JPH0715031B2 - A method for crosslinking reactive polyolefins via a rhodium-promoted hydrosilylation reaction using a polyorganosiloxane crosslinker. - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to a method of crosslinking reactive polyolefins with polyorganosiloxanes via a rhodium-promoted hydrosilylation reaction. The invention also relates to novel alkoxy-terminated polyorganosiloxanes that can be used in the crosslinking of reactive polyolefins as claimed herein.

BACKGROUND OF THE INVENTION Crosslinking of vinyl-containing polymers with sulfur in the presence of various catalysts, promoters and additives is well known. Sulfur-induced cross-linking of vinyl-containing polymers generally involves mono-, between vinyl groups on the polymer backbone.
Including formation of di- and tri-sulfide bridges, resulting in vulcanization of the polymer.
Sulfide crosslinking imparts greater strength and elasticity to the polymer, ready for its subsequent use in a variety of harsh applications. This method requires continuous heating of the polymer and is therefore energy intensive.

The crosslinking of vinyl-containing polymers with organic peroxides is also well known. The crosslinking mechanism caused by organic peroxides abstracts hydrogen atoms from the polymer, thereby further generating polymer bound radicals that bond together to form a covalent carbon-carbon bond,
Including the generation of radicals. The formation of carbon-carbon bonds produces the polymer crosslinks necessary to impart greater strength and elasticity to the cured substrate. Organic peroxide crosslinks are typically used when heat aging resistance or continuous cure is desired. This method also requires a continuous input of thermal energy.

A third method of crosslinking vinyl-containing polymers involves the use of moisture-crosslinkable silanes, such as vinylalkoxysilanes, which are grafted onto the polymer backbone via a peroxide coupling reaction. This method involves a peroxide-induced grafting reaction of a vinylalkoxysilane onto a polymer backbone and a blend of alkoxysilane hydrolysis catalysts such as tin compounds. The graft polymer is then provided to the processing step. Crosslinking of vinyl-containing polymers begins when the processed body is exposed to a source of moisture. However, the rate of crosslinking depends on the mass transfer of water into the inherently hydrophobic polymer matrix. This method of cross-linking is therefore limited to machined objects having a high surface area / volume ratio, such as those found in thin wall pipes or some wire insulation.

An alternative to the crosslinking method described above involves the use of platinum hydrosilylation catalysts to promote hydrosilylation crosslinking of poly-SiH containing siloxanes and vinyl containing polymers.
1,118,327. The vinyl-containing polymers mentioned in GB 1,118,327 are predominantly ethylene / propylene / diene monomer terpolymers (EPDM). EPDM
Sources of pendant unsaturation in rubber are diunsaturated, non-conjugated olefins such as ethylidene norbornene, dicyclopentadiene, 1,5-cyclooctadiene, 1,4-hexadiene, 1,7-octadiene. is there. Hydrosilylation crosslinking of vinyl-containing polymers is accomplished via the addition of multiple SiH groups on individual siloxane molecules to the pendant vinyl groups of EPDM terpolymers. The Si-C bond network formed from the hydrosilylation reaction is
The end result is a terpolymer crosslink.
GB 1,118,327 has the general formula: [RmSiO _{(4-m) / 2} ] where at least 5 units of the molecule are HRnSiO _{3-n / 2} (where n = 1 or 2, m = 0, 1, 2 or 3). , And R is a monovalent hydrocarbon radical free of aliphatic unsaturation. The most useful structures are the general _{formula: (CH 3) 3 SiO- (} CH 3 HSiO) x-Si (CH 3) ₃ wherein, x is a is a siloxane having a has an average value of 90 from 10 stated Has been. The catalysts disclosed as being useful in this process are various forms of platinum hydrosilylation catalysts, such as olefin complexed platinum, symmetrical-1,2-divinyl-.
Platinum or chloroplatinic acid complexed with 1,1,2,2-tetramethyldisiloxane. It has been found that this method results in foam formation in the processed body, which makes its use unattractive.

The use of Group VIII transition metal complexes as hydrosilylation catalysts is well described in the literature, as described in Lukevics et al., Organic Metal Chemistry Review No. 5, pages 1-179 (1977). It has been. For the most part, H ₂ PtCl ₆ .6H ₂ O dissolved in alcohols such as ethanol or isopropanol is the most widely used hydrosilylation catalyst. The use of other complexes of platinum with a wide range of additional ligands such as organophosphines, organosulfides, unsaturated organics such as alkenes and alkynes has also been widely used. Other containing similar ligands
Group VIII transition metal complexes have also been described as catalysts for hydrosilylation reactions.

These catalysts and their use in hydrosilylation reactions are well known to those skilled in the art. However, some of these hydrosilylation catalysts will also promote various side reactions, many of which result in the formation of volatile byproducts. And these by-products can cause undesired foam formation within the polymer substrate.

In addition to Group VIII transition metal catalysts, many inhibitors for hydrosilylation reactions are also known. The use of inhibitors for hydrosilylation reactions arises from the high activity of Group VIII transition metal catalysts; vinyl-containing substrates, S
Certain compositions containing an iH-containing substrate and a hydrosilylation catalyst are active enough to undergo a hydrosilylation reaction even at ambient temperatures. Thus, the incorporation of hydrosilylation catalyst inhibitors improves shelf life stability of the composition at ambient temperatures.

Hydrosilylation cross-linking of vinyl-containing polymers is GB 1,1
It is not limited to multi-SiH containing siloxanes or EPDM terpolymers as described in 18,327. Hydrosilylation cross-linking has also been reported for polymers, such as terminally unsaturated functionalized polyisobutylenes, utilizing various poly-SiH containing siloxanes and platinum hydrosilylation catalysts. In particular, HMe ₂ SiOMe ₂ SiOSiMe ₂ H and Si (OSiMe ₂ H)
₄ (described in Polymer Bulletin 1 575 (1979)); [MeHSiO] ₅ (macro molecular (Ma
cromolecules) 13 681-685 (1980) stated in); and _{HMe 2 Si (Me 2 SiO)} nOSiMe 2 H ( wherein, n = 3-
7) (described in the summary of the 20th Organosilicon Symposium, Tarryown, NY (1986)), and many others useful in olefin crosslinking.
All examples of SiH-containing siloxanes.

Most recently, hydrosilylated crosslinked vinyl containing polymer compositions were described in JP 61.60,727.
In particular, it is preferably per siloxane molecule
Crosslinking of polyolefins containing terminal or pendant unsaturation via hydrosilylation reactions using siloxanes containing 10 or more organohydrogensiloxane units and platinum catalysts is disclosed. It further discloses a method of avoiding hydrogen gas generation and thus foam formation due to adverse side reactions between the multi-SiH containing siloxane and the platinum hydrosilylation catalyst.

OBJECT OF THE INVENTION It is an object of the invention to provide a method for crosslinking reactive polyolefins using a rhodium-promoted hydrosilylation reaction with known and / or novel polyorganosiloxanes as crosslinking agents. Is.

Another object of the present invention is to provide a method for crosslinking reactive polyolefins which is suitable for crosslinking processed objects and which minimizes bubble formation therein.

Yet another object of the present invention is to provide novel siloxane compounds that are useful in the claimed method of crosslinking polyolefins.

Yet another object of the present invention is to provide a polyolefin composition crosslinked by the method of the present invention.

SUMMARY OF THE INVENTION The present invention is a novel method of crosslinking a reactive polyolefin comprising: 1) in the polyolefin, a) the formula: Or In the formula, R represents an alkyl group having 1 to about 4 carbon atoms, R ′ represents a hydrogen atom, an alkyl or alkoxy group having 1 to about 24 carbon atoms, and R ″ represents R or hydrogen. Represents an atom; D is a group Represents D; is a group Represents T; Represents Q; Represents an integer; x is an integer having a value in the range of about 2 to about 12; y is an integer having a value in the range of about 2 to about 12;
And z is an integer having a value in the range of 0 to about 6; a polyorganosiloxane represented by: or a mixture thereof, b) Formula L ₁ L ₂ RhX, wherein L ₁ and L ₂ are neutral Is a ligand that forms a coordinate bond, and X is a halogen atom or a pseudohalogen ligand, and 2) mixing a hydrosilyl catalyst represented by: and 2) between the polyorganosiloxane and the polyolefin. Initiating the hydrosilylation reaction is provided.

The present invention is also directed to a polyolefin composition comprising one or more polyorganosiloxane as defined above and a hydrosilylation catalyst.

The present invention is further directed to the crosslinked polyolefin composition produced by the above method.

The present invention is also directed to novel alkoxy-terminated polyorganosiloxanes that may be used in the claimed method of crosslinking reactive polyolefins.

DETAILED DESCRIPTION OF THE INVENTION Olefin polymers suitable for the purposes of the present invention are usually solid materials, and homopolymers of olefins, and one or more olefins with each other and / or copolymerizable with such olefins. Or copolymers with up to about 30% by weight of more monomers. Homopolymers and copolymers of olefins such as ethylene, propylene, butene-1, isobutylene, hexene-1, 4-methyl-pentene-1, pentene-1, octene-1, nonene-1, decene-1, and Copolymers of one or more such olefins with one or more other monomers copolymerizable with such olefins, such as vinyl and diene compounds, are suitable for the purposes of the present invention.

Examples of copolymers containing some unsaturation are ethylene copolymers such as ethylene-propylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene-1.
Copolymers, ethylene-octene-1 copolymers, polymers of ethylene with two or more of the following compounds: propylene, butene-1, hexene-1, 4-methyl-pentene-1, octene-1 and the like.

Particularly preferred reactive polyolefins for the purposes of the present invention
Is an ethylene / propylene / diene monomer polymer
-(EPDM). Diene component of a typical EPDM polymer
Is 1,4-hexadiene, dicyclopentadiene, ethyl
Ridene norbornene, 4 (5) -methyl-1,4-hexa
It is a diene or 1,5-cyclooctadiene. further
Also, these polymers are typically from about 60 to about
Contains 80% by weight of ethylene. EPDM polymer is Vistalo
(Vistalon) (Exxon), Nordel
(Shell) and Royalene (Uniroyya
Commercially available as).

Polyorganosiloxanes useful in the practice of the present invention have the formula: Or Wherein R represents an alkyl group having 1 to about 4 carbon atoms, preferably 1 carbon atom; R'is a hydrogen atom, an alkyl or alkoxy group having 1 to about 24 carbon atoms, preferably About 8 to about 14
Represents an alkyl or alkoxy group having a carbon atom of R; R ″ represents R or a hydrogen atom, preferably R; D represents a group Represents D; is a group Represents T; Represents Q; X is an integer having a value in the range of about 2 to about 12, preferably about 4 to about 8; y is a value in the range of about 2 to about 12, preferably about 4 to about 8. Is an integer; and z is an integer having a value in the range of 0 to about 6, preferably about 0 to about 4; or a mixture thereof.

Further, it is preferred that the sum of x , y and z does not exceed about 18, and preferably about 12.

Certain polyorganosiloxanes can be made by means well known to those skilled in the art. For example, each of the above formulas: Formula I Wherein the variables are as previously defined, wherein one type of silicone additive useful in the composition of the present invention is hexamethyldisiloxane, octamethylcyclotetrasiloxane, trimethyl endblocked It can be conveniently prepared by reacting a mixture containing methylhydrogenpolysiloxane and an acid catalyst. The number of repeating units can be varied as desired by varying the molar ratio of the reactants.
Detailed procedures for making precursors within the scope of the above formula are set forth in Example 2 of US Pat. No. 4,046,930.

Another class of polyorganosiloxanes reacts a compound of formula I with a stoichiometrically deficient amount of an unsaturated organic compound containing one terminal olefin group in the presence of a platinum catalyst such as chloroplatinic acid. It can be manufactured by The addition of this group, derived from an olefinic group, is useful to make the siloxane more compatible with certain polyolefins. This type of reaction is also described in Example 2 of US Pat. No. 4,046,930.

A third class of polyorganosiloxanes is the organohalosilane monomers, which are stoichiometrically deficient in C _1-24 alcohols, although these compounds are novel and useful in the methods claimed herein. It can be produced by reacting with. After that, the produced reaction product is hydrolyzed with water to cause a siloxane equilibrium reaction. At equilibrium, the hydrogen halide formed during the hydrolysis of the organosilane monomer may be removed by heating the reaction mixture. The final balance of hydrogen halide can be neutralized with conventional reagents such as sodium bicarbonate or potassium carbonate. This method is demonstrated in the examples in the preparation of siloxanes I and XIV.

The polyorganosiloxane is mixed with the polyolefin in an amount such that the molar ratio of polyorganosiloxane to pendant unsaturated groups present on the polyolefin is in the range of about 0.90: 1 to about 1: 0.90. Preferably, the ratio is in the range of about 0.95: 1 to about 1: 0.95, most preferably the ratio is about 1: 1. Any less than a 1: 1 ratio will result in an incompletely crosslinked composition. On the other hand, a composition containing excess polySiH-containing polyorganosiloxane will result in a fully crosslinked composition; however, excess polyorganosiloxane dilutes the crosslinked composition. Other than that, there will be no clear effect.

Hydrosilylation catalysts useful in the practice of the present invention have the formula L ₁ L ₂ RhX where L ₁ and L ₂ , which may be the same or different, are neutral coordinating ligands and X is , A halogen atom or a pseudo halogen atom.

The neutral coordinating ligand is a linear olefinic group containing from 2 to about 8 carbon atoms and an alicyclic hydrocarbon containing at least one double bond and having from 5 to about 12 carbon atoms. Contains. In addition, included in the definition of the ligand that has a neutral coordinate bond is carbon monoxide, and a compound of phosphine P (R) ₃ and phosphite P (OR) ₃ (wherein R is a phenyl group). , Or an alkyl-substituted phenyl group, where the alkyl group represents from 1 to about 6 carbon atoms. Preferably L ₁ and L ₂ are 2
Represents a linear olefinic group containing from about 8 to about 8 carbon atoms, an alicyclic hydrocarbon containing at least two double bonds and having from 6 to about 12 carbon atoms.

As mentioned above, X represents a halogen atom or a pseudo halogen atom. Therefore, X is a chlorine atom, a bromine atom,
It may represent an iodine atom or a cyano group. Preferably,
X represents a chlorine atom.

The desired concentration of catalyst used will depend on variables such as the temperature at which the polymer is processed or treated, the length of time the polymer is exposed to the treatment temperature, and the desired rate and degree of crosslinking. Typically, the catalyst charge is 25 to 1000 based on the total polyolefin composition (total amount of polyolefin, polyorganosiloxane and catalyst).
The range is ppm rhodium compounds, with 50 to 200 ppm rhodium compounds being the preferred range.

Also useful in the practice of the present invention are the rhodium catalysts and platinum-containing hydrosilylation catalysts described above, such as (C ₂ H ₅ S) ₂
It is a mixture with PtCl ₂ . These mixtures can include rhodium to platinum ratios varying from about 10: 1 to about 1:10. Mixtures having a ratio of rhodium to platinum compound of about 1: 1 are preferred. These mixtures may be used in the same amount as the pure rhodium catalyst, ie at a concentration of about 25 to about 1000 ppm based on the total polymer composition. Preferably, the mixture is used at a concentration of about 50 to about 200 ppm on the same basis. The use of the above mentioned mixture results in a substantial cost reduction and a shortened cure time over the use of the rhodium catalyst alone. Its use further results in an improved production of more highly crosslinked polymers as compared to the polymers produced by the use of platinum containing catalysts alone.

The method of adding the polyorganosiloxane to the reactive polyolefin can vary in that the polyorganosiloxane can be premixed with the reactive polyolefin. On the other hand, it may be added during the treatment of the reactive polyolefin by various methods, such as by direct injection or by using a cavity transfer mixer. Regardless of the method of addition of polyorganosiloxane, the important conditions to be met are:
(1) Sufficient mixing and dispersion of the polyorganosiloxane throughout the reactive polyolefin, and (2) if a catalyst is then present, ensure that no crosslinking reactions occur during the mixing or processing steps. That is, a sufficiently low temperature must be maintained. However, the claimed method and its use of the rhodium hydrosilylation catalyst require less stringent control of the reaction temperature as compared to most platinum hydrosilylation catalysts with respect to premature polymer crosslinking. In many cases, the use of platinum catalysts requires the addition of inhibitors to prevent premature crosslinking.

The rate of addition is maintained at the most advantageous rate to minimize the length of time required to produce the mixed reactive polyolefin; nevertheless
It is important to avoid adding too quickly. This is because this will ultimately prevent proper dispersion of the polyorganosiloxane in the reactive polyolefin.

The mixing of the polyorganosiloxane and the hydrosilylation catalyst can be carried out by various methods. For example, the polyorganosiloxane can be mixed into the reactive polyolefin at the recommended level of a 1: 1 molar ratio of SiH to C = C and the hydrosilylation catalyst added just prior to the treatment. You can It may be carried out by premixing the hydrosilylation catalyst into the reactive polyolefin and the polyorganosiloxane is added just before the treatment step. Different approaches may be taken to mix the polyorganosiloxane in a given weight of reactive polyolefin at twice the recommended concentration. The hydrosilylation catalyst is mixed in a similar weight portion of the reactive polyolefin at twice the desired concentration, and then an equal weight portion of the polyorganosiloxane-containing reactive olefin and the catalyst-containing reactive olefin are treated. It can be mixed thoroughly before the process. Yet another method is to mix the polyorganosiloxane into the reactive polyolefin at the recommended concentration, while adding the hydrosilylation catalyst as a concentrated mixture of catalyst in the reactive polyolefin (catalyst masterbatch). . Of course, the order of addition may be reversed,
This is the preferred method.

In the mixing process, the first important thing is that proper dispersion of the catalyst and the polyorganosiloxane in the vinyl-reactive polyolefin must occur in order to obtain a uniformly crosslinked polymer. Inappropriate dispersion can endow the bridge with an uneven distribution.
If the use of a catalyst masterbatch is adopted, the catalyst concentration in the masterbatch does not necessarily have to be within a narrow range, but two important factors are: (1) the rate of dispersion of the catalyst masterbatch in the reactive polyolefin. And (2) after considering the desired level of catalyst concentration in the final mixed reactive polyolefin, it is adjusted to the desired level.
If the mixing time of the catalyst masterbatch is short, it may be important to use a relatively low concentration of catalyst masterbatch. The thinner the catalyst masterbatch used, the easier it will be to disperse the desired amount of catalyst. If the mixing time of the catalyst masterbatch can be extended, it is preferred to use a more concentrated catalyst masterbatch to keep the total volume of material added in the form of the catalyst masterbatch to a minimum. Let's do it. The higher the concentration of the masterbatch, the longer the mixing step will be required to properly disperse the catalyst throughout the reactive polyolefin.

Hydrosilylation crosslinking of the reactive polyolefins described herein is accomplished by mixing the reactive polyolefin, polyorganosiloxane and hydrosilylation catalyst at a temperature below the point where the hydrosilylation reaction is initiated. It The composition is then shaped, formed, extruded, formed, or rolled into the desired shape and the hydrosilylation reaction is initiated by heating the composition. The temperature at which the hydrosilylation reaction is initiated depends primarily on the nature and / or composition of the hydrosilylation catalyst; some catalysts initiate the hydrosilylation reaction at relatively low temperatures, and some also at higher temperatures. Start with. The effective temperature for initiating the hydrosilylation crosslinking reaction is that temperature at which the polymer is molten, which increases the mobility of the catalyst during the hydrosilylation reaction. Although the polymer is flowable or meltable, the crosslinking reaction just confers mechanical integrity to the polymer melt. This induced mechanical integrity will be effective when polymer flow or sagging is not desired. After a period of time, which depends on the rate of the hydrosilylation reaction, the shaped, shaped, or extruded portion may be removed from the heat source and allowed to cool, while the other portion undergoes processing steps. it can. The hydrosilylation reaction will continue at a lower temperature, albeit at a much slower rate. Alternatively, the hydrosilylation reaction may go to completion while this part is undergoing the first heat treatment step. Furthermore, after removing the shaped article from the processing step, it may be brought to completion by a post-processing heat treatment step. In any case, it is important to complete the hydrosilylation reaction to give a fully crosslinked polymer composition.

Various materials commonly added to extrudable compositions can also be added to the compositions of the present invention. These materials include amounts of additives well known in the art such as pigments, plasticizers, antioxidants, as well as inorganic materials such as clay, talc, glass, silica, zinc oxide, titanium dioxide and the like.

The exact scope of the invention is set forth in the appended claims, but the following specific examples are provided to further illustrate certain aspects of the invention. These examples are given for illustrative purposes only and should not be construed as a limitation of the invention. Unless otherwise noted, all parts and percentages are by weight.

Definitions g. Grams mg. Milligrams mm. Millimeters psi. Pounds per square inch ° C Celsius degrees ODR Vibrating Discrete manufactured by Monsanto
Oscillating Disc Rheometer (COD) Cyclooctadiene P (Ph)_Three Triphenyl phosphate M (CH₃)₃Si (O)_1/2− Examples Reactive polyolefins used in the following examples
Is the Vistalon (Vistalo
n) Available commercially under the name 2504
Ethylene / propylene / ethylidene norbornene
It was a polymer rubber (EPDM). This terpolymer pair
The composition is ethylidene norbornene per 1000 carbon atoms.
Is 64.1% ethylene containing 5.82 C = C bonds.
The rest is said to consist of polypropylene. So
Therefore, this terpolymer is 4.58 x 10 per gram.^-Four
Includes moles of C = C.

Preparation of Siloxane I In a 3 liter three neck round bottom flask, a mechanical stirrer,
Friedrich addition funnel with nitrogen adapter
(Friedrich) with condenser (also nitrogen adaptor
Claisen adapter, which also has a
And a thermometer attached. In this flask, Me₂SiCl
₂(769.7g, 5.96mol) and MeSiHCl₂(686.6g, 5.96 models
Le) was charged. Add 1-dodecanol (55
4.9g, 2.983mol) was charged. Immerse the flask in an ice bath
I got it. When the contents of the flask reach 5 ℃ to 10 ℃
And slowly add dodecanol over 2 hours
The reaction mixture while maintaining the temperature below 10 ° C.
did. Once the addition is complete, the reaction mixture is further cooled below
Stir for 1 hour. Next, add distilled water (18
7.9g, 10.44mol) was charged. Reaction temperature below 10 ℃
While maintaining and allowing controllable release of HCl gas,
Add this water slowly to the flask for 1.5 hours.
Added When all the water has been added, stir the reaction mixture and
And allowed to warm to 20 ° C. for 16 hours. Addition
Replace the nozzle with a nitrogen sparging tube and spray loosely
The reaction mixture was slowly heated to 80 ° C. While spraying
After heating for 3 hours, allow the reaction mixture to cool to 50 ° C.
And while maintaining stirring, 1 g of aqueous NaHCO₃Add paste
Added After 1 hour, a part of the reaction mixture was dissolved in 0.1N NaOH.
Titrate the solution with pink phenolphthalene to the end point and add HCl.
The content was checked. This process is repeated until the HCl content falls below 0.2%.
Repeated. Celite Stir the filter aid
While adding to the reaction mixture and allowing the temperature to cool to about 25 ° C.
I tightened it up. Add the reaction mixture through a 0.1 micron pad.
When filtered under pressure, the white product of clear colorless water (1196
g, 90.0% yield) was produced. Low boiling point component of this product
Removed by vacuum stripping at 1 mmHg at 135 ° C
It had been.

Preparation of Siloxane X IV In a 5 liter three neck round bottom flask, mechanical stirrer,
Friedrichco, addition funnel with nitrogen adapter
With a condenser (also with a nitrogen adapter)
A Claisen adapter and a thermometer were attached. this
In a flask, add 1645.7 grams of MeSiHCl.₂A dry nitrogen atmosphere
I prepared it below. Add 1-dodecanol (132
9.7g) was charged. Then immerse the flask in an ice bath,
The chlorosilane was cooled to a temperature between 5 ° C and 10 ° C. Desired
When reaching the temperature range of 1-dodecanol, gently
Mechanically stirred for 2.5 hours.
Added to lorosilane. Allow the reaction mixture to continue for another 2 hours
It was stirred. Then add distilled water (193.02 g, 10.
72 mol) was charged. Then this water, whose temperature is still 5
Slowly into the reaction mixture which is maintained at ℃ to 10 ℃
Was added. The addition of water causes the release of HCl gas,
The gas is fried rather than through the side arm of the addition funnel.
It was discharged through the nitrogen outlet of the Richrich condenser. water
The rate of addition is such that the temperature of the reaction does not exceed 10 ° C and the HCl gas
The rate of release of the soot was maintained to be controllable. 2 hours
After complete addition of water over the period of time,
The mixture was stirred for 16 hours while slowly heating to 20 ° C. Next
The addition funnel was replaced with a nitrogen sparge tube. The reaction mixture
While gently sparging with nitrogen, keep the flask for 3 hours.
Heat slowly to 80 ° C. over. Reaction mixture at 50 ° C
1 g of aqueous NaHCO while allowing to cool and maintaining stirring.₃
The paste was added. After 1 hour, a portion of the reaction mixture was
0.1N NaOH solution to the end of pink phenolphthalene
The HCl content was checked by titration. This step has a HCl content of 0.2%
Repeated until the following. Celite Agitate filter aid
While adding to the reaction mixture and cooling the temperature to about 25 ° C
I'm sorry. Then add the reaction mixture to a 0.1 micron pad.
Clear colorless water, white product upon pressure filtration through
(2048.47 g, 95.8% yield) was produced. Next, low boiling point
Vacuum strip the product at 150 ° C / 1mmHg
Removed by.

Example 1 Brabender with mixing head Ps
40g. EPDM terpolymer in Chicorder (Plasticorder)
, And then add 4.0 g. Of Siloxane I to the syringe.
Therefore, it was added over a period of 2 minutes. Siloxane I
When fully incorporated into the terpolymer matrix, 250 mg
[(COD) RhCl]_TwoAdd hydrosilylation catalyst to composition
did. Mixing was continued for another 5 minutes. Mix final composition
Removed from the head, and 3 in. × 3 in. × 1/4 in. Cavity
It was placed in the cavity mold. Cavity mold to 180 ℃
Placed in a preheated press. Close the press and mold
Subjected to a pressure of 20,000 psi for 5 minutes. Then press the mold
Removed and allowed to cool. Rubber sample mold
Removed from the bridge and desired by cross-linking and gas generation
Inspected for the presence of non-existent bubbles. Heat treated sump
Le contained no bubbles.

The composition was then evaluated for cross-linking by cutting a 1/8 in. Strip and repeatedly pulling on the sample. Subsequent qualitative strength tests of comparison,
It was carried out by pulling or stretching a 1/8 in. Strip of untreated terpolymer. The heat-treated sample showed significantly increased strength compared to the untreated terpolymer.

Comparative Example A Using the same procedure as described in Example 1, H ₂ PtCl ₆
3.0 ml of a 10 mg / ml isopropanol solution of hexahydrate was used as the hydrosilylation catalyst. The heat-treated composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample was crosslinked, but it contained many bubbles due to gas formation.

Comparative Example B Using the same procedure as described in Example 1, 250 mg K
₂ PtCl ₄ was used as the hydrosilylation catalyst. The heat-treated composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles and showed little or no increase in strength. This is due to the apparently lower hydrosilylation cross-linking.

Using the same procedure as described in Comparative Example C Example 1 was used in 250mg of (PPh _{3) 3} RhCl hydrosilylation catalyst.
The heat treated rubber composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles and showed little or no increase in strength caused by hydrosilylation crosslinking.

Using the same procedure as described in Comparative Example D Example 1 was used in 250mg of (PPh _{3) 3} RhCOCl hydrosilylation catalyst. The heat-treated composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles and showed little or no increase in strength caused by hydrosilylation crosslinking.

Using the same procedure as described in Comparative Example E Example 1 was used in 250mg of _{(C 6 H 5 CN) 2} PtCl 2 as a hydrosilylation catalyst. The heat-treated composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles; however, it did contain appreciable amounts of strength caused by hydrosilylation crosslinking. This strength was less than that of the sample in which [(COD) RhCl] ₂ was used as the hydrosilylation catalyst.

Comparative Example F Using the same procedure as described in Example 1, 250 mg (COD) PtCl ₂ was used as the hydrosilylation catalyst. The heat treated sample was removed from the mold and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles. However, it did contain an appreciable amount of strength caused by hydrosilylation crosslinking. This strength was less than that of the sample in which [(COD) RhCl] ₂ was used as the hydrosilylation catalyst.

Using the same procedure as described in Comparative Example G Example 1 was used in 250mg of (PPh _{3) 2} IrCOCl hydrosilylation catalyst. The heat-treated composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles and no appreciable increase in strength compared to the untreated terpolymer.

Comparative Example H A masterbatch of H ₂ PtCl ₆ hexahydrate in the terpolymer of Example 1 was added to 2.0 mg H ₂ PtCl ₆ per gram of terpolymer.
Prepared with a catalyst concentration of hexahydrate. Using the same procedure as described in Example 1, 3.0 g of freshly prepared catalyst masterbatch was used as the hydrosilylation catalyst. The heat-treated composition was demolded and evaluated for the presence of crosslinks and bubbles. The sample contained many bubbles; however, it did contain an appreciable amount of strength. This strength was less than the sample of Example 1 using [(COD) RhCl] ₂ as the hydrosilylation catalyst.

Example 2 Using the same procedure as described in Example 1, 250 mg [(CO) ₂ RhCl] ₂ was used as the hydrosilylation catalyst. The heat treated sample was removed from the mold and evaluated for the presence of crosslinks and bubbles. The sample did not contain much foam, which did contain appreciable amounts of strength caused by hydrosilylation crosslinking.

Using the same procedure as described in Example 3 Example 1 was used in 250mg of (PPh _{3) 2} CORhCl hydrosilylation catalyst. The heat treated sample was removed from the mold and evaluated for the presence of crosslinks and bubbles. The sample contained a moderate amount of foam, which did show an appreciable amount of strength caused by the hydrosilylation cross-linking. This strength was less than the sample of the example using [(COD) RhCl] ₂ as the hydrosilylation catalyst.

Example 4 Brabender with mixing head To the plastic coder,
39 g. Of the terpolymer of Example 1 was charged. This tarpo
To the limmer, add 3.75 g. Of Siloxane I by syringe.
Added over a period of minutes. Siloxane I rubber matrix
2.5 mg [(COD) RhCl] when fully incorporated₂/ g
-2g of polymer masterbatch with hydrosilylation catalyst
Added to the composition and mixed for a further 5 minutes
I have Remove the final composition from the mix head and
Vibration of Monsanto preheated to 180 ℃
Placed in a disc rheometer. Close the system and mold
Exposed to a pressure of 80 psi. Remove the sample after 24 minutes
And let it cool down. Take sample from disc
And undesirable gas generation during the crosslinking process
Inspected for the presence of bubbles. The heat-treated composition,
By examining the maximum torque reading in rheometer units
I evaluated the bridge.

The sample was free of bubbles and had excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained was 20 rheometer units.

The heat treated samples were evaluated for gel content according to the procedure outline in ASTM test D1225. This procedure generally involves contacting the sample with boiling decalin for 6 hours, followed by
Including oven drying at 150 ° C and 1 mmHg for 10 hours or more. Then weigh the remaining material. The% extract of this sample was determined to be 4.1%. This is 95.9
Corresponds to a gel content of%.

Example 5 Using the same procedure outlined in Example 4, 5.17 g
Of Siloxane I was used as the siloxane crosslinker.
The heat-treated sample was free of bubbles and had excellent strength. The maximum torque obtained with ODR was 22 rheometer units.

The heat treated sample was then subjected to AS as outlined above.
Gel content was evaluated according to the procedure outline in TM test D1225. The% extract was determined to be 4.6%. This is 9
Corresponds to a gel content of 5.4%.

Example 6 Using the same procedure outlined in Example 4, 3.29 g
Of Siloxane II was used as the siloxane crosslinker.
The heat treated sample was free of bubbles and had excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained with ODR was 19.5 rheometer units.

Example 7 Using the same procedure outlined in Example 4, 4.69 g
Of Siloxane III was used as the siloxane crosslinker. The heat-treated sample contained no bubbles and
It had substantial strength caused by the hydrosilylation crosslinking process. The maximum torque obtained with ODR was 15.5 rheometer units.

Comparative Example I Using the same procedure as outlined in Example 4, 5.10 g
Of Siloxane IV was used as the siloxane crosslinker.
The heat treated sample was free of bubbles but had only moderate strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained by ODR is 9
It was in rheometer units.

Comparative Example J 1.21 g using the same procedure outlined in Example 4.
Of Siloxane V was used as the siloxane crosslinker.
The heat treated sample contained many bubbles and did not have substantial strength caused by the hydrosilylation crosslinking process. The maximum torque obtained with ODR was only 4 rheometer units.

Comparative Example K Using the same procedure outlined in Example 4, 2.91 g
Of Siloxane VI was used as the siloxane crosslinker.
The heat treated sample contained many bubbles and did not have substantial strength. The maximum torque obtained with ODR was 2 rheometer units.

Example 8 Using the same procedure outlined in Example 4, 3.36 g
Of siloxane VIII was used as the siloxane crosslinker. The heat-treated sample contained no bubbles and
It had excellent strength caused by the hydrosilylation crosslinking process. The maximum torque obtained with ODR was 24 rheometer units.

Example 9 Using the same procedure outlined in Example 4, 4.23 g
Of siloxane VIII was used as the siloxane crosslinker. The heat-treated sample contained no bubbles and
It showed excellent strength. The maximum torque obtained with ODR was 20 rheometer units.

Example 10 Using the same procedure as outlined in Example 4, 2.56 g
Of siloxane IX was used as the siloxane crosslinker.
The heat treated sample was free of bubbles and had substantial strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained with ODR was 17.5 rheometer units.

Example 11 Using the same procedure outlined in Example 4, 3.31 g
Of Siloxane X was used as the siloxane crosslinker.
The heat treated sample was free of bubbles and showed substantial strength. The maximum torque obtained with ODR was 16 rheometer units.

Example 12 Using the same procedure outlined in Example 4, 1.88 g
Of Siloxane XI was used as the siloxane crosslinker.
The heat treated sample was free of bubbles and exhibited excellent strength. The maximum torque obtained with ODR was 19 rheometer units.

Comparative Example M 2.23 g using the same procedure outlined in Example 4.
Of Siloxane XII was used as the siloxane crosslinker. The heat treated sample contained many bubbles,
It showed no substantial strength. The maximum torque obtained with ODR was 6 rheometer units.

Comparative Example N 1.68 g using the same procedure outlined in Example 4.
Of Siloxane XIII was used as the siloxane crosslinker. The heat treated sample contained many bubbles,
It showed no substantial strength. The maximum torque obtained with ODR was 4 rheometer units.

Example 13 Brabender with mixing head Plastic coder
To the above, 40 g. Of the terpolymer of Example 1 was charged. Mixer
, 4.00 g. Of Siloxane XII by syringe for 3 minutes
Was added over time. Siloxane XII in the matrix
2.5 mg [(COD) RhCl] when fully incorporated₂/ g tarpo
3g of Limmer Masterbatch as hydrosilylation catalyst
Add to this composition and mix for an additional 5 minutes
It was Remove final composition from mixing head and
Samples from Monsanto pre-heated to 180 ° C.
It was placed in the disk rheometer. Close ODR and mold 8
Exposed to a pressure of 0 psi. After 24 minutes, take a sample from the ODR.
Let out and let it cool. Rubber sample disk
And the gas production during the bridging process
Inspected for the presence of unwanted foam. Heat treated set
The maximum torque of the product can be measured on the ODR graph in rheometer units.
Evaluate the cross-linking by examining the
It was

The sample was free of bubbles and showed excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained was 22.5 rheometer units.

Example 14 Using the same procedure outlined in Example 13, the sample was cured at 160 ° C. in a vibrating disc rheometer. The heat-treated sample contained no bubbles and
It showed substantial strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained with ODR was 16 rheometer units.

Example 15 Using the same procedure outlined in Example 13, the sample was cured at 200 ° C. in a vibrating disc rheometer. The heat-treated sample contained no bubbles and
It showed excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained with ODR was 20 rheometer units.

Example 16 Brabender with mixing head To the plastic coder,
30 g. Of the terpolymer of Example 1 was charged. mixer
And 4.00 g. Of Siloxane I by syringe for 3 minutes
Added over time. Siloxane I is completely added to the rubber matrix.
2.5 mg [(COD) RhCl] when incorporated into all₂/ g tarpoly
3 g of Mermaster batch was used as a hydrosilylation catalyst.
Was added to the composition and allowed to mix for an additional 5 minutes.
At this point, 30 g of the calcined clay for 5 minutes
Slowly added to the mixed composition. When mixed thoroughly,
The final composition was removed from the mixing head.

A small sample was placed in a Monsanto Oscillating Disc Rheometer (ODR) preheated to 180 ° C. The ODR was closed and the mold was exposed to a pressure of 80 psi. After 24 minutes, the sample was removed from the ODR and allowed to cool. Samples were removed from the disks and inspected for the presence of unwanted bubbles due to gas formation during the crosslinking process. The heat-treated composition was evaluated for cross-linking by examining the maximum torque reading on the ODR graph, in rheometer units.

The heat treated sample was free of bubbles and showed excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained was 32.5 rheometer units.

The remaining system of the original sample was placed in a 6 in. × 6 in. × 0.075 in. Cavity mold and placed in a press preheated to 180 ° C. Expose the mold to 20,000 psi while heating for 15 minutes,
Then it was removed from the press and allowed to cool. Tensile bars were stamped from smooth gray cross-linked samples and evaluated for tensile strength and elongation. The sample exhibited a tensile strength of 1170 psi and a corresponding elongation value of 340%.

Example 17 Brabender with mixing head Plastic coder
To the above, 40 g. Of the terpolymer of Example 1 was charged. Mixer
, 4.00 g. Of Siloxane I by syringe for 3 minutes
Added over time. Complete siloxane I in the composition
2.5 mg [(COD) RhCl] when incorporated into all₂/ g tarpoly
2 g of Mermaster batch was used as a hydrosilylation catalyst.
Was added to the composition and allowed to mix for an additional 5 minutes.
When thoroughly mixed, remove final composition from mix head
did.

A small sample was placed in a Monsanto vibrating disc rheometer preheated to 180 ° C. The ODR was closed and the mold was exposed to a pressure of 80 psi. After 24 minutes, the sample was removed from the ODR and allowed to cool. Rubber samples were removed from the disks and inspected for the presence of unwanted bubbles due to gas formation during the crosslinking process. The heat treated rubber composition was evaluated for cross-linking by examining the maximum torque reading on an ODR graph, in rheometer units.

The sample was free of bubbles and showed excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained was 22.5 rheometer units over 24 minutes.

The rest of the original sample was placed in a 6 in. × 6 in. × 0.075 in. Cavity mold and placed in a press preheated to 180 ° C. The mold was exposed to 20,000 psi with heating for 15 minutes and then removed from the press and allowed to cool. Tensile bars were stamped from smooth clear cross-linked samples and evaluated for tensile strength and elongation. The sample exhibited a tensile strength of 320 psi and a corresponding elongation value of 380%.

Example 18 The same procedure as described in Example 15 was used except 4.0 ml of Siloxane X VI was used as the cross-linking agent. A small sample was placed in the ODR and evaluated for hydrosilylation crosslinking at 180 ° C for 24 minutes.

The heat treated sample was free of bubbles and had excellent strength resulting from the hydrosilylation crosslinking process. The maximum torque obtained was 22 rheometer units.

The rest of the original sample was placed in a 6 in. × 6 in. × 0.075 in. Cavity mold and placed in a press preheated to 180 ° C. The mold was exposed to 20,000 psi with heating for 15 minutes and then removed from the press and allowed to cool. Tensile bars were stamped from smooth clear cross-linked samples and evaluated for tensile strength and elongation.

The sample exhibited a tensile strength of 380 psi and a corresponding elongation value of 370%.

Comparative Example O A masterbatch of platinum hydrosilylation catalyst (C ₂ H ₅ S) ₂ PtCl ₆ in the terpolymer of Example 1 was prepared at a catalyst concentration of 2.5 mg / g terpolymer. Then 2.0 g of this catalyst masterbatch was used in the procedure of Example 4.

A portion of the mixed sample was heat cured in ODR. The sample contained little foam and showed a considerable degree of strength. However, the maximum torque obtained was only 16.9 rheometer units.

Example 19 The catalyst is a) 1.0 g of the platinum catalyst masterbatch of Comparative Example O,
And b) the procedure of Example 4 was repeated except that it consisted of 1.0 g of the rhodium catalyst masterbatch of Example 4.

The cured sample was free of bubbles and showed excellent strength. The maximum torque obtained was 26 rheometer units; this value was greater than that obtained with the same catalyst charge of either the platinum catalyst of Comparative Example O or the rhodium catalyst of Example 4. In addition, the bridging speed was enhanced such that about 90% of the bridging that occurred in the sample occurred within the first 6 minutes.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 83:04)

Claims (3)

[Claims] 1. A method for the cross-linking of reactive polyolefins comprising: 1) in the polyolefin, a) the formula: Or In the formula, R represents an alkyl group having 1 to about 4 carbon atoms, R ′ represents a hydrogen atom, an alkyl or alkoxy group having 1 to about 24 carbon atoms, and R ″ represents R or hydrogen. Represents an atom; D is a group Represents D; is a group Represents T; Represents Q; Represents an integer; x is an integer having a value in the range of about 2 to about 12; y is an integer having a value in the range of about 2 to about 12;
And z is an integer having a value in the range of 0 to about 6; a polyorganosiloxane represented by: or a mixture thereof, b) Formula L ₁ L ₂ RhX, wherein L ₁ and L ₂ are neutral Introducing a hydrosilylation catalyst represented by, which is a ligand for coordinate bond, and X is a halogen atom or a pseudohalogen ligand, and 2) the hydrosilylation reaction of the polyolefin therein. Exposure to an elevated temperature sufficient to initiate the reaction, wherein the amount of polyorganosiloxane or mixture a) is such that the molar ratio of polyorganosiloxane to bendant unsaturated groups present on the polyolefin is 0.90: 1. To 1: 0.90 and the amount of hydrosilylation catalyst b) is 25 based on the total amount of polyolefin, polyorganosiloxane and catalyst. A stone 1000 ppm, wherein the. 2. A) reactive polyolefin, b) formula: Or In the formula, R represents an alkyl group having 1 to about 4 carbon atoms, R ′ represents a hydrogen atom, an alkyl or alkoxy group having 1 to about 24 carbon atoms, and R ″ represents R or hydrogen. Represents an atom; D is a group Represents D; is a group Represents T; Represents Q; Represents an integer; x is an integer having a value in the range of about 2 to about 12; y is an integer having a value in the range of about 2 to about 12;
And z is an integer having a value in the range of 0 to about 6; a polyorganosiloxane represented by: or a mixture thereof, and c) Formula L ₁ L ₂ RhX wherein L ₁ and L ₂ are neutral. A hydrosilylation catalyst represented by: wherein X is a halogen atom or a pseudohalogen ligand, and X is a halogen atom or a pseudohalogen ligand, and the amount of polyorganosiloxane or a mixture thereof a) is a polyorganosiloxane. The amount of hydrosilylation catalyst b) is such that the molar ratio of the bendant unsaturated groups present on the polyolefin to the range of 0.90: 1 to 1: 0.90, and the amount of hydrosilylation catalyst b) is the total amount of polyolefin, polyorganosiloxane and catalyst. 25 to 1000 ppm based on 3. A polyorganosiloxane useful in crosslinking reactive polyolefin compositions, the polyorganosiloxane having the formula: Or In the formula, R represents an alkyl group having 1 to about 4 carbon atoms, R ′ represents a hydrogen atom, an alkoxy group having 1 to about 24 carbon atoms, and R ″ represents R or a hydrogen atom. Representation; D is a group Represents D; is a group Represents T; Represents Q; Represents an integer; x is an integer having a value in the range of about 2 to about 12; y is an integer having a value in the range of about 2 to about 12;
And z is an integer having a value in the range of 0 to about 6; a polyorganosiloxane represented by or a mixture thereof.