JPH07103181B2 - Liquid hydroxylated modified ethylene-based random copolymer and use thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid hydroxylated modified ethylene random copolymer and its use. More specifically, it provides a liquid hydroxylated modified ethylene-based random copolymer capable of exhibiting excellent performance in applications such as a lubricating oil compounding agent, a paint compounding agent, and a resin modifier, and the use thereof. Is.

[Prior Art] Various additives are added to lubricating oils such as gear oils, engine oils, greases, metalworking oils, and release agents in order to improve their performance according to the purpose of use. Most of the additives are polar compounds. In order for these additives to achieve their initial objectives, it is desirable that they be soluble in these lubricating base oils, but some of these additives have a low affinity for the base oil, In that case, many of them were not dissolved but simply dispersed in the base oil. Recently, the replacement of conventional mineral oils with conventional lubricating oils to synthetic lubricating oils represented by olefin polymer oils is in progress, but with these synthetic lubricating oils, the above tendency is becoming clearer. In many cases, the effect of improving the performance of oil did not appear sufficiently. Therefore, in the field of lubricating oil applications, there is a strong demand for compatibilizers capable of improving the solubility of various lubricating oil additives in base oils.

Also in the field of paints, additives are blended according to various purposes. For example, as a filler anti-sedimentation agent, an anti-sagging agent, and a low-temperature flexibility-imparting agent, ultrafine silica particles, ultrafine sedimentable calcium carbonate, bentonite, organic bentonites, etc. have been conventionally used. It is hard to say that each of them has sufficient performance. Therefore, also in the field of paint application, there is a strong demand for a compounding agent for paint which is excellent in the above performance.

[Problems to be Solved by the Invention] The inventors of the present invention have recognized that the conventional compounding agents for lubricating oil have the above-mentioned problems, and about these compounding examples capable of exhibiting further excellent performance. As a result of intensive studies, it was found that a liquid hydroxylated modified ethylene-based random copolymer having specific properties is a novel substance, and that the liquid hydroxylated modified ethylene-based random copolymer can achieve the above-mentioned object, and arrived at the present invention. It is a thing.

An object of the present invention is to provide a liquid hydroxylated modified ethylene-based random copolymer which is a novel substance.

Further, an object of the present invention is to provide a compounding agent for lubricating oil comprising a liquid hydroxyl variable ethylene random copolymer and a compounding agent for a coating material comprising the liquid hydroxylated modified ethylene random copolymer.

[Means for Solving the Problems] According to the present invention, a hydroxylated modified product of a liquid ethylene random copolymer composed of ethylene and α-olefin having 3 to 20 carbon atoms, comprising: i) The ethylene component of the liquid hydroxylated modified ethylene-based random copolymer is 10 to 85 mol% and α-
The olefin component is in the range of 15 to 90 mol%, (ii) two adjacent tertiary groups in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid hydroxylated modified ethylene random copolymer. Α based on methylene chains between carbon atoms
No signals of β and βγ are observed, (iii) Vapor pressure osmometer (VP) of the liquid hydroxylated modified ethylene random copolymer
Number average molecular weight (n) measured by O) is 200 to 10,000
And (iv) the hydroxyl group is bonded to a carbon atom derived from ethylene or α-olefin which is located at the molecular end of the liquid ethylene random copolymer, and the content ratio of the hydroxyl group is A liquid hydroxylated modified ethylene random copolymer characterized by being in the range of 0.01 to 1 mol per 100 g of liquid hydroxylated modified ethylene random copolymer is provided as a substance invention, and further, the liquid hydroxyl Provided as a use invention are a compounding agent for a lubricating oil comprising a modified ethylene-based random copolymer and a coating composition comprising the liquid hydroxylated modified random ethylene-based copolymer.

The liquid hydroxylated modified ethylene random copolymer of the present invention is a hydroxylated modified product of a liquid ethylene random copolymer composed of ethylene and α-olefin having 3 to 20 carbon atoms. The group is one in which at least one hydroxyl group is bonded to at least one carbon atom forming a carbon-carbon unsaturated bond derived from ethylene or α-olefin located at the molecular end of the liquid ethylene random copolymer. And
For example, the pour point measured according to JIS K-2269 is 50 ° C.
The kinematic viscosity at 100 ° C. measured according to JIS K-2283 is 1 × 10 ⁵ centistokes or less.

The content of the ethylene component constituting the liquid hydroxyl-modified ethylene-based random copolymer is 10 to 85 mol%,
It is preferably 20 to 80 mol%, particularly preferably 30 to 70 mol% and the content of the α-olefin component is 15 to 90 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%. is there. Even if the content of the ethylene component of the liquid hydroxylated modified ethylene random copolymer is less than 10 mol% and the content of the α-olefin component is more than 90 mol%, the liquid hydroxylated modified ethylene is also used. Even if the content of the ethylene component in the random copolymer is more than 85 mol% and the content of the α-olefin component is less than 15 mol%, the performance as a lubricating oil compounding agent or paint compounding agent decreases. Come to do.

In the ¹³ C-NMR spectrum of the liquid hydroxy-modified ethylene-based random copolymer, two adjacent groups in the main chain of the copolymer were
Α and β based on methylene chains between 3 carbon atoms
No γ signal is observed.

Further, the paper hydroxyl osmometer (VPO) of the liquid hydroxylated modified ethylene-based random copolymer
The number average molecular weight (n) measured by the method is 200 to 10,000, preferably 300 to 8,000, particularly preferably 500 to 50.
It is in the range of 00. When the number average molecular weight of the liquid hydroxyl-modified ethylene-based random copolymer is smaller than 200 or larger than 10,000, the performance as a lubricating oil compounding agent or coating material compounding agent deteriorates.
Also, the intrinsic viscosity [η] measured in decalin at 135 ° C is
0.01 to 0.4 dl / g, preferably 0.02 to 0.35 dl / g,
The range of 0.03 to 0.3 dl / g is particularly preferable.

The molecular weight distribution (w / n) of the liquid hydroxylated modified ethylene-based random copolymer measured by gel permeation chromatography (GPC) is 1.1 to 4.
The range is 0, preferably 1.2 to 3.0, particularly preferably 1.3 to 2.5.

The hydroxyl group content of the liquid hydroxyl-modified ethylene-based random copolymer is 0.01 to 1 per 100 g of the liquid hydroxyl-modified ethylene-based random copolymer.
The amount is preferably in the range of 0.015 to 0.5 mol, particularly preferably 0.02 to 0.4 mol. When the content ratio of the hydroxyl group in 100 g of the liquid hydroxyl-modified ethylene-based random copolymer is less than 0.01 mol, the performance as a lubricating oil formulation example or a coating formulation example is deteriorated. Further, when the content ratio of the hydroxyl group in 100 g of the liquid hydroxyl-modified ethylene-based random copolymer is more than 1 mol, the performance as a lubricating oil compounding agent or a paint compounding example is deteriorated.

The ethylene-based random copolymer constituting the liquid hydroxylated modified ethylene-based random copolymer is a liquid ethylene-based random copolymer formed from ethylene and α-olefin having 3 to 20 carbon atoms, and its ethylene component. (A) is in the range of 10 to 85 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%, and the α-olefin component (b) is 15 to 90 mol%, preferably 20 to 90 mol%. 80 mol%, particularly preferably 30
To 70 mol%.

The intrinsic viscosity [η] of the liquid ethylene random copolymer measured in decalin at 135 ° C. is usually 0.01 to 0.4 dl /
g, preferably in the range of 0.03 to 0.3 dl / g, and the number average molecular weight measured by a vapor pressure osmometer (VPO) is usually 200 to 10,000, preferably 30.
0 to 8000, particularly preferably 500 to 5000,
The molecular weight distribution (w / n) measured by the GPC method is usually 4.0 or less, preferably 3.0 or less, and particularly 2.5 or less.

The liquid ethylene random copolymer has an iodine value of 1 to
It is in the range 125, preferably 2 to 85. The liquid ethylene-based random copolymer has a carbon-carbon unsaturated bond based on an ethylene unit or an α-olefin unit at one end of the copolymer molecule, or has an ethylene unit or an α-terminal at one end. Carbon based on olefin units
It is a mixture of one having a carbon unsaturated bond and one not having a carbon-carbon unsaturated bond at one end of the copolymer molecule.

When used in the modification reaction to obtain the liquid hydroxylated modified ethylene-based random copolymer of the present invention, it is preferred that one end of the copolymer molecule is all carbon-carbon unsaturated bonds.

Specific examples of the α-olefin component having 3 to 20 carbon atoms which is a constituent part of the liquid ethylene random copolymer include propylene, 1-butene, 1-hexene and 4-.
Methyl-1-pentene, 3-methyl-1-pentene, 1
Examples thereof include octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Further, as the non-conjugated polyene component, specifically, 1,4-hexadiene, 1,4
-Pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-hexadiene, 5-ethylidene-2-
Norbornene, dicyclopentadiene, 5-vinyl-2
-Norbornene, 5-methylene-2-norbornene, 1,
Examples thereof include 5-cyclooctadiene and 5,8-endomethylenehexahydronaphthalene.

In the ¹³ C-NMR spectrum of the liquid ethylene random copolymer, αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not observed. For example, in a copolymer of ethylene and 1-hexene, the following bond: Is the central three methylene groups at the positions α, β, γ from the left when viewed from the tertiary carbon on the left derived from 1-hexene, while α, β from the right when viewed from the tertiary carbon on the right. ,
It is in the γ position. Therefore, although there are methylene groups in the above binding units that give the signals of αγ and ββ, αβ
And there is no methylene group giving the βγ signal.

Similarly 1-hexene comrades bound head-to-tail with the following bonds: Exists only in methylene groups that give α and α signals, and there is no methylene group that gives αβ and βγ signals.

On the other hand, the following combination Each have a methylene group that provides a βγ signal and an αβ signal.

Furthermore, the liquid ethylene-based random copolymer has the following formula (I): Wherein, P _E represents the molar fraction of the ethylene component in the copolymer, P ₀ is α- olefin indicates molar fraction of component, P _0E the total dyad chain α- olefin-ethylene chain The molar fraction of is shown. (However, the content mole fraction of each component in the formula (I) is a value calculated excluding the end component)], the B value represented by the following formula (II) 1.03 ≤ B ≤ 2 ( It is within the range that satisfies II).

The larger the B value, the smaller the number of blocky chains, and the more uniform the distribution of ethylene and α-olefin, indicating that the copolymer has a narrow composition distribution.

The liquid ethylene-based random copolymer preferably has the following B value.

When the ethylene content of the copolymer is 50 mol% or less: 1.0 + 0.3 × P _E ≦ B ≦ 1 / (1-P _E ), more preferably the general formula 1.0 + 0.4 × P _E ≦ B ≦ 1 / (1-P _E ), particularly preferably the general formula 1.0 + 0.5 × P _E ≦ B ≦ 1 / (1-P _E ), when the ethylene content of the copolymer is 50 mol% or more: 1.3-0.3 × P _E ≦ B ≦ 1 / P _E , more preferably the general formula 1.4−0.4 × P _E ≦ B ≦ 1 / P _E , particularly preferably the general formula 1.5−0.5 × P _E ≦ B ≦ 1 / P _E , the liquid ethylene Random copolymers of the type have ethylene and 3 to 20 carbon atoms in the presence of (A) a zirconium compound having a conjugated π electron group as a ligand, and (B) an aluminoxane catalyst. It can be prepared by copolymerizing α-olefin and optionally a non-conjugated polyene.

The liquid ethylene-based random copolymer is prepared by the method proposed in Japanese Patent Application Laid-Open No. 61-221207 and Japanese Patent Application No. 60-259835, specifically, [A] IV of the periodic table. a compound of a transition metal selected from the group consisting of b group, V b group and Vl b group, and [B] general formula (III) or general formula (IV) R ₂ AlOAl _m O—AlR ₂ (III) (Wherein R represents a hydrocarbon group, and m is preferably an integer of 5 or more), and a method of copolymerizing ethylene and α-olefin in the presence of a catalyst formed from It can be manufactured by appropriately selecting the conditions in.

The following method can be specifically exemplified as a method for producing the liquid hydroxylated modified ethylene random copolymer of the present invention.

(1) Hydroborane such as diborane or 9-BBN (9-borabicyclo [3.3.1] nonane) is added to the liquid ethylene random copolymer, and a hydrovolatization reaction is performed, followed by oxidation with hydrogen peroxide. how to.

(2) A method in which a mixture of an organic acid such as formic acid or acetic acid and hydrogen peroxide is added to the liquid ethylene random copolymer to oxidize it.

(3) The liquid ethylene-based random copolymer is added to peracetic acid,
A method of adding an organic peroxide such as m-chloroperbenzoic acid to epoxidize it, and then hydrolyzing it.

In the method (2), a liquid modified ethylene random copolymer in which hydroxylation and esterification proceed at the same time and monohydroxyl monoesterification is obtained. Further, the ester group can be converted into a hydroxyl group by saponification, whereby a dihydroxylated liquid modified ethylene-based random copolymer is obtained.

More specifically, in the method (1), the amount of hydroboron added is 1 to 10 mol, preferably 2 to 5 mol, based on 1 mol of the unsaturated bond of the liquid ethylene random copolymer. The amount of hydrogen peroxide added is 1 to 10 moles, preferably 2 to 5 moles per mole. The temperature of the hydrovola- tion and the oxidation reaction is -20 to 60 ° C, preferably 0 to 40.
The temperature is 0.5 ° C. and the time required is 0.5 to 20 hours, preferably 1 to 10 hours. Further, the polymer concentration is in the range of 5 to 200 g /, preferably 10 to 100 g /.

In the method (2), the amount of the organic acid added is 1 to 200 mol, preferably 5 to 100 mol, and the amount of hydrogen peroxide added is 1 mol with respect to 1 mol of the unsaturated bond of the liquid ethylene random copolymer. Is 1 to 50 mol, preferably 2 to
It is in the range of 20 moles. The reaction concentration is 0 to 60 ℃,
It is preferably 10 to 50 ° C., and the time required for this is 0.
It is 5 to 20 hours, preferably 1 to 10 hours. Further, the polymer concentration is in the range of 5 to 400 g /, preferably 10 to 300 g /.

In the method (3), the addition amount of the organic peroxide is in the range of 1 to 10 mol, preferably 1 to 5 mol per 1 mol of unsaturated bond of the liquid ethylene random copolymer. The reaction temperature is 0 to 100 ° C., preferably 10 to 80 ° C., and the time required is 0.1 to 10 hours, preferably 0.5 to 5 hours. Further, the polymer concentration is in the range of 5 to 400 g /, preferably 10 to 300 g /. Next, in the hydrolysis, an aqueous solution having an alkali concentration of 0.5 to 5N, preferably 1 to 4N is added in an amount of 10 to 100 m per 1 g of the above polymer.
1, preferably 5 to 50 m. The reaction temperature is 20 to 100 ° C, preferably 40 to 80 ° C, and the time required for this is 1 to 20 hours, preferably 2 to
10 hours.

The solvent used in producing the liquid hydroxylated modified ethylene-based random copolymer of the present invention is benzene,
Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and ether solvents such as ethyl ether, tetrahydrofuran and dioxane.

The liquid hydroxylated modified ethylene random copolymer of the present invention can be used as a compounding agent for lubricating oil.
As a compounding agent for lubricating oil, any of mineral oil lubricating base oil, olefin-based synthetic circulating oil such as olefin polymer or copolymer oil, silicone-based synthetic lubricant, synthetic lubricant such as ester-based synthetic lubricant, etc. Can also be used for The mixing ratio of the liquid hydroxylated modified ethylene random copolymer is usually 0.5 to 300 parts by weight, preferably 0.8 to 200 parts by weight, particularly preferably 1 to 150 parts by weight based on 100 parts by weight of the lubricating base oil. It is a range. In addition to the liquid hydroxylated modified ethylene-based random copolymer, various additives known to be added to lubricating oils can be added to the lubricating oil. Specific examples of the lubricant additive include mineral oil (Neutra oil), low molecular weight α-olefin polymer, silicon synthetic lubricant, ester synthetic lubricant, oxidation stabilizer, extreme pressure agent, and rust additive. Agents, antifoaming agents, antiwear agents, etc. can be added.
The blending ratio of these components is in an appropriate range.

The lubricating oil containing the liquid hydroxylated modified ethylene-based random copolymer is used for gear oils, engine oils, greases, metal working oils, release agents and the like.

The liquid hydroxylated modified ethylene-based random copolymer of the present invention can be used as a compounding agent for paints. As the coating material to which the liquid hydroxylated modified ethylene random copolymer of the present invention is added, specifically, an alkyd resin or a modified product thereof, an unsaturated polyester or a modified product thereof, a phenol resin, an epoxy resin is used as a resin component for forming a coating film. Resins or modified products thereof, amino resins such as urea resins and melamine resins, polyurethane resins, resins for condensation paints such as drying oil; paints containing resins for polymerization paints such as acrylic resins and resins for rubber paints It can be illustrated. The blending ratio of the liquid hydroxylated modified ethylene-based random copolymer is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the coating film forming element component in the coating composition. In addition to the conventionally known various additives such as pigments, solvents (in the case of solvent-based paints), dispersion media (emuldienes), the paints containing the liquid hydroxylated modified ethylene random copolymer of the present invention are added. In the case of a mold paint), an appropriate amount of a leveling agent, a weather resistance stabilizer, etc. is added.

The liquid hydroxyl-modified ethylene-based random copolymer of the present invention has various uses in addition to the above-mentioned compounding agent for lubricating oil and the above-mentioned compounding agent for coating, for example, dispersant for solid additive to lubricating oil, processing of rubber or resin. Auxiliaries, fiber processing aids, rubber or resin modifiers, plasticizers, ink additives, metal ion scavengers, ion exchangers, agricultural chemical spreaders, paint plasticizers, paint primer modifiers It can be used for applications such as adhesive modifiers.

(Example) Next, the present invention will be specifically described with reference to examples.

The method for measuring the composition and physical properties of the liquid hydroxylated modified ethylene random copolymer of the present invention and the liquid ethylene random copolymer as the raw material and the evaluation method thereof are shown below.

(1) The content of ethylene, α-olefin, hydroxyl group and ester group was determined by ¹³ C-NMR measurement.
Usually, the measurement conditions are the same as the B value measurement conditions described below.

(2) Measuring method of number average molecular weight Using a vapor pressure osmometer (VPO),
Using benzyl and squalane as standard samples of known molecular weight, the number average molecular weight (n) was measured by a conventional method under the conditions of a toluene solvent and 80 ° C.

(3) The molecular weight distribution (w / n) was measured by Takeuchi, "Gel Permeation Chromatography," published by Maruzen.
The procedure is as follows.

Standard polystyrene with known molecular weight (Toyo Soda Co., Ltd.)
Made of monodisperse polystyrene) and its molecular weight M and its GP
The C (Gel Permeation Chromatograph) count is measured, and a correlation diagram calibration curve of the molecular weight M and Ve (Elution Volum) is prepared. The concentration at this time is 0.02 wt%.

GPC chromatograph of the sample by GPC measurement method,
The number average molecular weight n and weight average molecular weight w in terms of polystyrene are calculated by the above (1), and the w / n value is obtained. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation] (a) Collect a sample in an Erlenmeyer flask together with a toluene solvent so as to be 0.1 wt%.

(B) After heating the Erlenmeyer flask at 70 ° C for 1 hour, it is filtered with a stainless steel filter (pore size 0.5 µ), and the filtrate is applied to GPC.

(GPC conditions) The conditions were as follows.

(A) Equipment: Waters (150C-ALC / GPC) (b) Column: Toyo Soda (G4000H, G3000H, G200
0H) (C) Concentration: 70 ° C. (D) Flow rate: 1.5 ml / min (4) B value The B value of the liquid low molecular weight ethylene copolymer is defined as follows.

Wherein, P _E represents the molar fraction of the ethylene component in the copolymer, P ₀ is α- olefin indicates molar fraction of component, P _0E the total dyad chain α- olefin-ethylene chain The B value is an index of the distribution state of each monomer component in the copolymer. GJRay (Macromolecules, 10 , 773 (197
7), JCRandall (Macromolecules, 15 , 353 (198
2), J. Polymer Science, Polymer Phyics, Ed., 1
1 , 275 (1973), K. Kimura (Polymer, 25 , 441 (19
84)) et al. Based on P _E , P ₀ and P defined above.
It is calculated by finding _0E . The larger the B value is, the less the blocky chain is, and the more uniform the distribution of ethylene and α-olefin is.

The B value is a ¹³ C-NMR spectrum of a sample in which about 200 mg of the copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
Measurement frequency 25.05MHz, spectrum width 1500Hz, filter width 1500Hz, pulse repetition time 4.2sec, pulse width 7μse
c, the number of times of integration is measured under the measurement conditions of 2000 to 5000 times, and P _E , P ₀ , and P _0E are calculated from this spectrum.

Reference Example 1 liquid modified ethylene random copolymer produced [aluminoxane preparation] thoroughly purged with nitrogen flask _{400ml Al 2 (SO 4) 3} · 1
Charge 4H ₂ O 37g and toluene 125ml, cool to 0 ℃, dilute with toluene 125ml trimethylaluminum 500mmol.
Was dripped. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours. After the reaction, solid solution was separated by filtration, and toluene was removed from the filtrate to obtain 13 g of white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the catalyst component [B]
The m value shown therein was 14. It was redissolved in toluene and used for the polymerization.

[Polymerization] Using a continuous polymerization reactor of 4, purified toluene 4 / h
r, aluminoxane 20 mg atom / hr in terms of aluminum atom, dissolved in toluene, and bis (cyclopentadienyl) zirconium dichloride is continuously supplied at a rate of 0.16 mg atom / hr in terms of zirconium atom, and polymerized. At the same time, ethylene 200 / hr and propylene 500 / hr are continuously fed at a polymerization temperature of 40 ° C,
Polymerization was carried out under conditions of atmospheric pressure, residence time of 0.5 hours and polymer concentration of 26 g /. Water was added to the resulting polymer solution for deashing, toluene was removed, and the pressure was reduced at 120 ° C. for 12 hours to reduce ethylene content 45 mol%, propylene content 55 mol%, number average molecular weight 700, [η] 0.05. dl / g, w /
A liquid ethylene random copolymer having n1.80, iodine value of 35 and B value of 1.25 was obtained. The copolymer was used for modification in Example 1.

Reference Example 2 The procedure of Reference Example 1 was repeated except that the ethylene supply rate was changed to 100 / hr and the polymerization was carried out under the condition that the polymer concentration was 22 g /, and the ethylene content was 41 mol%.
Propylene content 59 mol%, number average molecular weight 620, [η] 0.0
A liquid ethylene random copolymer having 4 dl / g, w / n 1.78, an iodine value of 41 and a B value of 1.24 was obtained. The copolymer was used for modification in Example 2.

Reference Example 3 In Reference Example 1, the ethylene supply rate was 100 / hr, 1-butene was used instead of propylene, and the supply rate was 400 / h.
r, except that the polymerization temperature was changed to 22 ° C. and the polymerization was carried out under the condition that the polymer concentration was 25 g /,
Ethylene content 58 mol%, 1-butene content 42 mol%, number average molecular weight 1500, [η] 0.09 dl / g, w / n1.89, iodine value 1
7, a liquid ethylene-based random copolymer having a B value of 1.28) was obtained.

The copolymer was used for modification in Example 3.

Example 1 In a 400 ml glass flask thoroughly replaced with nitrogen, 0.5M was added.
42 ml of a THF solution of 9-BBN (9-borabicyclo [3.3.1] nonane) was added and cooled to 10 ° C. THF1 while keeping at 10 ℃
5.0 g of a liquid ethylene random copolymer (Reference Example 1) diluted with 07 ml was added dropwise over 5 minutes. After finishing the dropping, 5 at 23 ℃
Stirring was continued for hours. Then, it cooled at 0 degreeC, 3N NaOH aqueous solution was added, and also 35 g of hydrogen peroxide water 7.1g was dripped in 15 minutes. At that time, the temperature in the reaction system rose from 0 ° C to 22 ° C. Subsequently, the temperature was raised to 30 ° C., and the reaction was continued at that temperature for 2 hours. After the reaction was completed, the temperature was lowered to 15 ℃ and saturated K ₂ CO
50 ml of ₂ aqueous solution was added. Then, the polymer was extracted with hexane, hexane was further removed, and the residue was dried to give an ethylene content of 45 mol% and a propylene content of 55 mol%.
A colorless and transparent liquid hydroxylated modified ethylene random copolymer having a number average molecular weight of 720, w / n1.84, a hydroxyl group of 0.13 mol / 100 g, and [η] of 0.05 dl / g was obtained. The ¹³ C-NMR spectrum of the copolymer had α
No peaks based on β and βγ were detected.

Example 2 THF21 was placed in a 300 ml glass flask thoroughly purged with nitrogen.
ml and liquid ethylene-based random copolymer (Reference Example 2) 16.2
Then, 37.3 g of formic acid and subsequently 7.9 g of 35 wt% hydrogen peroxide solution were added at room temperature. Then, the temperature was raised to 40 ° C., and vigorous stirring was continued at that temperature for 8 hours. Next, the temperature was lowered to 0 ° C., and 205 ml of a 10 wt% Na ₂ SO ₃ aqueous solution was added dropwise over 15 minutes.
At that time, the temperature in the system rose from 0 ° C to 20 ° C. After further stirring at room temperature for 30 minutes, by extracting the polymer with hexane and drying, ethylene content 41 mol%, propylene content 59 mol%, number average molecular weight 670, w / n 1.76, hydroxyl group 0.15 mol / 100 g Copolymer, formate ester group
0.15 mol / 100g copolymer, [η] 0.05dl / g colorless transparent liquid hydroxylated modified ethylene random copolymer 1
7.1 g was obtained. No peaks due to αβ and βγ were detected in the ¹³ C-NMR spectrum of the copolymer.

Example 3 In a 100 ml glass flask thoroughly purged with nitrogen, THF 7 m
l and liquid ethylene random copolymer (Reference Example 3) 5.4 g
Then, 12.4 g of formic acid and 2.6 g of 35 wt% hydrogen peroxide solution were further added at room temperature. Then, the temperature was raised to 40 ° C., and vigorous stirring was continued at that temperature for 8 hours. Next, the temperature was lowered to room temperature, and 68 ml of a 10 wt% Na ₂ SO ₃ aqueous solution was added dropwise over 5 minutes. The operation at that time was performed in the same manner as in Example 2, with an ethylene content of 58 mol%, a 1-butene content of 42 mol%, a number average molecular weight of 1600,
w / n1.93, hydroxyl group 0.056 mol / 100 g copolymer,
Formic acid ester group 0.056 mol / 100g copolymer, [η] 0.10dl
5.5 g of colorless and transparent liquid hydroxylated modified ethylene-based random copolymer was obtained. Incidentally, ¹³ C-N of the copolymer
No peaks based on αβ and βγ were detected in the MR spectrum.

Evaluation Example 1 The performance of the liquid hydroxylated modified ethylene random copolymer of the present invention as a blending example for lubricating oil was evaluated by the following method.

(1) Preparation of sample Add poly-α-olefin oligomer A (Mob
Mobil SHF-1001 manufactured by il Chemical Co., Ltd.) 65 parts by weight and poly α
-Olefin Oligomer B (Syn from Chevron Chemical)
fluid6cst PAO) 35 parts by weight and mixed well with a glass rod, and then commercially available gear oil package type additive (Texaco
TC9535; S24.1%, P1.8%) and 2 parts by weight of the hydroxylated modified copolymers obtained according to Examples 1 and 3, respectively, and further stirred for two evaluations. A lubricating oil sample (I) was prepared. Also, in the same way,
A lubricating oil sample (II) for comparative evaluation was obtained by preparing without adding a hydroxylated modified copolymer.

(2) Evaluation method (i) Compatibility 100 ml of a sample was placed in a glass container with a diameter of 40 mm, left overnight, and then, using a spectrophotometer, the absorbance of light with a wavelength of 660 nm (cell: glass 50 mm, symmetry: hexane). Was measured and the transparency was examined.

<Evaluation> (Ii) Heating stability After the compatibility test, place the glass container with the sample in it at 80 ° C.
After being placed in the constant temperature bath for 1 month, it was taken out and allowed to cool to room temperature overnight, and the transparency was evaluated by the same method as in (i) above.

(Iii) Emulsification resistance The disappearance time of the emulsified layer was examined according to the method of JIS K 2520.

<Evaluation> (3) Evaluation result Evaluation Example 2 The performance of the liquid hydroxylated modified ethylene random copolymer of the present invention as a compounding agent for coating materials was evaluated by the following method.

(1) Preparation of sample Epoxy resin A (Mitsui Petrochemical Co., Ltd., Epomic R-140) 85 parts by weight, epoxy resin (Epomic R-094) 15 parts by weight and Example 2 After thoroughly mixing 3 parts by weight of the obtained hydroxylated modified copolymer, silica powder (Crystallite A- manufactured by Tatsumori Industry Co., Ltd.
1) 35 parts by weight was added and stirred well to obtain an epoxy coating (I) for evaluation. Further, in the same manner, a commercially available vegetable oil polymerization type anti-settling agent was used in place of the hydroxylated modified copolymer to prepare an epoxy coating (II) for comparative evaluation.

(2) Evaluation method (i) Pigment sedimentation rate A glass container with a cap having an inner diameter of 18 mm and a height of 45 mm has a height of 40 mm.
The sample was placed so that the thickness became mm, and the pigment sedimentation rate after standing for 1 month was determined by the following formula.

Where l ₀ : filling height of the pigment (40 mm) l: height of the upper clearing layer formed by the pigment settling due to static value for 1 month (mm) (ii) for 100 parts by weight of the coating material for sagging evaluation Modified polyamine-based curing agent (Mitsui Petrochemical Co., Ltd., Epomic Q-636) 2
8 parts by weight were added and mixed well, and a glass plate was coated, and immediately after that, it was fixed vertically and cured while standing still, and the maximum coating thickness without sagging was determined while observing the degree of sag.

(3) Evaluation result [Effect of the Invention] According to the present invention, a novel liquid hydroxylated modified ethylene random copolymer can be obtained.

The liquid hydroxylated modified ethylene random copolymer of the present invention exhibits excellent effects as a lubricant compounding agent and a paint compounding agent.

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Claims (3)

[Claims] 1. Ethylene and α-containing 3 to 20 carbon atoms.
A hydroxylated modified product of a liquid ethylene-based random copolymer composed of olefins, comprising: (i) 10 to 85 mol% of ethylene component of the liquid hydroxylated-modified ethylene-based random copolymer and α-
The olefin component is in the range of 15 to 90 mol%, (ii) two adjacent tertiary groups in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid hydroxylated modified ethylene random copolymer. Α based on methylene chains between carbon atoms
No signals of β and βγ are observed, (iii) Vapor pressure osmometer (VP) of the liquid hydroxylated modified ethylene random copolymer
Number average molecular weight (n) measured by O) is 200 to 10,000
And (iv) the hydroxyl group is bonded to a carbon atom derived from ethylene or α-olefin which is located at the molecular end of the liquid ethylene random copolymer, and the content ratio of the hydroxyl group is A liquid hydroxylated modified ethylene random copolymer, characterized by being in the range of 0.01 to 1 mol per 100 g of liquid hydroxylated modified random ethylene copolymer. 2. Ethylene and α-containing 3 to 20 carbon atoms.
A hydroxylated modified product of a liquid ethylene-based random copolymer composed of olefins, comprising: (i) 10 to 85 mol% of ethylene component of the liquid hydroxylated-modified ethylene-based random copolymer and α-
The olefin component is in the range of 15 to 90 mol%, (ii) two adjacent tertiary compounds in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid hydroxylated modified ethylene random copolymer. Α based on methylene chains between carbon atoms
No signals of β and βγ are observed, (iii) Vapor pressure osmometer (VP) of the liquid hydroxylated modified ethylene random copolymer
Number average molecular weight (n) measured by O) is 200 to 10,000
And (iv) the hydroxyl group is bonded to a carbon atom derived from ethylene or α-olefin which is located at the molecular end of the liquid ethylene random copolymer, and the content ratio of the hydroxyl group is A compounding agent for a lubricating oil comprising a liquid hydroxylated modified ethylene random copolymer characterized by being in the range of 0.01 to 1 mol per 100 g of the liquid hydroxylated modified ethylene random copolymer. 3. Ethylene and α-containing 3 to 20 carbon atoms.
A hydroxylated modified product of a liquid ethylene-based random copolymer composed of olefins, comprising: (i) 10 to 85 mol% of ethylene component of the liquid hydroxylated-modified ethylene-based random copolymer and α-
The olefin component is in the range of 15 to 90 mol%, (ii) two adjacent tertiary groups in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid hydroxylated modified ethylene random copolymer. Α based on methylene chains between carbon atoms
No signals of β and βγ are observed, (iii) Vapor pressure osmometer (VP) of the liquid hydroxylated modified ethylene random copolymer
Number average molecular weight (n) measured by O) is 200 to 10,000
And (iv) the hydroxyl group is bonded to a carbon atom derived from ethylene or α-olefin which is located at the molecular end of the liquid ethylene random copolymer, and the content ratio of the hydroxyl group is A compounding agent for paints comprising a liquid hydroxylated modified ethylene random copolymer, characterized by being in the range of 0.01 to 1 mol per 100 g of the liquid hydroxylated modified random ethylene copolymer.