JPH0791338B2 - Liquid epoxidized modified ethylene random copolymer and its use - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid epoxidation-modified ethylene-based random copolymer and its use. More specifically, the present invention provides a liquid epoxidized modified ethylene random copolymer capable of exhibiting excellent performance as a lubricant compound, a paint compound, a resin modifier, and the like, and a use thereof. Is.

[Prior Art] Various additives are added to lubricating oils such as gear oils, engine oils, greases, metalworking oils, and release agents 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 in a state of being simply dispersed in the base oil without being dissolved. Recently, the replacement of conventional mineral oils with conventional lubricating oils to synthetic lubricating oils represented by olefin polymer oils is progressing. However, with these synthetic lubricating oils, the above tendency is becoming clearer and 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 that can improve 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, but depending on the purpose of use, However, it is hard to say that they are showing sufficient performance. Therefore, also in the field of paint application, there is a strong demand for a paint compound having 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 agents capable of exhibiting further excellent performance. As a result of diligent studies, the inventors have found that the liquid epoxidized modified ethylene random copolymer having a specific property is a novel substance, and that the liquid epoxidized modified ethylene 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 epoxidation-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 epoxidized modified ethylene random copolymer and a compounding agent for a coating comprising the liquid epoxidized modified ethylene random copolymer.

[Means for Solving Problems] According to the present invention, an epoxidized 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 epoxidized modified ethylene random copolymer is in the range of 10 to 85 mol% and the α-olefin component is in the range of 15 to 90 mol%, and (ii) the liquid epoxidized modified ethylene random copolymer. No signal of αβ and βγ based on a methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer is observed in the ¹³ C-NMR spectrum of the copolymer, (iii) the liquid epoxidation The modified ethylene random copolymer has a number average molecular weight (n) measured by a vapor pressure osmometer (VPO) of 200 to 10,000, and (iv) an epoxy group It is located at the molecular end of the liquid ethylene random copolymer, and is characterized in that the content ratio of epoxy groups is in the range of 0.01 to 0.5 mol per 100 g of the liquid epoxidation-modified ethylene random copolymer. A liquid epoxidation-modified ethylene-based random copolymer is provided as a substance invention, and further, a lubricating oil compounding agent comprising the liquid epoxidation-modified ethylene-based random copolymer and the liquid epoxidation-modified ethylene-based random copolymer are used. The following coating compound is provided as a use invention.

The liquid epoxidized modified ethylene random copolymer of the present invention is an epoxidized modified product of a liquid ethylene random copolymer composed of ethylene and α-olefin having 3 to 20 carbon atoms. Is formed via a carbon-carbon unsaturated bond derived from ethylene or α-olefin located at the molecular end of the liquid ethylene random copolymer, and is a product in which at least one epoxy group is bonded, For example, the pour point measured according to JIS K-2269 is 50 ° C. or less, and 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 epoxidized modified ethylene random copolymer is 10 to 85 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%.
The content of mol% and α-olefin component is 15 to 90.
It is in the range of mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%. Even when the content of the ethylene component of the liquid epoxidized modified random copolymer is less than 10 mol% and the content of the α-olefin component is more than 90 mol%, the liquid epoxidized modified ethylene is also used. Even if the ethylene content of the random copolymer is more than 85 mol% and the content of the α-olefin component is less than 15 mol%, the performance of the compounding agent for lubricating oil or the compounding agent for coating composition is deteriorated. Like

^{13 of the} liquid epoxidized modified ethylene-based random copolymer
Αβ and β based on a methylene chain between two adjacent tertiary carbon atoms in the copolymer backbone in the C-NMR spectrum
No γ signal is observed.

The liquid epoxidized modified ethylene random copolymer has a number average molecular weight (n) measured by a vapor pressure osmometer (VPO) of 200 to 10000, preferably 300 to 8000, particularly preferably 500 to 5000. In range. Even when the number average molecular weight of the liquid epoxidized modified ethylene random copolymer is smaller than 200 or larger than 10,000, the performance as a lubricant blending agent or a paint blending agent is deteriorated. Also, 13
The intrinsic viscosity [η] measured in decalin at 5 ° C is in the range of 0.01 to 0.4 dl / g, preferably 0.02 to 0.35 dl / g, particularly preferably 0.03 to 0.3 dl / g.

The molecular weight distribution (w / n) of the liquid epoxidized modified ethylene random copolymer measured by gel permeation chromatography (GPC) is 1.1 to 4.0, preferably 1.2 to 3.0, and particularly preferably 1.3 to 2.5.
Is the range.

The content ratio of epoxy groups in the liquid epoxidized modified ethylene random copolymer is 0.01 to 0.5 mol, preferably 0.015 to 0.3 mol, and particularly preferably 0.02 to 100 g of the liquid epoxidized modified ethylene random copolymer.
It is in the range of 0.2 mol. The content ratio of the epoxy group in 100 g of the liquid epoxidized modified ethylene random copolymer is 0.
When it is less than 01 mol, the performance as a lubricant compounding agent or a paint compounding agent is deteriorated, and the content ratio of the epoxy group in 100 g of the liquid epoxidized modified ethylene random copolymer is less than 0.5 mol. When the amount is large, the performance as a lubricant compound or a paint compound becomes poor.

The ethylene-based random copolymer constituting the liquid epoxidized modified ethylene-based random copolymer is a liquid ethylene-based random copolymer formed from ethylene and α-olefin having 3 to 20 carbon atoms. Component (a) is in the range of 10 to 85 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%,
The α-olefin component (b) is 15 to 90 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 90 mol%.
It is in the range of 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 10000, 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 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-olefin unit at one end. It is a mixture of those having a carbon-carbon unsaturated bond based on the above and those having no carbon-carbon unsaturated bond at one end of the copolymer molecule.

When used in a modification reaction to obtain the liquid epoxidized modified ethylene random copolymer of the present invention, it is preferred that one end of the copolymer molecule is carbon / carbon unsaturated bond.

Specific examples of the α-olefin component having 3 to 20 carbon atoms, which is a constituent component 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-1,4-hexadiene, 5-ethylidene-2-norbornene, di Examples include cyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, and 5,8-endomethylenehexahydronaphthalene.

In the ¹³ C-NMR spectrum of the liquid ethylene random copolymer, αβ and βγ signals based on a methylene chain between two adjacent tertiary carbon atoms in the copolymer main chain are not observed.

For example, in a copolymer of ethylene and 1-hexene,
Combine the following: 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 left 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): [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE is the α-olefin / ethylene chain of the entire dyad 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 of satisfying (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 The random copolymer of the type is a copolymer of (A) a zirconium compound having a group having a conjugated π electron as a ligand, and (B) an aluminoxane catalyst in the presence of ethylene and 3 to 20 carbon atoms. It can be prepared by copolymerizing α-olefin and optionally a non-conjugated polyene.

The liquid ethylene-based random copolymer is disclosed in Japanese Patent Application Laid-Open No. 61-221207 and Japanese Patent Application No. 60-259835.
Specifically, [A] a compound of a transition metal selected from the group consisting of groups IVb, Vb and VIb of the periodic table, and [B] the general formula (III) or Formula (IV) (In the formula, R represents a hydrocarbon group and m is preferably an integer of 5 or more.) In the method of copolymerizing ethylene and α-olefin in the presence of a catalyst formed from: It can be manufactured by selecting appropriate conditions.

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

(1) A method of reacting the liquid ethylene random copolymer with a mixture of an organic acid such as formic acid and acetic acid and hydrogen peroxide.

In the reaction, sodium hydrogen phosphate, sodium carbonate, sodium hydrogen carbonate and the like are preferably made to coexist as a buffer.

(2) A method of reacting the liquid ethylene-based random copolymer with an organic peroxide such as m-chloroperbenzoic acid.

More specifically, in the reaction of (1), hydrogen peroxide 1
The amount of the organic acid is 2 to 50 mol, preferably 5 to 25 mol, and the reaction temperature is 0 to 60 ° C., preferably 10 to 50 ° C., and the time required for this is 0.5 to 20 hours, preferably 1 To 10 hours.
The amount of the hydrogen peroxide added is 1 to 10 mol, preferably 2 to 5 mol, and the amount of the organic acid added is 1 mol based on 1 mol of the unsaturated bond of the liquid ethylene random copolymer.
10 to 100 mol, preferably 20 to 50 mol,
The amount of buffer added is 0.05 to 0.1 per mol of the organic acid.
It is 5 mol, preferably in the range of 0.1 to 0.3. Also,
The reaction temperature is 0 to 100 ° C, preferably 20 to 80 ° C
And the time required for this is in the range of 1 to 30 hours, preferably 2 to 20 hours. Further, the concentration of the polymer is in the range of 5 to 400 g / l, preferably 10 to 300 g / l.

In the method of (2), the addition amount of the organic peroxide is 1 with respect to 1 mol of the unsaturated bond of the liquid ethylene random copolymer.
To 10 mol, preferably 1 to 5 mol. 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 / l, preferably 10 to 300 g / l.

Examples of the solvent used for producing the liquid epoxidized modified ethylene random copolymer of the present invention include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and ether solvents such as ethyl ether, tetrahydrofuran and dioxane. it can.

The liquid epoxidized 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, mineral oil lubricating base oil, olefin-based synthetic lubricating oil such as olefin polymer or copolymer oil,
It can be used for any of synthetic lubricating oils such as silicone synthetic lubricating oil and ester synthetic lubricating oil. The mixing ratio of the liquid epoxidized 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 the lubricating oil, in addition to the liquid epoxidized modified ethylene random copolymer,
Various additives known to be incorporated into lubricating oils can be incorporated. 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 epoxidized modified ethylene-based random copolymer is used for gear oil, engine oil, grease, metalworking oil, release agent and the like.

The liquid epoxidized modified ethylene random copolymer of the present invention can be used as a paint compounding agent. As the coating material to which the liquid epoxidized 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 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 mixing ratio of the liquid epoxidation-modified ethylene-based random copolymer is usually 100 parts by weight of the coating film forming element component in the paint.
It is in the range of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight. In the coating material containing the liquid epoxidized modified ethylene random copolymer of the present invention, various other conventionally known additives such as pigments, solvents (in the case of solvent type coating materials), dispersion media (emulsion) 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 epoxidized modified ethylene random copolymer of the present invention has various uses in addition to the lubricating oil compounding agent and the paint compounding agent, such as a dispersant for a solid additive to a lubricating oil, a rubber or a resin. Processing aids, 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 agents and modifiers for adhesives.

[Examples] Next, the present invention will be specifically described with reference to Examples.

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

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

(2) Method of measuring 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) is measured according to “Gel Permeation Chromatography” published by Maruzen by Takeuchi 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 the 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] (b) Collect a sample in an Erlenmeyer flask together with a toluene solvent so that the concentration of the sample becomes 0.1 wt%.

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

[GPC conditions] It was carried out under the following conditions.

(A) Device: Waters (150C-ALC / GPC) (b) Column: Toyo Soda (G4000H, G3000H, G2000H) (C) Temperature: 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.

[In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE is the α-olefin / ethylene chain of the entire dyad chain. The B value is an index showing the distribution state of each monomer component in the copolymer, and G value of GJRay (Macromolecules, 10 , 773 (19
77), JCRandall (Macromolecules, 15 , 353 (1982),
J. Polymer Science, Polymer Physics.Ed., 11 , 275 (197
3)), K. Kimura (Polymer, 25 , 441 (1984)) and others, and is calculated by determining P _E , P _O and P _OE defined above. 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 integrations is measured under the measurement conditions of 2000 to 5000 times, and it is calculated by _obtaining P _E , P _O , and P _OE from this spectrum.

Reference Example 1 Production of Liquid Modified Ethylene Random Copolymer [Preparation of Aluminoxane] Al ₂ (SO ₄ ) ₃ · 14H _{2 was} added to a 400 ml flask which was sufficiently replaced with nitrogen.
37 g of O and 125 ml of toluene were charged and after cooling to 0 ° C., 500 mmol of trimethylaluminum diluted with 125 ml of toluene was added dropwise. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the liquid to obtain 13 g of a white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in the catalyst component [B] was 14. It was redissolved in toluene and used for the polymerization.

[Polymerization] Purified toluene was added at 4 l / hr using a 4 l continuous polymerization reactor.
Aluminoxane is 20 mg atom / hr in terms of aluminum atom, and bis (cyclopentadienyl) zirconium dichloride dissolved in toluene is continuously supplied at a rate of 0.16 mg atom / hr in terms of zirconium atom,
At the same time in the polymerization vessel ethylene 110l / hr, propylene 5
Supply continuously at a rate of 00l / hr, polymerization temperature 30 ℃, normal pressure,
Polymerization was carried out under the condition that the residence time was 0.5 hours and the polymer concentration was 23 g / l. Water was added to the resulting polymer solution for deashing, toluene was removed, and the mixture was dried under reduced pressure at 120 ° C for 12 hours to give an ethylene content of 42 mol% and a propylene content of 58%.
Mol%, number average molecular weight 1100, [η] 0.07dl / g, w / n
A liquid ethylene-based random copolymer having 1.78, an iodine value of 23 and a B value of 1.26 was obtained.

The copolymer was used for modification in Example 1.

Reference Example 2 Polymerization was carried out in the same manner as in Reference Example 1 except that the ethylene feed rate was changed to 140 l / hr, the polymerization temperature was changed to 45 ° C., and the polymerization was carried out under the conditions that the polymer concentration was 26 g / l. And then
Ethylene content 55 mol%, propylene content 45 mol%, number average molecular weight 600, [η] 0.04 dl / g, w / n1.81, iodine value 4
A liquid ethylene-based random copolymer having a B value of 1.27 was obtained.

The copolymer was used for modification in Example 2.

Reference Example 3 Purified toluene (500 ml) and 1-hexene (500 ml) were charged into a glass autoclave having an internal volume of 1.5 l equipped with a cooling tube, and a mixed gas of ethylene and nitrogen (100 l / hr and 200, respectively)
(l / hr) was circulated and the temperature was raised to 45 ° C. After that, 5.0 mg of aluminoxane in terms of aluminum atom, bis (cyclopentadienyl) dissolved in toluene
Zirconium dichloride 0.02 in terms of zirconium atom
Polymerization was initiated by charging milligram atom. Polymerization was carried out at 50 ° C. for 1 hour while continuously supplying the above mixed gas. Subsequent operations were carried out in the same manner as in Reference Example 1, with an ethylene content of 65 mol%,
1-hexene content 35 mol%, number average molecular weight 950, [η]
105 g of a liquid ethylene random copolymer having 0.06 dl / g, w / n 1.75, an iodine value of 26 and a B value of 1.28 was obtained.

The copolymer was used for modification in Example 3.

Example 1 To a 200-ml glass flask thoroughly purged with nitrogen was charged 54 ml of toluene and 5.4 g of a liquid ethylene random copolymer (Reference Example 1), and the temperature was raised to 70 ° C. 1.1 g of m-chloroperbenzoic acid dissolved in 33 ml of toluene while maintaining at 70 °
Was added dropwise over 3 hours. Further, after reacting at 70 ° C for 1 hour, it was cooled to 25 ° C, then 1.7 g of Na ₂ SO ₃ was added, and the temperature was changed to 25 ° C.
The stirring was continued for 30 minutes. Then add 5 wt% of polymer solution
After washing with NaHCO ₃ aqueous solution and water, removing toluene and drying, ethylene content 42 mol%, propylene content 58 mol%, number average molecular weight 1100, w / n1.80, epoxy group 0.09 mol / 100 g Combined, [η] 0.07 dl / g colorless and transparent liquid epoxidized modified ethylene random copolymer
5.4 g was obtained. Incidentally, no peaks due to αβ and βγ were detected in the ¹³ C-NMR spectrum of the copolymer.

Example 2 A 100 ml glass flask thoroughly purged with nitrogen was charged with acetic acid 1
6.2 g, concentrated sulfuric acid 0.19 ml and 35 wt% hydrogen peroxide water 2.6 g were added, and the mixture was stirred at room temperature for 4 hours. Then, 2.3 g of sodium acetate trihydrate was added, and the mixture was stirred at room temperature for 20 minutes. Next, after adding 7.2 g of Na ₂ HPO ₄ and stirring for 5 minutes, 7 ml of toluene
And 5.4 g of a liquid ethylene-based random copolymer (Reference Example 2) were added. Subsequently, the temperature was raised to 40 ° C. and stirring was continued for 17 hours.
Then the polymer solution was transferred into 100 ml of toluene. Subsequent operations were carried out in the same manner as in Example 1, ethylene content 55 mol%, propylene content 45 mol%, number average molecular weight 610, w /
n1.82, epoxy group 0.15 mol / 100 g copolymer, [η] 0.
As a result, 5.2 g of a colorless transparent liquid epoxidized modified ethylene-based random copolymer of 04 dl / g was obtained. The ¹³ C-
No peaks based on αβ and βγ were detected in the NMR spectrum.

Example 3 The procedure of Example 1 was repeated except that the liquid ethylene random copolymer of Reference Example 3 was used, and the ethylene content was 65 mol%, the 1-hexene content was 35 mol%, and the number average molecular weight was 1. 970, w / n1.82, epoxy group 0.09 mol / 100 g copolymer, and colorless transparent liquid epoxidized modified ethylene random copolymer 5.3 g having [η] 0.07 dl / g were obtained. The copolymer ¹³ C-NMR spectrum shows αβ, β
No γ-based peak was detected.

Evaluation Example 1 The performance of the liquid epoxidized modified ethylene random copolymer of the present invention as a compounding agent 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 (Synflu manufactured by Chevron Chemical
id 6cst PAO) 35 parts by weight, mixed well with a glass rod, and then 1 part by weight of a commercially available gear oil package type additive (Texaco, TC9535; S24.1%, P1.8%) and each Two parts of lubricating oil samples (I) for evaluation were prepared by adding 3 parts by weight of the epoxidized modified copolymers obtained in Examples 1 and 3 and further stirring. A lubricating oil sample (II) for comparative evaluation was prepared in the same manner as above but without the addition of the epoxidized 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.

(Ii) Heating stability After the compatibility test, the glass container containing the sample is kept 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) Anti-emulsification property The disappearance time of the emulsified layer was examined according to the method of JIS K2520.

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

(1) Preparation of sample Epoxy resin A (manufactured by Mitsui Petrochemical Co., Ltd., Epomic R-140) 85 parts by weight, epoxy resin (Epomic R-094) 15 parts by weight and Example 2 were obtained. After thoroughly mixing 5 parts by weight of the epoxidized modified copolymer,
In addition to this, silica powder (Crystallite A-1 made by Tatsumori Industry Co., Ltd.) 35
A weight part was added and the mixture was further stirred 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 epoxidized 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 put in such a manner that the pigment precipitation rate after standing for 1 month was determined by the following formula.

Here, l ₀ : Height of filling of pigment (40 mm) l: Height of upper clearing layer formed by sedimentation of pigment by standing for 1 month (mm) (ii) Sagging property based on 100 parts by weight of paint Modified polyamine-based curing agent (Mitsui Petrochemical Co., Ltd., Epomic Q-636) 2
8 parts by weight were added and mixed well, and the mixture was coated on a glass plate. Immediately after that, it was fixed vertically and cured while standing still.

(3) Evaluation result EFFECTS OF THE INVENTION According to the present invention, a novel liquid epoxidized modified ethylene random copolymer can be obtained.

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

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C10M 143/08 143/18 9159-4H // C10N 40:00 40:04 40:20

Claims (3)

[Claims] 1. Ethylene and α-containing 3 to 20 carbon atoms.
An epoxidized modified product of a liquid ethylene-based random copolymer composed of olefin, comprising: (i) 10 to 85 mol% of ethylene component of the liquid epoxidized modified ethylene-based random copolymer and α-olefin component. It is in the range of 15 to 90 mol%, (ii) between two adjacent tertiary carbon atoms in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid epoxidized modified ethylene random copolymer. No αβ and βγ signals based on the methylene chain of (3) the number average molecular weight (n) of the liquid epoxidation-modified ethylene-based random copolymer measured by a vapor pressure osmometer (VPO) is 200. And (iv) the epoxy group is located at the molecular end of the liquid ethylene random copolymer, and the content of the epoxy group is A liquid epoxidized modified ethylene random copolymer is characterized by being in the range of 0.01 to 0.5 mol per 100 g of liquid epoxidized modified ethylene random copolymer. 2. Ethylene and α-containing 3 to 20 carbon atoms.
An epoxidized modified product of a liquid ethylene-based random copolymer composed of olefin, comprising: (i) 10 to 85 mol% of ethylene component of the liquid epoxidized modified ethylene-based random copolymer and α-olefin component. It is in the range of 15 to 90 mol%, (ii) between two adjacent tertiary carbon atoms in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid epoxidized modified ethylene random copolymer. No αβ and βγ signals based on the methylene chain of (3) the number average molecular weight (n) of the liquid epoxidation-modified ethylene-based random copolymer measured by a vapor pressure osmometer (VPO) is 200. And (iv) the epoxy group is located at the molecular end of the liquid ethylene random copolymer, and the content of the epoxy group is A compounding agent for a lubricating oil comprising a liquid epoxidized modified ethylene random copolymer, which is characterized by being in the range of 0.01 to 0.5 mol per 100 g of the liquid epoxidized modified ethylene random copolymer. 3. Ethylene and α-containing 3 to 20 carbon atoms.
An epoxidized modified product of a liquid ethylene-based random copolymer composed of olefin, comprising: (i) 10 to 85 mol% of the ethylene component of the liquid hydroxylated-modified ethylene-based random copolymer and α-olefin component. It is in the range of 15 to 90 mol%, (ii) between two adjacent tertiary carbon atoms in the main chain of the copolymer in the ¹³ C-NMR spectrum of the liquid hydroxylated modified ethylene random copolymer. Α based on the methylene chain of
No β and βγ signals are observed, and (iii) the number average molecular weight (n) of the liquid epoxidized modified ethylene random copolymer measured with a vapor pressure osmometer (VPO) is in the range of 200 to 10,000. And (iv) the epoxy group is located at the molecular end of the liquid ethylene-based random copolymer, and the content of the epoxy group is 0.01 to 0.5 mol per 100 g of the liquid epoxidized modified ethylene-based random copolymer. The compounding agent for paints, which comprises a liquid epoxidized modified ethylene-based random copolymer characterized by the following.