52. Olefin chlorosilane has the structural formula CH2=CH-(CRR')n-SiR has xCl3-x, where i) x is in the range 0-2, ii) n is greater than or equal to 0; iii) R and R' are the same or different; and each of R and R' is saturated or unsaturated and branched or unbranched. selected from aliphatic, aromatic, cyclic and polycyclic hydrocarbons Composition according to paragraph 49. 53. Olefin chlorosilane, vinyldimethylchlorosilane, vinylethyl Dichlorosilane, 5-hexenyldimethylchlorosilane, 5-hexenyltric Rorosilane, 7-octenyltrichlorosilane, and phenylallyldichloro Silane, 5-trichlorosilyl-2-norporene, and 5-methyldichloro of claim 52 selected from the group consisting of silyl-2-norporene. Composition. 54. At least one halogen-containing monomer is an olefinic hydrocarbon halide. The composition according to claim 40. 55. Olefinic hydrocarbon halides include 5-chloromethyl-2-norporene and and 5-parachloromethylphenyl-2-norporene. A composition according to claim 54. 56. at least one composition selected from the group consisting of ZnO and a polyfunctional nucleophile A cured colloid comprising the composition according to claim 54, which is crosslinked by reaction with a substance. Polymer composition. 57. Claim 56, wherein the copolymer chains are crosslinked by reaction with ZnO. composition. 58. Are the copolymer chains diamines, polyamines other than diamines, and thiourea? cross-linked by reaction with at least one polyfunctional nucleophile selected from the group consisting of 57. The copolymer composition of claim 56. 59. 55. The cured copolymer chain of claim 54, wherein the halogen is chlorine. 60. 55. The cured copolymer chain of claim 54, wherein the halogen is bromine. 61. Ethylene and α-olefin, and a) structural formula SiRR′xCl3-x and where i) x is in the range 0-2; ii) R is a Ziegler copolymerizable olefin; iii) R' is saturated or unsaturated; and branched or unbranched aliphatic, aromatic, cyclic and polycyclic hydrocarbons. a hydrocarbon containing 1-30 carbon atoms, selected from the group consisting of an olefinic chlorosilane, b) has the structural formula RR'x, where i) R is a Ziegler copolymerizable olefin, ii) R' is saturated or unsaturated as well as branched or branched aliphatic, aromatic; 1-30 carbon atoms selected from the group consisting of aromatic, cyclic and polycyclic hydrocarbons is a hydrocarbon having a iii) x is halogen olefin hydrocarbon halide and at least one halogen-containing monomer selected from the group consisting of A polymerization method for producing a copolymer chain from a compound, the polymerization method comprising: a) at least one mix-free reactor; tor); b) substantially one active catalyst; c) a transfer-age using at least one reaction mixture substantially free of d) sufficient that substantially all of the propagation reactions of the copolymer chains are initiated simultaneously; A method of polymerization comprising carrying out the method and conditions. 62. Mix-free reactor (mix-freereactor) ethylene, alpha-olefin, and at least one halogen-containing moiety. Nomer, and essentially one active catalyst from the inlet of the tubular reactor. 62. The method of claim 61 as introduced. 63. 62. The method of claim 61 comprising adding a non-conjugated diene to the reaction mixture. Method. 64. Contains ethylene, alpha-dimensional olefins, non-conjugated dienes and at least one halogen At least one compound selected from the group consisting of monomers is 64. The method of claim 63, which is installed at one location. 65. The claimed at least one halogen-containing monomer is an olefinic chlorosilane. The method according to scope item 62. 66. The copolymer chain is a group consisting of water and a selected polyfunctional proton donor. curing by reaction with at least one composition selected from The method according to item 85. 67. At least one halogen-containing monomer is an olefinic hydrocarbon halide. The method according to item 62. 68. The copolymer chains are selected from the group consisting of ZnO and polyfunctional nucleophiles. 67. The method of claim 66, comprising the step of curing with at least one composition. . 69. 63. The method of claim 62, wherein the reactor is a batch reactor.