JPH047311A - Preparation of graft copolymer - Google Patents

Abstract

PURPOSE:To easily and stably prepare a graft copolymer excellent in thermal stability, impact strength, etc., by graft polymerizing a vinyl monomer onto a powdered crystalline ethylene-alpha-olefin copolymer rubber in an aq. suspension in the presence of a specified compd. CONSTITUTION:A vinyl monomer (e.g. styrene and acrylonitrile) is graft polymerized onto a powdered crystalline ethylene-alpha-olefin (e.g. propylene) copolymer rubber in an aq. suspension in the presence of a nonpolymerizable (halogenated) hydrocarbon (e.g. toluene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a graft copolymer having excellent impact resistance and heat resistance stability, and a method for producing the same.

[Prior Art] Impact-resistant resins (ABSM4 resins) have been known that are made by copolymerizing diene rubber with styrene and acrylonitrile. Weather-resistant and impact-resistant resins (AES resins) using ethylene-propylene-diene copolymer rubber (EPDM) as a rubber component are also known.

Among these resins, ABS resins are generally manufactured by emulsion polymerization, and AES resins are manufactured by solution polymerization.

[Problems to be Solved by the Invention] In recent years, there has been a strong demand for improving the heat resistance of these resins, and studies are progressing on methods using polymer alloys or various copolymerization techniques.

However, since AES resin uses diene-based rubber as a rubber component, its thermal stability is low, and its preferred range of use is narrow due to phenomena such as burning (coloring) and deterioration of physical properties during high-temperature molding. It has become.

The AES resin uses EPDM as a rubber component, so it has high heat resistance and stability, but it is different from ordinary EPD.
Since M is completely unqualified and can only be obtained in the form of a solution or veil, the solution polymerization method is generally used as the polymerization method for AES resin (Japanese Patent Publication No. 48-181).
Publication No. 18, No. 52-18751, No. 52-3054
No. 9, No. 52-30994, No. 52-30995,
JP-A-50-61492, JP-A No. 54-94596, JP-A No. 56-50906).

However, the solution polymerization method is economically disadvantageous because it requires separation and recovery of the polymer from the produced solution, purification and recycling of the solvent, etc.

Furthermore, in order to increase the grafting rate and degree of crosslinking, it is necessary to introduce a large amount of a diene component as a comonomer into the EPDM used, which leads to an increase in cost economically.

Regarding the polymerization method of AES resin, the bulk polymerization method (Japanese Patent Publication No. 46-33571), the bulk suspension polymerization method (Japanese Patent Publication No. 46-33571),
No. 8-32434, No. 49-14874, No. 49-2
5189), suspension polymerization method (Japanese Patent Publication No. 49-10831, Japanese Patent Publication No. 48-80189), emulsion polymerization method (Japanese Patent Publication No. 48-80189),
Although economically more advantageous methods such as EPDM No. 3-16394 and No. 48-35718 have been attempted, it is difficult to carry out bulk polymerization due to the low solubility of EPDM in monomers. There are problems in that it is impossible to increase the rubber concentration, or the viscosity increases during bulk polymerization, making it difficult to remove heat and making stable polymerization difficult.

Regarding suspension polymerization, pulverizing completely non-quality EPDM is a major factor in increasing costs, and it is not possible to obtain completely non-quality EPDM in powder form without mutual adhesion. In order to create a uniform dispersion state, complicated steps such as suspending the solution (Japanese Patent Application Laid-Open No. 4817895) have to be taken, and this has not been successful.

Further, in the emulsion polymerization method, it is necessary to convert EPDM obtained in a hot liquid or solid state into an emulsion state, and the process is complicated, making it an economically disadvantageous method.

Under these circumstances, the present inventors graft-copolymerized a vinyl monomer to ethylene-α-olefin copolymer rubber (hereinafter referred to as the present copolymer rubber).
We have discovered that when this copolymer rubber, which has crystallinity and is in powder form, is used as the raw material for the graft copolymer, a graft copolymer with excellent performance can be obtained. Furthermore, it has been found that by carrying out aqueous suspension polymerization of the present copolymer rubber together with the monomer to be grafted in the presence of a dispersant, it is possible to stably carry out the suspension polymerization. (Japanese Patent Application No. 63-219891) [Means for Solving the Problems] When carrying out the above-mentioned aqueous suspension polymerization, the present inventors investigated the use of non-polymerizable hydrocarbons and/or non-polymerizable halogenated hydrocarbons (
By coexisting with non-polymerizable hydrocarbons (hereinafter referred to as non-polymerizable hydrocarbons), the dispersion stability of this copolymer rubber is dramatically increased, and the resulting kraft copolymer and graft copolymer can be used as one component. The present invention was achieved based on the discovery that the composition has a well-balanced fluidity and impact strength.

That is, the present invention provides crystalline, powdery ethylene-
A graft copolymer characterized by coexisting a non-polymerizable hydrocarbon and/or a non-polymerizable halogenated hydrocarbon in a method of graft polymerizing a vinyl monomer to an α-olefin copolymer rubber by an aqueous suspension method. Relating to a manufacturing method.

The present invention will be explained in detail below.

a) Ethylene-〇olefin copolymer rubber The present copolymer rubber used in the present invention is obtained by copolymerizing ethylene and α-olefin, and has crystallinity and powder properties. This copolymer rubber has various properties.

Here, the α-olefin used in the production of this copolymer rubber is an α-monoolefin having at most 12 carbon atoms, such as propylene, butene-
Mention may be made of 1,4-methylpentene-1, hexene-1 and octene-1, but preferably propylene or butene-1 is used.

The present copolymer rubber used in the present invention is an ethylene-α olefin copolymer rubber that has crystallinity, and because it has crystallinity, it is possible to maintain powder properties without mutual adhesion. Moreover, it has high strength as a rubber and easily exhibits impact resistance. In particular, those having polyethylene crystals are preferred).

Although this copolymer rubber having polyethylene crystals is an ethylene α-olefin copolymer rubber without a diene component, it has good crosslinking properties during kraft polymerization, and the resulting kraft copolymer The gel fraction of the combined product is quite high, making it possible to obtain a graft copolymer with high impact resistance.

The ethylene content in this copolymer rubber is usually 40 to 90% by weight, more preferably 55 to 85% by weight. If the ethylene content is less than 40% by weight, there will be no polyethylene crystals, resulting in tackiness. As a result, it tends to adhere to each other and form lumps, making it difficult to obtain the present copolymer rubber in powder form.

For this reason, workability and economical efficiency during the production of the graft copolymer are lowered, and at the same time, the dispersibility of the present copolymer rubber and the degree of crosslinking of the graft copolymer are lowered. Furthermore, if the ethylene content exceeds 90% by weight, the obtained copolymer rubber becomes hard, and the impact resistance of the finally obtained graft copolymer is not sufficient.

Another important factor is the ratio of polyethylene crystals in the copolymer rubber. This polyethylene crystallinity is determined by the heat of fusion (cal/g) of polyethylene crystals measured by DSC (scanning differential calorimetry).
/g). Here, the present copolymer rubber has a polyethylene crystallinity of 1 to 20%, which is preferred.

The number of these polyethylene crystals is determined by the ethylene content in the copolymer rubber, but if it is less than 1%, it tends to form lumps, and if it exceeds 20%, the copolymer rubber becomes hard (the impact resistance of the graft copolymer is Sexual improvement becomes insufficient.

Here, the term "powder-like" refers to a powdery state with an average particle size of 1000 μm or less, and the present copolymer rubber has crystallinity and is produced by the method shown below. It can be used as is.

As a preferred method for producing the present copolymer rubber which has crystallinity and is in the form of a powder, the example disclosed in JP-A-57-179207 can be mentioned.

According to this method, ethylene and α-olefin are copolymerized in a slurry state in a saturated or unsaturated hydrocarbon having 4 or less carbon atoms at a reaction temperature of 50° C. or less in the presence of a Ziegler type catalyst. By polymerizing in a slurry state, the present invention makes it possible to easily produce a copolymer rubber containing polyethylene crystal parts, unlike conventional solution polymerization methods.

Furthermore, it is easy to increase the molecular weight of the copolymer rubber, which is advantageous for improving impact resistance, and the present copolymer rubber suitable for the present invention can be produced.

A catalyst system suitable for such a method includes at least Ti.
A catalyst system consisting of a solid component containing , Mg, and CI and an organic AI is desirable, preferably a catalyst system shown in JP-A-56-151707 or JP-A-59-215304, more preferably JP-A-59-215304. This is the catalyst system proposed in No.

In addition, the melt flow index (MFI) of a single copolymer rubber measured at 230°C is usually 0.005 to 10.
g/10 min, preferably 0.01 to 8 g/10 min. If the MFI is less than 0.005, the dispersion of the present copolymer rubber in the graft polymer becomes poor, which is not preferable. Furthermore, if the MFI exceeds 8, the impact strength of the graft polymer decreases, which is undesirable.
The HLMFI/MFI measured in is usually 10 or more, but preferably 35 or more. HLMF1/MF-I is 1
If it is less than 0, the impact strength decreases, which is not preferable.

b) Monomer to be grafted The vinyl monomer used in the production of the graft copolymer of the present invention consists of an aromatic vinyl compound, an unsaturated nitrile compound, an unsaturated carbon # (ester) compound, and a maleimide compound. One or more monomers selected from the group.

Examples of aromatic vinyl compounds include styrene, a-methylstyrene, and their nuclear-substituted derivatives; nuclear alkyl-substituted styrenes include p-methylstyrene and 0-methylstyrene; nuclear halogen-substituted styrenes include p-chlorostyrene and p-chlorostyrene; Examples include -bromostyrene, and styrene, a-methylstyrene, and p-methylstyrene are preferred.

Examples of the unsaturated nitrile compound include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

Examples of unsaturated carboxylic acids (esters) include acrylic acid,
Examples include methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, and methyl acrylate and methyl methacrylate are preferred.

Examples of maleimide compounds include maleimide and N-substituted maleimides, specifically maleimide, N-2
enylmaleimide, N-methylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N
-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N-2-chlorophenylmaleimide and the like can be mentioned, with N-phenylmaleimide and N-cyclohexylmaleimide being preferred.

These monomers can be used alone or in combination of two or more, depending on the properties required for the graft copolymer. However, when producing the graft copolymer of the present invention by a suspension polymerization method, the monomers (mixture) are mixed with ethylene-a olefin copolymer rubber under polymerization temperature conditions in order to obtain a homogeneous or raft copolymer. It is hoped that this will penetrate to some extent. For this purpose, it is desirable that the monomers (mixture) to be grafted be in a liquid state at room temperature.6 C) Non-polymerizable hydrocarbons In the present invention, the non-polymerizable hydrocarbons coexisting during aqueous suspension polymerization are: One or more hydrocarbons selected from the group consisting of hydrocarbons having 100 or less carbon atoms and halogenated hydrocarbons, which do not have a polymerizable unsaturated group.

Non-polymerizable hydrocarbon means a hydrocarbon that does not react with non-polymerizable hydrocarbons or with vinyl monomers under polymerization conditions.

In addition, halogenated hydrocarbons include chlorinated hydrocarbons,
There are brominated hydrocarbons, iodinated hydrocarbons, etc., but brominated and iodinated hydrocarbons are not preferred because they have a large chain transfer effect during graft polymerization and are also highly corrosive.
Chlorinated hydrocarbons are preferred.

The carbon number of these non-polymerizable hydrocarbons is selected from those having 100 or less, but preferably 70 or less. Carbon number 1
If it exceeds 00, the viscosity of the non-polymerizable hydrocarbon itself becomes high, resulting in poor dispersion during suspension polymerization, which is not preferable. For reasons such as economy, operability of the reaction, or the need to use a special polymerization reactor, it is preferable to use a polymer that is liquid at room temperature.

Further, these non-polymerizable hydrocarbons may remain in the kraft copolymer without requiring a removal step after polymerization unless they pose a particular problem in molding or handling. However, for substances that are expected to remain in the kraft copolymer and cause problems such as odor, smoke, and foaming during molding, a step is required to remove them after the polymerization is completed.

Specific examples of non-polymerizable hydrocarbons include n-pentane, n-hexane, n-octane, n-decane, paraffin oil, and the like as aliphatic non-polymerizable hydrocarbons.

Examples of the alicyclic non-polymerizable hydrocarbon include cyclohexane, cyclopentane, and naphthenic oil.

Examples of aromatic non-polymerizable hydrocarbons include benzene, toluene, p-xylene, mixed xylene, and aromatic oils.

The non-polymerizable halogenated hydrocarbon is preferably a chlorinated hydrocarbon, such as methylene chloride, chloroform, 1.2. −
Examples include dichloroethane and chlorinated paraffin.

d) Polymerization conditions The method for producing the graft copolymer of the present invention is a method in which a vinyl monomer is graft-polymerized to the present copolymer rubber, which has crystallinity and is in the form of powder, by an aqueous suspension method. In this method, it is possible to coexist non-polymerizable hydrocarbons to stabilize the dispersibility during polymerization, and in such a method, chain transfer graft polymerization is usually performed using a non-polymerizable dispersion medium (such as a solvent). ) (because the monomer concentration decreases), it is normal that the grafting rate decreases and the impact strength decreases, but the method of the present invention surprisingly contrary to this expectation. In addition, it has made it possible to produce a graft copolymer that exhibits excellent impact strength and high fluidity.

The amount of the copolymer rubber used in the production of the graft copolymer of the present invention is preferably 5 to 80 parts by weight based on 100 parts by weight of the mixture of the copolymer rubber and the monomer to be grafted. ]0 to 60 parts. If it is less than 5 parts by weight, the effect of improving impact resistance is low (unfavorable,
If it exceeds 80 parts by weight, the ethylene-a olefin copolymer rubber will be crosslinked as large particles, making it impossible to obtain a graft copolymer with good performance.

In addition, monomers to be grafted used in the production of the graft copolymer of the present invention include aromatic vinyl compounds, unsaturated nitrile compounds, and unsaturated carboxyl compounds! ! ! (
ester) compounds and maleimide compounds, and the types of monomers used and the combination thereof depending on the performance required as a graft copolymer. The combination and usage amount thereof can be selected, for example, the following combinations and usage amounts can be exemplified. However, the present invention is not limited to these examples.

An example of grafting only one type of monomer is the use of only one type of aromatic vinyl compound. Further, it is possible to exemplify the use of only one type of unsaturated carboxyl l1l (ester) compounds.

An example of a combination of two or more types of monomers is a combination of 40 parts by weight or more of an aromatic vinyl compound and 60 parts by weight or less of an unsaturated nitrile compound as monomers to be grafted. Preferably, the aromatic vinyl compound is 60 to 8
An example is a combination of 0 parts by weight and 20 to 40 parts by weight of an unsaturated nitrile compound. Here, if the amount of the aromatic vinyl compound is less than 40 parts by weight, the graft copolymer will be colored, which is not preferable. Suitable examples of these include combinations of styrene and acrylonitrile.

Another example is a combination of 40 parts by weight or more of an aromatic vinyl compound, 60 parts by weight or less of an unsaturated nitrile compound, and 70 parts by weight or less of a maleimide compound as monomers to be grafted.

Preferably, 50 to 80 parts by weight of the aromatic vinyl compound,
An example is a combination of 20 to 40 parts by weight of an unsaturated nitrile compound and 10 to 40 parts by weight of a maleimide compound. If the amount of the aromatic vinyl compound is less than 40 parts by weight, the graft copolymer will become colored, which is undesirable. If the amount of the maleimide compound exceeds 70 parts by weight, the performance of the graft copolymer will deteriorate. A good example of these is a combination of styrene, acrylonitrile, and phenylmaleimide.

In the present invention, the amount of non-polymerizable hydrocarbons coexisting during aqueous suspension polymerization is 100% of the graft copolymer.
The amount is 50 parts by weight or less, preferably 30 parts by weight or less, and more preferably 20 parts by weight or less. If the non-polymerizable hydrocarbon is present in an amount exceeding 50 parts by weight, monodispersed particles tend to stick together, causing poor dispersion.

In the method for producing the graft copolymer of the present invention, the present copolymer rubber, monomer mixture, and non-polymerizable hydrocarbons are suspended in water and polymerized, or the water used at this time is The amount is 0.8 to 1 by weight based on the total of the copolymer rubber, the monomer to be grafted, and the non-polymerizable hydrocarbon.
O times the amount, preferably the same amount to 5 times the amount. If the amount of water used is less than 0.8 times the amount, the suspension state becomes unstable, dispersion is broken, the system aggregates, and polymerization becomes difficult.

On the other hand, if the amount exceeds 10 times, the amount of graft copolymer produced in one polymerization will decrease, which is not preferable because productivity will decrease.

As a dispersant used to maintain a suspended state in the production of a graft copolymer, a dispersant generally used in suspension polymerization can be used. in particular,
Water-soluble polymers include gelatin, starch, polyvinyl alcohol, polyacrylates, etc., and sparingly soluble inorganic compounds include barium sulfate, calcium phosphate, calcium carbonate, calcium sulfate, etc., and it is also possible to use these in combination. Among these, polyvinyl alcohol,
Calcium phosphate is preferred, and the amount used thereof is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, per 100 parts by weight of water.

Moreover, these dispersants can also be used in combination with cationic, anionic, or nonionic surfactants. When used in combination, the amount of surfactant used is preferably 1/100 to 1/1000 l/1000 to 1/1000 of the weight of the dispersant, and 1/20
0 to I/600 is more preferable.

In the suspension graft polymerization method, this copolymer rubber, a monomer, and a non-polymerizable hydrocarbon are suspended in water and heated in the presence of a radical generator that is easily soluble in the monomer. Although the polymerization reaction is carried out, it is desirable that the inside of the polymerization system be purged with an inert gas such as nitrogen gas. The presence of oxygen active against radical polymerization is undesirable because it exhibits a polymerization inhibiting effect.

The polymerization temperature is preferably 50 to 200°C, and 1
More preferably, the temperature is 80°C or lower.

If the polymerization temperature is lower than 50°C, the polymerization reaction progresses slowly and is not economical. If the temperature exceeds 200°C, the performance of the resulting graft copolymer deteriorates, which is undesirable.

The polymerization time is preferably 1 to 20 hours, more preferably 2 to 10 hours; polymerization times of less than 1 hour are not preferred because it is difficult to advance the polymerization reaction to a sufficient conversion rate, and polymerization times exceeding 20 hours are not preferred. It is not economical and undesirable to employ time.

The monomer-easily soluble radical generator used in the polymerization reaction generates radicals at an appropriate rate within the above polymerization temperature and polymerization time range, and the conversion rate of the monomer used is determined according to the polymerization conditions. It is possible to select from among radical generators that account for at least 70% or more of the following: in particular,
Among organic peroxides, diacyl peroxides include lauroyl peroxide, pen-puil peroxides: dicumyl peroxide, 1,3-bis-(t-butylperoxy-isopropyl)-benzene, Di-t-butyl peroxide: As an alkyl perester, t-butyl peroxybivalate, di-t-butyl peroxyazelate, t-butyl peroxybenzoate, etc., and as an azo compound, 2-2°-azobis Examples include isobutyronitrile, azobisisobutanol diacetate, 1,1-azobiscyclohexanecarbonitrile, and these can be used alone or in combination of two or more.

In addition, the amount of radical generator used is 1:1 of the monomer mixture.
00! It is 0.05 to 10 parts by weight per part i, and 0
1 to 3 parts by weight is preferred. The amount of radical generator used is 0
If the amount is less than 0.5 parts by weight, the polymerization rate is slow and uneconomical, which is not preferable. Further, if the amount exceeds 10 parts by weight, the polymerization rate becomes too high and there is a risk of runaway polymerization reaction, which is not preferable.

Furthermore, it is possible to use mercaptans which are commonly used for the purpose of controlling molecular weight in suspension graft polymerization. Specific examples include primary, secondary, and tertiary mercaptans having an alkyl group or substituted alkyl group, such as n-butyl mercaptan, inbutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, 5ec
-dodecylmercaptan, tert-dodecylmercaptan: aromatic mercaptans, such as phenylmercaptan, thiocresol: thioglycolic acid and its esters: mercaptans such as thioglycol. These can be used alone or in a mixture of two or more.6 The amount used is 5 parts by weight or less, preferably 3 parts by weight or less, per 100 parts by weight of the monomer (mixture). ,5
If the amount exceeds 1 part by weight, the polymer chain of the monomer becomes short and the strength decreases, which is not preferable.

After the suspension graft polymerization reaction shown above, the generated graft copolymer is dispersed in water as particles, so it is very easy to separate it from water. After undergoing treatment and washing steps for the purpose of removing non-polymerizable hydrocarbons, dispersants, or unreacted monomers, it is dried.

e) Graft copolymer In general, in graft polymerization, it is difficult to achieve 100% graft polymerization of branch monomers with respect to the trunk polymer. Since it is considered that homopolymer by-products are unavoidable, the weight of the graft copolymer in the present invention refers to the total weight of the copolymer rubber and the monomers used.

The present invention relates to a method for producing a graft copolymer by graft copolymerization using a powdery ethylene-a olefin copolymer rubber having crystallinity as a raw material.

The graft copolymer thus obtained has a graft ratio defined below of 20 to 150%, preferably 50 to 100%. Further, the gel fraction, which is also defined below, is 40 to 200%, preferably 50 to 170%.

If the grafting ratio is less than 20%, the impact resistance will not be sufficient,
If it exceeds 150%, fluidity becomes poor. In addition, if the gel fraction is less than 40%, the impact resistance will not be sufficient (200%
If it exceeds this, the fluidity becomes poor.

Graft rate Niger raft copolymer (fiW1) is ME
The value calculated by the following formula from the amount of insoluble matter (weight 1 tW2) obtained as a result of Soxhlet extraction with K for 7 hours, provided that Fl
is the weight fraction of this copolymer rubber contained in the graft copolymer.

Gel fraction ・Value calculated from the following formula from the insoluble content (weight 1iW3) obtained as a result of Soxhlet extraction of the graft copolymer with toluene for 7 hours 9 or more The method for producing the graft copolymer of the present invention and I explained the kraft copolymer obtained by the manufacturing method,
The graft copolymer produced by the present invention itself has high impact strength, high thermal stability, and weather resistance, and can be used as a molding material as it is, and can also be used with polystyrene and various styrene-based materials. Polymers, acrylic resins, polyamide resins, polycarbonate resins, etc.
It is also possible to mix it with various thermoplastic resins to obtain a composition with a balance of physical properties that match the intended use.

Furthermore, stabilizers, WTL agents, plasticizers, lubricants, glass fibers, and inorganic fillers may be added to the graft copolymer obtained by the production method of the present invention or to a composition containing the graft copolymer as one component. It is also possible to add and use colorants, ultraviolet absorbers, etc.

[Examples] The present invention will be explained below using examples. It should be noted that the present invention is not limited to the following examples unless it departs from the spirit thereof.

(Example 1) (a) (Production of ethylene-a olefin copolymer rubber) Anhydrous magnesium chloride (obtained by drying commercially available anhydrous magnesium chloride at about 500°C for 15 hours in a dry nitrogen stream) 2.1kg and 0
．． 9 kg of AA type chloride buried titanium (manufactured by Toyo Stofa Co., Ltd.) was co-pulverized for 8 hours in a vibrating ball mill to obtain a homogeneous co-pulverized product (Ti atom content 72% by weight, chlorine atom content M73).
7% by weight, Mg atomic content 177% by weight, hereinafter referred to as "solid component (F)").

Of the solid component (F) thus obtained, 600 g was placed in a 100 liter glass-lined container, 40 liters of n-hexane was added, and the mixture was stirred to form a uniform suspension. 100 g of γ-glycidoxypropyltrimethoxysilane was added to this suspension, and the mixture was thoroughly stirred at room temperature for 1 hour. After that, let it stand, remove the supernatant liquid, and
0 liters of toluene was added. Then, 2 kg of tetrahydrofuran was added, and the mixture was thoroughly stirred at room temperature for 1 hour. The treatment system was cooled to room temperature, and the product was thoroughly washed with n-hexane (until almost no Ti atoms were observed in the washing solution) to obtain a solid catalyst component (A).

A 290 liter tubular loop continuous reactor was filled with liquid propylene, propylene was kept at 60 Kg/H, ethylene was kept at a concentration of 10 mol% in the liquid layer, and hydrogen was kept at a concentration of 0.02 mol% in the liquid layer. 360 mmol/H of triethylaluminum (hexane quenching liquid), 180 mmol/H of tetrahydrofuran/H1 solid catalyst component (A
) was supplied to this reactor at a reaction temperature of 30 g/H1.
The 0 polymer polymerized at 0.degree. C. was intermittently discharged into a flash hopper in the form of a slurry, and the polymer was taken out from the bottom, passed through an fAN2A flow, and dried at 40.degree. C. to obtain a polymer powder. These were in the form of a smooth powder without sticking to each other, and the yield was 6 kg/h. Therefore, the average polymerization activity per solid catalyst (A) was 49.3 Kg/g-Ti.

The ethylene content of this is 61% by weight, and the MFI
is 0.02g/10min, HLMFI/MFI is 40, M
w/Mn is 5.3, and the crystallinity calculated from the heat of fusion of the crystal by DSC measurement is 7°0%, the same < DSC
The measured melting point was 110°C, and the intrinsic viscosity at 135°C in decalin was 5.4 dl/g. This ethylene-propylene copolymer rubber is referred to as rubber (A).

Furthermore, an ethylene-propylene copolymer rubber with a high ethylene content was produced using the same polymerization conditions and method as rubber (A), except that the ethylene concentration in the liquid layer was 18 mol%. . The ethylene content of this product is 80% by weight, MF'T is 0.8g/10min, H
LMFI/MFI is 37, Mw/Mn is 5.0
, DSC? The degree of crystallinity calculated from the heat of fusion of the crystal according to the temperature measurement is 18%, which is the same.The melting point according to DSC measurement is 108%.
The intrinsic viscosity at 135° C. in decalin was 2.2 dl/g. This ethylene-propylene copolymer rubber is
B).

Furthermore, an ethylene-propylene copolymer rubber with a low ethylene content was produced using exactly the same polymerization conditions and method as rubber (A), except that the ethylene concentration in the liquid layer was 8 mol%. . The ethylene content of this product is 55% by weight, the MFI is 1.0g/10min, and the HLM
FI/MFI is 38, M w / M n is 4.9, D
The degree of crystallinity calculated from the heat of fusion of the crystal according to S CII+ constant is 28%, the same < The melting point according to D S Ci++ constant is 107 °C, and the intrinsic viscosity at 135 °C in decalin is 2.0
It was dl/g. This ethylene-propylene copolymer rubber is referred to as rubber (C).

(b) Production of graft copolymer In a pressurized reactor equipped with a stirrer with a capacity of 10 liters,
Rubber (A) as ethylene-α olefin copolymer rubber
200g of styrene, 6DOg of acrylonitrile, and 20g of acrylonitrile as a mixture of monomers and polymerization initiator to be grafted.
0g, t-butyl peroxybenzoate 4.96g,
A water slurry with a concentration of 10% by weight containing a mixture of 0.40 g of t-doceyl butane, 100 g of toluene as a non-polymerizable hydrocarbon, and tribasic calcium phosphate as a dispersant 5
00g and sodium dodecylbenzenesulfonate 0.1
Charge 25 g of the mixture and 3500 g of pure water as a dispersion medium, pressurize with nitrogen to a pressure of 4 g/CII + 2, and then remove the pressure). Repeat this operation 5 times to fully purge the reactor system with nitrogen and remove oxygen. The state was made virtually non-existent.

Thereafter, the temperature of the reactor was raised to 135° C. over about 40 minutes, and the polymerization reaction was continued at that temperature for 4 hours. After 4 hours of polymerization, the reactor was cooled to room temperature and the contents were taken out.

The graft copolymer was dispersed in water as fine particles with uniform particle size. The obtained graft copolymer was washed with hydrochloric acid water for the purpose of removing tertiary calcium phosphate, which is a dispersant, and
After repeated washing with water to remove sodium dodecylbenzenesulfonate, it was dried in a hot air dryer at 80° C. for 24 hours to remove toluene and water. The obtained graft copolymer was 982 g, and the yield was 98 g.
．． It was 2%. In addition, the kraft rate and gel fraction obtained as a result of Soxhlet extraction are: graft rate = 77%;
The dried graft copolymer with a gel fraction of 150% was heated at 200°C using a Labo Plus' Tomil (Labo Blasto Mill ME type manufactured by Toyo Seiki Co., Ltd.).
Knead for homogenization for 10 minutes at
A test piece was prepared by hot press molding at 0°C. The physical properties of the test pieces were measured according to the following methods and conditions. The measured physical property values (1) are shown in Table 2.

Melt flow rate: JIS K6970 (230℃
5Kg load) Izot impact strength: JIS K6871 (with notch) Bending strength, elastic modulus: JIS K7203 (Example 2)
．． 3) As an example of changing the type of ethylene-α-olefin copolymer rubber, as an ethylene-α-olefin copolymer rubber,
Polymerization was carried out in the same manner as in Example 1, except that Rubber (B) (Example 2) and Rubber (C) (Example '3) were used to obtain a graft copolymer. Table 1 also shows the kraft ratio and gel fraction of the obtained graft copolymer.

In addition, test pieces were prepared for these kraft copolymers according to the same procedure as in Example 1, and their physical properties were measured. The measured physical property values are shown in Table 2.

(Example 4.5) As an example in which the amount of non-polymerizable hydrocarbons used was changed, the amount of toluene used was 300g (Example 4), 50g
(Example 5) Polymerization was carried out in the same manner as shown in Example 1, except that a graft copolymer was obtained. Table 1 also shows the graft ratio and gel fraction of the obtained graft copolymer.

In addition, test pieces were prepared for these graft copolymers according to the same procedure as in Example 1, and their physical properties were measured. The measured physical property values are shown in Table 2.

(Examples 6 to 10) As an example in which the number of carbon atoms and the type of non-polymerizable hydrocarbons were changed, the following non-polymerizable hydrocarbons were used, and Example 1
Polymerization was carried out in the same manner as shown in , to obtain a graft copolymer. The grafting rate of the obtained kraft copolymer,
Table 1 also shows the gel fraction.

(Left below) Paraffin oil: Idemitsu Kosan PW380 Aroma oil: Idemitsu Kosan N5100 Chlorine paraffin: Toyo Soda Oil The carbon number is the average value. For these graft copolymers, the same procedure as in Example 1 was followed. Test pieces were prepared and their physical properties were measured according to the following. The measured physical property values are shown in Table 2.

(Examples 11 to 14) Polymerization was carried out in the same manner as in Example 1 using the charged composition ratio, polymerization temperature, and time shown in Table 1 to obtain graft copolymers. Table 1 also shows the graft ratio and gel fraction of the obtained kraft copolymer.

In addition, these kraft copolymers were prepared using a Labo Blast Mill (Labo Blast Mill ME type manufactured by Toyo Seiki Co., Ltd.) using the thermoplastic resins shown in Table 2 and the ratios also shown in Table 2.
The wires were cross-wired at 00°C for 10 minutes, and then hot press molded at 230°C to prepare test pieces. The measured physical property values are shown in Table 2.

The thermoplastic resin used here was manufactured based on the method shown below as a reference example.

(Reference example) AS (styrene-acrylonitrile copolymer) used as a thermoplastic resin contains styrene and acrylonitrile in a weight ratio of 75/25, and monomers of lauroyl peroxide and t-butyl peroxylaurate as polymerization initiators. 0.25 parts by weight per 100 parts by weight of the body mixture,
0.35 parts by weight and 0.2 parts by weight of t-dodecyl mercaptan as a chain transfer agent were added to 100 parts by weight of the monomer mixture, and the polymerization was carried out at 80°C for 4 hours at 120°C for 2 hours according to a known suspension polymerization method. It is obtained by polymerization over time. Its molecular weight is 0.76 dl [η] in chloroform at 30°C.
/g.

(Comparative Example 1) As a comparative example, polymerization was carried out in the same procedure as shown in Example 1, without using a non-polymerizable hydrocarbon, at the charging composition ratio shown in Table 1 and at the polymerization temperature for 1 hour, A graft copolymer was obtained. However, dispersion during polymerization is unstable, and stirring blades,
There was a lot of resin adhering to the walls of the polymerization tank, etc., and the properties of the obtained kraft copolymer were poor. Table 1 shows the graft ratio and gel fraction of the graft copolymer obtained in barely granular form. ing.

In addition, test pieces were prepared for these graft copolymers according to the same procedure as in Example 1, and their physical properties were measured. The measured physical property values are shown in Table 2.

(The following is a blank space) Further, a weather resistance test was conducted on the test piece of Example 7.13.

Test conditions: Sunshine Weatherometer (manufactured by Suga Test Instruments) Test temperature: 63°C Measurement item: Izod impact strength (with notch) Table 3 shows the Izod impact strength change and retention rate with respect to test time. It is clear that the retention rate of impact strength was high in the test of C, and the weather resistance was excellent.

(Left below) f Effects of the Invention According to the production method of the present invention, a crystalline and powdery ethylene-α-olefin copolymer rubber is used as a starting material, and non-polymerizable hydrocarbons are coexisted. By doing so, the graft copolymer can be produced stably and easily.

In addition, compositions containing the graft copolymers and kraft copolymers of the present invention as one component have excellent heat resistance stability, weather resistance, and impact resistance, so they can be used, for example, in automobile parts, electrical/electronic parts, and household use. It can be preferably used for electrical equipment, office electrical equipment, etc.

Claims (1)

[Scope of Claims] (1) In a method of graft polymerizing a vinyl monomer to a crystalline, powdery ethylene-α-olefin copolymer rubber by an aqueous suspension method, a non-polymerizable hydrocarbon and/or a non-polymerizable halogenated hydrocarbon. (2) Ethylene-α-olefin copolymer rubber has an ethylene content of 40
90% by weight, and the crystallinity as measured by DSC is 1 to 20% in terms of polyethylene. (3) The vinyl monomer is an aromatic vinyl compound, an unsaturated nitrile compound, an unsaturated carboxylic acid (ester) compound,
The method for producing a graft copolymer according to claim 1, wherein the monomer is one or more monomers selected from the group consisting of maleimide compounds. (4) The amount of coexisting non-polymerizable hydrocarbon and/or non-polymerizable halogenated hydrocarbon is 10
The method for producing a graft copolymer according to claim 1, wherein the amount is 50 parts by weight or less relative to 0 parts by weight. (5) The graft according to claim (1) or (4), wherein the non-polymerizable hydrocarbon and the non-polymerizable halogenated hydrocarbon are non-polymerizable hydrocarbons and non-polymerizable halogenated hydrocarbons having 100 or less carbon atoms. Method for producing copolymer.