JPS61246215A - Liquid modified ethylene random copolymer - Google Patents

Abstract

PURPOSE:The title copolymer useful as a modifying agent (aid) for resins or silicon-containing rubbery polymers, prepared by graft-copolymerizing an unsaturated silane compound component with an ethylene random copolymer comprising ethylene and an alpha-olefin. CONSTITUTION:0.2-300pts.wt. 2-20c unsaturated silane compound component (e.g., trimethoxyvinylsilane) is graft-copolymeized with 100pts.wt. ethylene ran dom copolymer comprising 25-75mol% ethylene and 75-25 mol% 3-20C alpha-olefin (e.g., propylene) at 120-200 deg.C for 30 min-8 hr in the presence of 0.04-15pts.wt. radical initiator (e.g., di-tert-butyl peroxide) to obtain the title copolymer of an intrinsic viscosity [eta] as determined in decalin at 135 deg.C of 0.01-1.5 dl/g, a number-average MW of 200-10,000 and a MW distribution (M'w/M'n) as determined by a GPC method of 1.2-4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid modified ethylene random copolymer. More specifically, it exhibits excellent performance in applications such as a modifier for resins or silicon-containing rubber-like polymers, a modification aid, a lubricating oil additive, and a dispersion aid for aqueous dispersions of resins or rubber-like polymers. The present invention relates to a liquid modified ethylene random copolymer that can be

[Conventional technology]

Conventionally, modified olefin polymers, which are obtained by graft copolymerizing various unsaturated silane compound components onto high molecular weight olefin polymers such as polyethylene and polypropylene, have been used as resin modifiers, adhesive agents, and other uses. ing.

However, since these modified olefin polymers have a high molecular weight and are solid, sufficient performance may not be obtained depending on the field of use. In addition, modified olefin polymers obtained by graft copolymerizing an unsaturated silane compound component to olefin polymers such as polybutene and polyisobutylene are disclosed in JP-A-53-144995 and JP-A-54-
No. 83089, Japanese Unexamined Patent Publication No. 149741/1983,
It has been proposed in JP-A No. 54-28386, etc., that the modified low molecular weight olefin polymer is converted into a rubber-like polymer,
In particular, it has excellent performance when used in fields such as a modifier for silicon-containing rubbery polymers, a modification aid, a lubricating oil additive, and a dispersion aid for aqueous dispersions of resins or rubbery polymers. Not shown. In particular, in the field of compounding technology for rubber-like polymers, weather resistance, weather resistance, and Attempts have been made to provide a rubbery polymer composition that has excellent aging resistance and excellent rubber elasticity, but the drawback is that simply blending both of them results in a decrease in the mechanical properties of the resulting composition. Usually, a modifying agent is added to improve this drawback. Even if the conventionally known modified low molecular weight olefin polymer is blended as the modification aid, the modification effect is extremely small.

[Problem that the invention seeks to solve]

The present inventors have investigated modified low molecular weight ethylene copolymers that are excellent as modifiers for various resins or rubbery polymers, especially as modifiers for silicon-containing rubbery polymer compositions. A liquid modified ethylene-based random copolymer with the properties of The inventors have discovered that a polymer composition can be obtained, and have arrived at the present invention. Also.

The liquid modified ethylene random copolymer of the present invention also exhibits excellent performance in other uses such as a lubricating oil additive and a dispersion aid for aqueous dispersions of resins or rubbery polymers.

[Summary of the invention]

The present invention uses ethylene and α-
A liquid modified ethylene random copolymer obtained by graft copolymerizing an unsaturated silane compound component unit having 3 to 10 carbon atoms onto an ethylene random copolymer composed of an olefin, comprising: (1) the ethylene random copolymer; The ethylene component of the random copolymer is 25 to 75 mol% and α-
The olefin component is in the range of 25 to 75 mol%, (ii) The grafting ratio of the unsaturated silane compound component is in the range of 0.2 to 300 parts by weight based on 100 parts by weight of the ethylene random copolymer. and aID of the liquid modified ethylene random copolymer.
Intrinsic viscosity [ma] measured in decalin at 35℃ is 0.0
1 to 1.5617 g.

[Means and effects for solving the problems] The liquid modified ethylene random copolymer of the present invention is an ethylene random copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms; It is a modified ethylene-based random copolymer obtained by graft copolymerization of an unsaturated silane compound component having 3 to 10 carbon atoms. The grafting ratio of the unsaturated silane compound component of the liquid modified ethylene-based random copolymer is 0.2 to 300 parts by weight per 100 M parts of random copolymer,
Preferably it is in the range of 1 to 200 parts by weight. Even if the grafting ratio of the unsaturated silane compound component is less than 0.2 parts by weight or more than 300 parts by weight, when it is blended as a modifier for a silicon-containing rubbery polymer composition, the composition The effect of improving the mechanical properties of objects becomes inferior.

Specifically, the unsaturated silane compound component unit having 2 to 20 carbon atoms which is a graft copolymerization component of the liquid modified ethylene random copolymer includes trimethoxyvinylsilane, triethoxyvinylsilane, trimethylvinylsilane, diethylmethylvinylsilane. , diacetoxymethylvinylsilane, jetoxymethylvinylsilane, ethoxydimethylvinylsilane, triacetoxyvinylsilane, tris(2-methoxyethoxy)vinylsilane,
Examples include monovinylsilanes such as triphenylvinylsilane and triphenoxyvinylsilane, and polyvinylsilanes such as diphenyldivinylsilane and allyloxydimethylvinylsilane.

The intrinsic viscosity [η] of the liquid modified ethylene random copolymer measured in decalin at 135°C is 0.01 to 1.
．． 5 (51/g, preferably 0.02 to 1.Od
The range is J/I. Even if the intrinsic viscosity [ma] of the liquid modified ethylene random copolymer becomes smaller than 0.01 C1l/g or larger than 1.5617 g, it can be used as a modification aid for silicon-containing rubbery polymer compositions. If it is blended, the effect of improving the mechanical properties of the composition will be inferior.

Further, the number average molecular weight of the liquid modified ethylene random copolymer is usually 300 to 1oooo.

Preferably it is in the range of 500 to 8000.

The ethylene random copolymer constituting the liquid modified ethylene random copolymer is a liquid ethylene random copolymer formed from ethylene and an α-olefin having 3 to 20 carbon atoms.

The ethylene component (b) should be in the range of 25 to 75 mol%, preferably 30 to 70 mol% of the α-
) of the olefin component ranges from 25 to 75 mol%, preferably from 30 to 70 mol% [here @, )
The total of component and component (b) is 100 mol%]. The intrinsic viscosity [η] of the liquid ethylene random copolymer measured in decalin at 135°C is usually 0.01 to 1.
5 C1l/I, preferably 0.02 to 1.0 (
The number average molecular weight is usually in the range of 200 to 1oooo, preferably 400 to 8000, and the molecular weight distribution (MW
/Mn) is usually 1.2 to 4. Preferably 1.2
It is in the range of 3 to 3. The liquid ethylene-based random copolymer is mostly liquid at room temperature, and may be semi-solid at room temperature when the content of ethylene component is high and the intrinsic viscosity [ma] is high. In this case, the crystallinity of the ethylene random copolymer measured by X-ray diffraction is usually 5% or less, preferably 2% or less. The content of the ethylene component in the liquid ethylene random copolymer is 25
The content of α-olefin component is less than mol% and the content of α-olefin component is 7.
Even if the content of the ethylene component is greater than 75 mol%, and even if the content of the α-olefin component is less than 25 mol%, the liquid modified ethylene random copolymer is If it is blended as a modifier or a modifier for a rubber-like polymer composition containing it, the effect of improving the mechanical properties of the composition will be poor. Specifically, the α-olefin component having 3 to 20 carbon atoms, which is a constituent component of the liquid ethylene-based random copolymer, includes:
Propylene, 1-ptecy, 1-hexene, 4-methyl-
1-pentene, 3-methyl-1-pentene, 1-octene% 1-7 cen.

1-dodecene, 1-tetradecene, 1-hexadecene,
Examples include 1-octadecene and 1-eicosene. The liquid ethylene random copolymer can be prepared by the method proposed by the present applicant in JP-A-57-123205. The liquid modified ethylene random copolymer of the present invention can be prepared by the liquid ethylene random copolymer The reaction can be produced by reacting the copolymer with the unsaturated silane compound component in the presence of a radical initiator.The reaction can be carried out in the presence of a solvent or in the absence of a solvent. You can also do that. An example of the reaction method is a method in which the unsaturated silane compound and the radical initiator are continuously or intermittently supplied to a heated liquid ethylene-based random copolymer while stirring. The proportion of the unsaturated silane compound supplied to the graft reaction is usually 0.2 to 3 parts by weight per 100 parts by weight of the liquid ethylene random copolymer.
The proportion of the radical initiator is usually 0.04 to 15 parts by weight, preferably 0.00 parts by weight, preferably 0.00 parts by weight, preferably 1 to 200 parts by weight, based on 100 parts by weight of the liquid ethylene random copolymer. The temperature during the reaction is 120 to 200°C, preferably 130 to 180°C, and the time required for the reaction is usually 30 minutes to 80 hours, preferably 1 to 10 parts by weight.
50 hours.

Organic peroxides are usually used as radical initiators for the grafting reaction, and those whose decomposition temperature is in the range of 150 to 270°C at which their half-life is 1 minute are particularly preferred. , organic bersesters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert
-butylperoxide, 2,5-dimethyl-2,5-di(beroxybenzoate)hexyne-3,1,4-bis(tert-butylperoxyimprovil)benzene, lauroylperoxide, tart-butylberacetate, 2. 5-dimethyl-2,5-di(tert-
butylperoxy)hexyne-3% 2.5-dimethyl-
2,5-di(tart-butylperoxy)hexane,
tert-7'tilberbenzoate, tert-
Butylberphenylace7- ) s je r j
-butylberysoptile) star t-7”
Chilperu 8eC-octoate, tert-butylvelpivalate, cumylvelpivalate and tert-
Bunalberg diethyl acetate is mentioned.

The use of the rubber-like polymer composition of the liquid modified ethylene random copolymer of the present invention as a modification aid will be explained.

The rubbery polymer composition includes an ethylene/α-olefin-based or ethylene/α-olefin/diene-based elastic copolymer (T), a silicon-containing rubbery polymer 0, and the liquid modified ethylene-based random copolymer. 0 and other components 0. The proportion of the rubbery polymer (1) to 100 parts by weight of the elastic copolymer is usually 2 to 50 parts by weight, preferably 5 to 40 parts by weight, and the liquid modified ethylene random copolymer ( The blending ratio of Q is usually 1 to 60 parts by weight, preferably 2 to 20 parts by weight.

Elastic copolymer (2) blended into the rubbery polymer composition
Examples include ethylene-propylene copolymer, ethylene-propylene copolymer,
Crystallinity of 1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/1-hexene copolymer, ethylene/1-decene copolymer, etc. is 0 to 10. % of ethylene/α-olefin elastic copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene-2-norbornene combined, ethylene/propylene/1,4-hexadiene The diene component content of copolymers, ethylene/1-butene/dicyclopentadiene copolymers, ethylene/1-butene/5-ethylidene-2-norbornene copolymers, etc. is usually in the range of 0.5 to 10 mol%. Examples include ethylene/α-olefin/diene elastic copolymers.

Specific examples of other components blended into the rubbery polymer composition include crosslinking agents, crosslinking accelerators, heat stabilizers, oxidation stabilizers, stabilizers such as anti-aging agents, and fillers. be able to. The blending ratio of these components is arbitrary.

Specific examples of the crosslinking agent blended into the rubbery polymer composition include peroxide, sulfur, sulfur such as sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Compounds, metal compounds such as magnesium oxide, zinc white, and red lead can be mentioned.

Sulfur is usually 0.05 to 10 parts by weight per 100 parts by weight of the rubber component consisting of component (8) and component ◎.
It is preferably used in an amount of 0.1 to 5 parts by weight.

Further, a crosslinking accelerator can be used if necessary. Examples of crosslinking accelerators include N-cyclohexyl-2-, henzothiazole-sulfene 7m), N-oxydiethylene-2-
Benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole-sulfenamide,
2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2
Thiazole series such as ゜6-diethyl-4-morpholinothio)benzothiazole and benzothiazyl-disulfide; diphenylguanidine, triphenylguanidine, dioruntolylguanidine.

Guanidine type such as ortho-tolyl biguanide and diphenylguanicine phthalate; acetaldehyde-aniline reaction product; butyraldehyde-aniline condensate; aldehyde amine or aldehyde-ammonia type such as hexamethylenetetramine and acetaldehyde ammonia; 2-mercaptoimine Imidacillin series such as dacilin; thiourea series such as thiocarbamic acid, diethylthiourea, adipylthiourea, trimethylthiourea, dioruntolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetra Thiuram series such as butylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate,
Examples include dithioate salts such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; xanthate salts such as zinc dipylxanthate; and the like.

These crosslinking accelerators are generally used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 M parts of the rubber component consisting of the above-mentioned active component and zero component.

Peroxides used for peroxide crosslinking include dicumyl peroxide, 1,1'-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, di(t-butylperoxy)diisopropylbenzene, 2
,5-dimethyl-2,5-di(1-butylperoxy)
Examples include hexane%2.5-dimethyl-2,5-di(t-butylperoxy)hexyne.

In addition, as a crosslinking aid at that time, sulfur, a sulfur compound such as dipentamethylenethiuram tetrasulfide, a polyfunctional monomer such as ethylene dimethacrylate, divinylbenzene, diallyl phthalate, metaphenylene bismaleimide, toluylene bismaleimide, p-quinonedioxime %p.

Oxime compounds such as p'-dibenzoylquinone oxime can be used alone or in combination.

The rubber-like polymer composition may contain other activators, as necessary.
Dispersion cutting, fillers, plasticizers, tackifiers, colorants, foaming agents, foaming aids, lubricants, anti-aging agents.

Other additives may also be used.

Fillers include inorganic fillers such as carbon black, white carbon (silicic acid compound), calcium carbonate, talc, and clay; high styrene resin, coumaron indene resin, phenolic resin, lignin, modified melamine resin,
Organic fillers such as petroleum resins may be mentioned. Among these, inorganic fillers are particularly preferably used.

Softeners include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil,
Fatty oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, and zinc laurate; petroleum Examples include synthetic polymeric substances such as resins.

Plasticizers include phthalate esters, adipate esters, sebacate IIJ acid esters, etc. Tackifiers include coumaron indene resin, chirhen phenol resin, + silene formalin resin, etc. Colorants include As blowing agents, such as inorganic and organic pigments,
bicarbonate) IJum, ammonium carbonate, N, N'
- Dinitrosopentamethylenetetramine, azocarbonamide, asohisisophthyronitrile, benzenesulfonylhydrazide, toluenesulfonylhydrazide, calcium amide, halatoluenesulfonyl azide, etc. As foaming aids, use salicylic acid, phthal@, urea, etc. be able to.

Further, the compound can be manufactured by a known method using an open roll mill, a Banbury mixer, a kneader, or the like.

The crosslinking method is usually 100°C to 250°C, preferably 120°C.
At a temperature of ℃ to 200℃, crosslinking time is usually 10 minutes to 60 minutes,
Preferably, it can be carried out under conditions of 20 minutes to 40 minutes.

In particular, when peroxide crosslinking is performed, the crosslinking time is preferably about four times the half-life of the peroxide.

〔Effect of the invention〕

The modified liquid ethylene random copolymer of the present invention can be used as a modifier for resins or rubbery polymers, as a modification aid, as a lubricating oil additive,
Demonstrates excellent performance as a dispersion aid for aqueous dispersions of resins or rubbery polymers. In particular, by blending the ethylene/α-olefin/diene based elastic copolymer (3) and the silicon-containing rubbery polymer (B) as a modifier into a rubbery polymer composition, rubber elasticity, In particular, it is characterized by markedly improved permanent elongation (ps) and heat aging resistance.

〔Example〕

Next, the liquid modified ethylene random copolymer of the present invention will be specifically explained with reference to Examples.

Example 1 Ethylene composition: 40 mol%, number average molecular weight: 1600, Mw/
Mn 2.05, (v) 0.11 dl/g.

Ethylene-propylene copolymer 800I having a kinematic viscosity of 300 cst at 100° C. is introduced, and nitrogen substitution is performed for 2 hours to drive out dissolved oxygen. After that, reduce the internal temperature of the flask to 16
The temperature was raised to 0°C, and trimethoxyvinylsilane 320P and GTE were charged in advance into two dropping funnels.
Add rt-butyl peroxide 609 dropwise over 4 hours.After the completion of the dropwise addition, the reaction was carried out for another 4 hours, and the temperature inside the flask was raised to 180°C.S O, 5mmH9
Unreacted trimethoxyvinylsilane and decomposition products of di-tert-butyl peroxide are removed under reduced pressure.

The modified ethylene/propylene copolymer product is [η]
It was a colorless transparent liquid weighing 0.41617 g, and the grafting ratio of the tritoxyvinylsilane component was 25 parts by weight based on 100 parts by weight of the ethylene-propylene copolymer.

Example 2 In Example 1, the number average molecular weight was 390, Mw/Mn1
．． 15, (=7) 0.03 dl/g, using an ethylene-propylene copolymer with a kinematic viscosity of 1 to 4.5 cst at 100°C, 465 g of triethoxyvinylsilane in place of trimethoxyvinylsilane, and di-tert-butyl peroxide. 90. The same procedure was carried out except that F was added. The product modified ethylene/propylene copolymer has (v) 0.2
It was a colorless transparent liquid of 8 dl/.9, and the grafting ratio of the triethoxyvinylsilane component was 34 parts by weight based on the negative part of the ethylene/propylene copolymer '100M.

Example 3 In Example 1, the ethylene composition was 50 mol% and the number average molecular weight was 810. Mw/Mn 1.40, (v) 0.0
4 dl/, 9. Kinematic viscosity at 100°C 22. Bcst
The same procedure was carried out except that the ethylene-propylene copolymer of 1 was used, and the amounts of trimethoxyvinylsilane and di-tert-butyl peroxide were changed to 230 g and 40 g, respectively. The modified ethylene/propylene copolymer produced is [η) 0.16617 g of a colorless transparent liquid, and the grafting ratio of the trimethoxyvinylsilane component is ethylene/propylene.
The amount was 25 parts by weight per 100 parts by weight of the propylene copolymer.

Example 4 In Example 1, an ethylene-propylene copolymer with an ethylene composition of 50 mol%, a number average molecular weight of 810, and [η) 0.04 C1l/11 was used, and the amounts of trimethoxyvinylsilane and di-tert-butyl peroxide added were changed. The same procedure was carried out except that 120.OI and 240I were used. The product, a modified ethylene/propylene copolymer, is [
η) Q, is a colorless transparent liquid with 32 d6/'j,
The grafting ratio of the trimethoxyvinylsilane component was 127 parts by weight based on 100 parts by weight of the ethylene/propylene copolymer.

Example 5 In Example 1, an ethylene/1-hexene copolymer of 52 mol% ethylene and [η) 0.04 dl/9 was used instead of the ethylene/propylene copolymer, and trimethoxyvinylsilane and di-tert- The same procedure was carried out except that the amounts of butyl peroxide added were 230Ii and 40g, respectively. The modified ethylene/propylene copolymer of the product is a colorless transparent liquid of [η)Q, 15 dl#, and the grafting ratio of the trimethoxyvinylsilane component is 25 parts by weight per 100 parts by weight of the ethylene/propylene copolymer. Met.

Evaluation Examples 1 to 2 The products obtained in Examples 1 and 2 were evaluated as modifiers when blending silicone rubber and EPDM. The formulation is shown in Table 1, and the evaluation results are shown in Table 2.

Evaluation Ratio 9 Examples 1 In Evaluation Example 1, the same procedure was carried out except that the unmodified ethylene/propylene copolymer used in Example 1 was used instead of the product obtained in Example 1. The evaluation results are shown in Table 2.

Comparative Evaluation Example 2 The same procedure as in Evaluation Example 1 was carried out except that the product obtained in Example 1 was not blended. The evaluation results are shown in Table 2.

Evaluation Comparative Example 3 In Evaluation Example 1, the same procedure was carried out except that the unmodified ethylene-propylene copolymer used in Example 1 was used instead of the product obtained in Example 1, and silicone rubber was not blended. Ta. The evaluation results are shown in Table 2.

Claims (1)

[Claims] (1) An ethylene-based random copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms,
A liquid modified ethylene random copolymer obtained by graft copolymerizing an unsaturated silane compound component having 2 to 20 carbon atoms, wherein (i) the ethylene component of the ethylene random copolymer is 25 to 75 mol%; The α-olefin component is in the range of 25 to 75 mol%; (ii) the grafting ratio of the unsaturated silane compound component is 0 to 100 plate parts of the ethylene random copolymer;
．． 2 to 300 parts by weight, and (iii) 1 of the liquid modified ethylene random copolymer.
Intrinsic viscosity [η] measured in decalin at 35°C is 0.0
A liquid modified ethylene random copolymer characterized by: being in the range of 1 to 1.5 dl/g.