JP2006176578A - Maleimide copolymer composition, its preparation method and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a maleimide copolymer composition which has extremely low contents of unreacted monomer and other volatile components and shows extremely high heat resistance and a good hue, its industrial preparation method and a molded product thereof. <P>SOLUTION: The maleimide copolymer composition is obtained by adding 0.01-4 pts.mass liquid polydiene to 100 pts.mass maleimide copolymer comprising 55-35 pts.mass aromatic vinyl monomer unit, 45-65 pts.mass maleimide monomer unit and 0-10 pts.mass monomer unit copolymerizable with these monomers. The maleimide copolymer composition has a maleimide monomer content of 0.1-300 ppm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a maleimide copolymer composition excellent in the balance of various physical properties, a production method thereof, and a molded body thereof.

Conventionally, a maleimide copolymer has been used as a heat resistance imparting material for the purpose of improving the heat resistance of an ABS resin or the like. The maleimide copolymer can be obtained by copolymerizing maleimide monomer, aromatic vinyl monomer and other copolymerizable monomers, unsaturated dicarboxylic acid anhydride, aromatic vinyl monomer There is a method in which an unsaturated dicarboxylic acid anhydride group is imidized with a primary amine or the like after copolymerization of the monomer and other copolymerizable monomers. On the other hand, volatile components such as maleimide monomers contained in maleimide copolymers are low in molecular weight, rich in reactivity, irritating, and odorous, so they are generally reduced in terms of environmental issues. Is desired. Therefore, when the maleimide copolymer is granulated with a vent type screw type extruder after the polymerization is completed, unreacted monomers such as maleimide monomers and solvents are often removed. When the temperature is raised, the solvent is efficiently removed. However, when the resin temperature is raised, there is a problem that depolymerization due to thermal degradation of the resin occurs, and as a result, the remaining amount of the maleimide monomer cannot be reduced. Even when a maleimide copolymer in which the polymerization rate is increased and the unreacted maleimide monomer is used is the same, it is difficult to reduce the volatile components as a result.

In order to solve this problem, a method of obtaining a maleimide copolymer with a small amount of unreacted maleimide monomer by adding a diene compound that reacts with a maleimide monomer and Diels-Alder during the production of the maleimide copolymer (Patent Document) 1, Patent Document 2) has been proposed. Although this method can reduce the unreacted maleimide monomer immediately after polymerization, it can be depolymerized during granulation to generate a new maleimide monomer, or the Diels-Alder reaction adduct produced by the reaction has a low molecular weight. Therefore, irritation and odor problems could not be solved.
JP-A-12-248010 WO99 / 60040

Provided is a maleimide copolymer in which both a volatile component caused by a solvent and a volatile component generated by depolymerization during granulation are reduced.

That is, the present invention
1) Maleimide copolymer comprising 55 to 35 parts by weight of aromatic vinyl monomer units, 45 to 65 parts by weight of maleimide monomer units, and 0 to 10 parts by weight of monomer units copolymerizable with these monomers. A maleimide copolymer composition in which 0.01 to 4 parts by mass of a liquid polydiene is added to 100 parts by mass of the coalescence, and the content of the maleimide monomer is 0.1 to 300 ppm.
2) The maleimide copolymer composition of 1), wherein the number average molecular weight of the liquid polydiene is 500 to 10,000 and the viscosity is 500 to 5000 mPa · s.
3) The maleimide copolymer composition of 1) or 2) wherein the maleimide copolymer has a glass transition temperature of 180 to 230 ° C. and a weight average molecular weight of 60000 to 200,000.
4) The maleimide copolymer composition according to any one of 1) to 3), wherein the volatile component other than the maleimide monomer is 0.1 to 1000 ppm and the yellowness is less than 5.
5) The maleimide copolymer composition according to any one of 1) to 4), wherein the liquid polydiene is polybutadiene.
6) 0.01 to 4 mass of liquid polydiene is added to 100 mass parts of maleimide copolymer produced by maleimide-forming a copolymer of aromatic vinyl monomer and unsaturated dicarboxylic anhydride with primary amine. Of a maleimide copolymer composition, wherein 0.01 to 2 parts by mass of a part and a radical scavenger are added.
7) A process for producing a maleimide copolymer composition according to 6), wherein the liquid polydiene is polybutadiene.
8) The manufacturing method of the maleimide-type copolymer composition of 6) or 7) using the radical scavenger whose 1% loss-on-heating temperature exceeds 290 degreeC.
9) The manufacturing method of the maleimide-type copolymer composition in any one of 6) -8) which uses together 2 or more types of radical scavengers.
10) Any of 6) to 9) which is maleimidated with 1.0 to 1.4 molar equivalents of aniline in the presence of 0.01 to 0.10 molar equivalents of triethylamine with respect to the unsaturated dicarboxylic anhydride group. A method for producing such a maleimide copolymer composition.
11) After blending a liquid polydiene and a radical scavenger with the maleimide copolymer, remove the volatile components at a resin temperature of less than 360 ° C. and a reduced pressure of 4000 Pa or less using a vent type screw extruder. 6) The manufacturing method of the maleimide-type copolymer composition in any one of 6-10.
12) A molded product obtained by molding the maleimide copolymer according to any one of 1) to 5).
13) A molded article obtained by molding the maleimide copolymer composition obtained by any of the production methods of 6) to 11).

According to the present invention, it is possible to obtain a maleimide copolymer composition having a low maleimide monomer content and other volatile component content, a large number of maleimide monomer units, and extremely high heat resistance. It can be suitably used as a heat-imparting material for various molded products, food containers, and food packaging materials that are required to have heat resistance to cope with range heating.

The maleimide copolymer has an aromatic vinyl monomer unit, a maleimide copolymer having a maleimide monomer unit as an essential unit, and an aromatic vinyl monomer unit at the time of production of the maleimide copolymer. Add liquid polydiene to 100 parts by weight of maleimide copolymer consisting of 55-35 parts by weight, 45-65 parts by weight of maleimide monomer units and 0-10 parts by weight of monomer units copolymerizable with these monomers And a maleimide copolymer having a glass transition temperature of 180 to 230 ° C., a maleimide monomer content of 0.1 to 300 ppm, and a weight average molecular weight of 60 to 200,000.

The maleimide copolymer contains an aromatic vinyl monomer unit, a maleimide copolymer having a maleimide monomer unit as an essential unit, and a liquid polydiene. The liquid polydiene may be added either during or after the production of the maleimide copolymer, or both. Unlike the solid polydiene, the liquid polydiene can be directly supplied to the reaction vessel without the need for a prior dissolution step and pulverization step. Therefore, it is desirable to use the liquid polydiene in the present invention. When solid polydiene is used, the resin temperature at the time of devolatilization extrusion rises remarkably and tends to be undesirable.
Further, the liquid polydiene can efficiently capture the maleimide monomer generated by thermal degradation when the maleimide copolymer composition is granulated with a vent type screw extruder.

The liquid polydiene mainly used in the present invention is not particularly limited, and examples thereof include polybutadiene, polyisoprene, poly (2,3-dimethylbutadiene), polycyclohexadiene, polycyclopentadiene, polychloroprene and the like. These liquid polydienes may be used in combination of two or more, but are preferably used alone, and most preferably liquid polybutadiene is used alone.

The timing of addition of the liquid polydiene during the production of the maleimide copolymer is not particularly limited, and may be added to the polymerizable monomer mixture at the initial stage of polymerization, and the reaction mixture during or after polymerization. You may add to. Moreover, when granulating the maleimide copolymer composition containing a volatile component with a vent type screw extruder, a liquid polydiene may be added.

Since the maleimide copolymer composition has liquid polydiene added at the time of production, the maleimide copolymer composition contains liquid polydiene or liquid polydiene derivative. Here, the liquid polydiene derivative is not particularly limited as long as it is a substance obtained using liquid polydiene as a starting material. For example, a monomer such as an aromatic vinyl monomer or a maleimide monomer is added to the liquid polydiene. Examples thereof include a graft polymerization product obtained by graft polymerization, a thermal decomposition product of the graft polymerization product, a reaction product of a liquid polydiene and a maleimide monomer, and a thermal decomposition product of a free liquid polydiene. The liquid polydiene content and the liquid polydiene derivative content can be qualitatively quantified by halogen addition method, Soxhlet extraction method, high performance liquid chromatography-mass spectrometry, high performance liquid chromatography-infrared spectroscopic analyzer, GPC or the like.

The liquid polydiene refers to one that does not contain a volatile component such as an organic solvent, and it is preferable to use a liquid polydiene having a purity of 99% or more. The number average molecular weight of the liquid polydiene used in the present invention is 500 to 10,000, preferably 1,000 to 5,000. Moreover, the viscosity of liquid polydiene is 500-5000 mPa * s, and 1000-3000 mPa * s is more preferable.
When the number average molecular weight exceeds 10,000 or when the viscosity exceeds 5000 mPa · s, handling may be difficult. When the number average molecular weight is less than 500 or the viscosity is less than 500 mPa · s, the odor may increase. There is.

The addition amount of the liquid polydiene is 0.01 to 4 parts by mass with respect to 100 parts by mass of the maleimide copolymer. A preferable addition amount is 0.5 to 4 parts by mass, and a particularly preferable addition amount is 2 to 4 parts by mass. If the amount added is small, the maleimide monomer content in the maleimide copolymer composition may be insufficiently reduced. Moreover, when there is much addition amount, there exists a tendency for the heat resistance of a maleimide-type copolymer composition to deteriorate.

The maleimide monomer unit in the maleimide copolymer is required to be 45 to 65 parts by mass of the total monomer units. Preferably it is 50-65 mass parts, Most preferably, it is 53-60 mass parts. When there is little content, the function as a heat-resistant provision material of the maleimide-type copolymer composition obtained will fall, and the objective of this invention may not be achieved. When the content is large, the heat resistance of the resulting maleimide copolymer is improved, but the moldability of the resulting maleimide copolymer composition and a molded product using the composition may deteriorate.
The maleimide monomer unit in the maleimide copolymer can be controlled mainly by the charge composition of the monomer, and the content of the maleimide monomer unit in the maleimide copolymer is determined by NMR measurement, elemental analysis, It can be determined by pyrolysis gas chromatography or the like.

The glass transition temperature of the maleimide copolymer is 180 to 230 ° C, preferably 190 to 220 ° C, more preferably 200 to 220 ° C.
When the glass transition temperature is lower than 180 ° C., the heat resistance of the resulting maleimide copolymer composition tends to be lowered, and the effect of imparting heat resistance may not be sufficient. When the temperature is higher than 230 ° C., the resin temperature tends to be high in the step of granulating the resulting maleimide copolymer composition, and the volatile component in the reimide copolymer is caused by thermal degradation accompanied by depolymerization of the resin. There is a tendency to increase. The glass transition temperature of the maleimide copolymer can be controlled by the content of maleimide monomer units in the maleimide copolymer, the molecular weight of the maleimide copolymer, and the amount of additives such as a plasticizer. The glass transition temperature of the copolymer can be determined by differential scanning calorimetry, dynamic viscoelasticity analysis, or the like.

The maleimide monomer in the maleimide copolymer is 0.1 to 300 ppm. Preferably it is 0.1-100 ppm, More preferably, it is 0.1-70 ppm, Most preferably, it is 0.1-10 ppm. When there is more content than 300 ppm, the hue of the maleimide-type copolymer composition obtained may deteriorate, and an odor may become a problem.

The weight average molecular weight of the maleimide copolymer is 60,000 to 200,000, preferably 90000 to 140000, and more preferably 80000 to 120,000. If the weight average molecular weight exceeds 200,000, the maleimide copolymer may be thermally deteriorated in the step of granulating with a bent screw type extruder, and volatile components may increase. If the weight average molecular weight is lower than 60000, maleimide alone There exists a tendency for content of volatile components other than a monomer content and a maleimide monomer to increase.

The content of volatile components other than the maleimide monomer in the maleimide copolymer composition is 0.1 to 1000 ppm, preferably 0.1 to 800 ppm, more preferably 0.1 to 500 ppm, particularly preferably. 0.1 to 300 ppm. If the content is more than 800 ppm, the use of the resulting maleimide copolymer composition may be limited.
As volatile components other than maleimide monomers, in addition to monomers of aromatic vinyl monomers, monomers copolymerizable with maleimide monomers and aromatic vinyl monomers, these Any combination of dimer to hexamer oligomers selected from the monomer group, solvent used when employing the solution polymerization method, and amines when employing the post-imidation method as described later Is mentioned. Among these volatile components, for oligomers, non-polymerizable solvents, and amines, the resin temperature at the time of devolatilization of the maleimide copolymer composition should be about 320 to 360 ° C., and the degree of vacuum should be about 2000 Pa. Can be reduced to the order of several ppm. However, under the same devolatilization conditions, monomers in the maleimide copolymer composition, such as aromatic vinyl monomers, increase due to thermal degradation of the resin accompanying depolymerization. It is preferable to use a scavenger.
The maleimide monomer residual amount, aromatic vinyl monomer residual amount, and other volatile component residual amount in the maleimide copolymer composition of the present invention are gas chromatography, gas chromatography-mass spectrometer, It can be quantified by high performance liquid chromatography.

The radical scavenger is mainly used for the purpose of reducing monomers such as an aromatic vinyl monomer generated due to thermal deterioration in a granulation process in a vent type screw type extruder.
Although the radical scavenger used by this invention is not specifically limited, For example, antioxidants, such as a phenol type compound, an organic phosphorus type compound, an organic sulfur type compound, an amine type compound, are mentioned. These radical scavengers may be used alone or more preferably in combination of two or more. These radical scavengers preferably have a 1% heat loss temperature exceeding 290 ° C, more preferably a radical scavenger having a 5% heat loss temperature exceeding 330 ° C.

The addition amount of the radical scavenger is 0.01 to 2 parts by mass, the preferable addition amount is 0.3 to 2 parts by mass, and the particularly preferable addition amount is 0.6 to 2 parts by mass. When the addition amount is less than 0.01 parts by mass, the reduction of volatile components is insufficient, and when the addition amount is more than 2 parts by mass, the hue of the maleimide copolymer tends to deteriorate.

The timing of adding the radical scavenger is not particularly limited, but it is preferably added when granulating the maleimide copolymer product composition with a vent type screw extruder.

The resin temperature in the step of granulating the maleimide copolymer product composition with a vent-type screw extruder is the maximum temperature of the maleimide copolymer in a molten state in the extruder. This resin temperature can be adjusted by the glass transition temperature of the resin, the melt viscosity, the screw rotation speed of the extruder, and the heating temperature of the extruder. The resin temperature in the method for producing a maleimide copolymer composition is preferably less than 360 ° C, preferably less than 355 ° C, and more preferably less than 350 ° C.

Although it does not specifically limit as an aromatic vinyl monomer, For example, although styrene, (alpha) -methylstyrene, vinyl toluene, t-butyl styrene, chlorostyrene etc. are mentioned, these aromatic vinyl monomers are Although it may be used alone or in combination of two or more, it is particularly preferable to use styrene or α-methylstyrene alone. These aromatic vinyl monomer units are required to be 35 to 55 parts by mass in the maleimide copolymer composition. Preferably it is 35-50 mass parts, Most preferably, it is 40-55 mass parts. If the content is large, the function of the resulting maleimide copolymer composition as a heat-resistance imparting material is lowered, and the object of the present invention may not be achieved. Moreover, when there is little content, although the heat resistance of the maleimide-type copolymer composition obtained will improve, the moldability of the maleimide-type copolymer composition obtained and a molded article using the same may deteriorate.

The polymerization mode of the maleimide copolymer is not particularly limited, and can be produced by a known method such as solution polymerization or bulk polymerization, but solution polymerization is more preferable. The solvent used in the solution polymerization is preferably non-polymerizable. Further, the polymerization process may be any of batch polymerization method, semi-batch polymerization method and continuous polymerization method.

The polymerization method of the maleimide copolymer is not particularly limited, but is preferably obtained by radical polymerization. The polymerization initiator is not particularly limited, for example, known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobismethylbutyronitrile, Benzoyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2- Known organic peroxides such as ethyl hexanoate, di-t-butyl peroxide, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate can be used. These polymerization initiators may be used in combination of two or more, but those commonly used in the production of conventional styrene resins, such as azo compounds and organic peroxides having a 10-hour half-life temperature of 70 to 120 ° C. It is preferable to use an oxide. The amount used is not particularly limited, but it is preferably 0.1 to 1.5 parts by weight, more preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of all monomer units. is there. If the amount is less than 0.1 parts by mass, a sufficient polymerization rate may not be obtained. If it exceeds 1.5 parts by mass, the polymerization rate increases and the reaction control becomes difficult, and the target molecular weight of the maleimide copolymer may not be obtained.

A chain transfer agent can be used as needed for the production of the maleimide copolymer. Although it does not specifically limit as a chain transfer agent used, For example, well-known chain transfer agents, such as n-dodecyl mercaptan, t-dodecyl mercaptan, and 2, 4- diphenyl-4-methyl- 1-pentene, are used. Can be used. The amount used is not particularly limited, but it is preferably 0.01 to 0.8 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of all monomer units. is there. When the amount is less than 0.01 parts by mass, the molecular weight of the maleimide copolymer of the present invention increases, and the mixing with ABS resin or the like may deteriorate. When the content is large, the molecular weight of the maleimide copolymer is remarkably lowered, and the physical properties after mixing with ABS resin or the like may deteriorate.

The polymerization temperature during the production of the maleimide copolymer is preferably 60 to 150 ° C, more preferably 70 to 120 ° C. If it is less than 60 ° C., a sufficient polymerization rate cannot be obtained, and the time required for the polymerization becomes long, which is not preferable from the viewpoint of productivity. When the polymerization temperature exceeds 150 ° C., the ratio of thermal polymerization increases remarkably, so that a sufficient molecular weight may not be obtained.

The type of non-polymerizable solvent is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, benzene, toluene, and xylene , Aromatic hydrocarbons such as chlorobenzene, solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc. from the viewpoint of ease of handling such as volatility and copolymer solubility, Methyl isobutyl ketone is particularly preferred.

Maleimide monomer units can be introduced by copolymerizing maleimide monomer with an aromatic vinyl monomer or other copolymerizable monomer (direct method), or by unsaturated unsaturated dicarboxylic acid anhydride. Copolymerization with an aromatic vinyl monomer or other copolymerizable monomer in advance, and further reacting the unsaturated dicarboxylic acid anhydride group with a primary amine to convert the unsaturated dicarboxylic acid anhydride group to maleimide monomer. There is a method (post-imidization method) for converting to a monomer unit. A maleimide copolymer obtained by a post-imidization method in which a small amount of unsaturated dicarboxylic acid tends to remain is often more excellent in compatibility with an ABS resin. The maleimide monomer unit is not particularly limited. For example, N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N- Butylmaleimide, N-isobutylmaleimide and the like can be mentioned, but these maleimide monomers may be used alone or in combination of two or more, but N-phenylmaleimide and N-cyclohexylmaleimide are used. It is particularly preferable to use it.
Although it does not specifically limit as a primary amine used for a post-imidation method, For example, a methylamine, an ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n -Alkylamines such as hexylamine, n-octylamine, cyclohexylamine, and decylamine, and aromatic amines such as chloro or bromo-substituted alkylamine, aniline, toluidine, and naphthylamine, among which aniline and cyclohexylamine are listed. Particularly preferred. In addition, these primary amines may be used alone or in combination of two or more. The addition amount of the primary amine is not particularly limited, but if the imidization is carried out by adding a large excess (equal mole or more) of the primary amine to the unsaturated dicarboxylic anhydride group, Saturated dicarboxylic anhydride groups can be completely converted to maleimide monomer units. When introducing a maleimide monomer unit by a post-imidation method, in the reaction between a primary amine and an unsaturated dicarboxylic acid anhydride group, particularly in the reaction for converting an unsaturated dicarboxylic acid anhydride group to a maleimide group, A catalyst can be used as needed for the purpose of improving the reaction. Although the kind of catalyst is not specifically limited, For example, a tertiary amine can be used. The tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline and the like. The amount of primary amine used for the unsaturated dicarboxylic acid anhydride group in the post-imidization method is not particularly limited, but is 1.0 to 1.4 molar equivalents, preferably 1.0 to 1.2 molar equivalents. is there.
The amount of tertiary amine added is not particularly limited, but is 0.01 to 0.110 molar equivalents, preferably 0.01 to 0.04 molar equivalents relative to the unsaturated dicarboxylic anhydride group. .
The temperature of the imidization reaction is preferably 80 to 250 ° C, more preferably 100 to 200 ° C. When the temperature is lower than 80 ° C., the reaction rate is slow, and it takes a long time to complete the reaction, which is not preferable in terms of productivity. On the other hand, when the temperature exceeds 250 ° C., the physical properties of the maleimide resin may deteriorate due to thermal deterioration.

The maleimide copolymer has an aromatic vinyl monomer and a maleimide monomer as essential units, but a monomer unit that can be copolymerized with these two monomers may be copolymerized. The type of the copolymerizable monomer is not particularly limited. For example, unsaturated dicarboxylic acid anhydride monomers such as maleic anhydride, itaconic anhydride, citraconic anhydride, acrylonitrile, methacrylonitrile, Unsaturated nitriles such as ethacrylonitrile and phenylacrylonitrile, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid An acid, acrylic acid, etc. can be mentioned. Among these monomers, unsaturated dicarboxylic anhydride monomers such as maleic anhydride are more preferable because they are highly reactive and can be used for various polymer reactions. These monomer units in the maleimide copolymer composition are 0 to 10 parts by mass, preferably 0 to 8 parts by mass, particularly preferably 0 to 5 parts by mass.

The maleimide copolymer composition includes styrene-acrylonitrile copolymer resin (SAN resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-butadiene-styrene-α-methylstyrene copolymer resin, acrylonitrile-acrylic. Rubber-styrene copolymer resin, acrylonitrile-ethylene / propylene rubber-styrene copolymer resin, styrene-methyl methacrylate copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, aromatic polycarbonate, aromatic polyester, polyphenylene sulfide, It can also be mixed with polyamide, polyurethane, etc., and can be used as a heat imparting material for these resins.

When manufacturing maleimide copolymers by post-imidization, it is easy to adjust the content of reactive functional groups such as unsaturated dicarboxylic acid anhydride groups. It can also be used as a compatibilizing agent.
In addition, when the maleimide copolymer composition is used as a heat resistance imparting material such as ABS resin or a compatibilizer for various alloys, it is further provided with a stabilizer, ultraviolet absorber, flame retardant, plasticizer, lubricant, glass fiber, inorganic Fillers, colorants, antistatic agents, etc. may be added.

The yellowness of the maleimide copolymer composition is not particularly limited, but is preferably less than 5, more preferably less than 3.5, and particularly preferably less than 2.5. If the yellowness is high, the hue of the resulting maleimide copolymer composition tends to deteriorate, which may be undesirable.

Hereinafter, the present invention will be described by way of examples. Note that the present invention is not limited to these examples.

  Example 1 In a 300 l autoclave equipped with a stirrer, 60.0 kg of styrene, 11.2 kg of methyl ethyl ketone, 0.16 kg of 2,4-diphenyl-4-methyl-1-pentene, liquid polybutadiene (poly oil 110 manufactured by Nippon Zeon Co., Ltd., number (Average molecular weight 1600, viscosity 800 mPa · s) 0.06 kg, the inside of the system was sufficiently replaced with nitrogen gas, and then the internal temperature of the can was raised to 92 ° C. A solution prepared by dissolving 40 kg of maleic anhydride and 0.16 kg of t-butylperoxy-2-ethylhexanoate in 126 kg of methyl ethyl ketone in a separate container was added at a uniform addition rate over 5 hours. After the addition, the temperature was raised to 120 ° C., and the mixture was further reacted for 1 hour, and then 1.2 molar equivalents of aniline with respect to the maleic anhydride group and 0.02 molar equivalents of triethylamine with respect to the maleic anhydride group were added. . Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After completion of the reaction, the imidization reaction liquid was charged into a vent type screw extruder to remove volatile matter, thereby obtaining a pellet-like maleimide copolymer composition. The resin temperature during devolatilization was 358 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

  Example 2 0.36 kg of liquid polybutadiene was used, and Sumidizer GA-80 manufactured by Sumitomo Chemical Co., Ltd. as a radical scavenger in the imidation reaction solution after completion of the imidation reaction, chemical name: 3,9-bis [2- [3- ( 3-tertiarybutyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl] 2,4,8,10, 0.08 kg of tetraoxaspiro [5.5] undecane) was added. Except for the above, a pellet-like maleimide copolymer composition was obtained in the same manner as in Example 1. The resin temperature during devolatilization was 357 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

  Example 3 By the same method as in Example 2, except that 0.25 kg of 2,4-diphenyl-4-methyl-1-pentene, 0.78 kg of liquid polybutadiene, and 0.4 kg of the radical scavenger were changed. A pellet-like maleimide copolymer composition was obtained. The resin temperature during devolatilization was 353 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

  Example 42, 0.25 kg of 4-diphenyl-4-methyl-1-pentene, 0.78 kg of liquid polybutadiene, 0.2 kg of Sumilizer GA-80 as a radical scavenger, Sumitizer TP-D manufactured by Sumitomo Chemical Co., Ltd. Name: Pentaerythylyltetrakis (Pellet-like maleimide copolymer composition was obtained in the same manner as in Example 2 except that 0.2 kg of 3-laurylthiopropionate was added. Resin temperature during devolatilization Was 355 ° C. and the degree of vacuum was 2000 Pa. Table 1 shows the analysis results of the obtained maleimide copolymer composition.

  Example 5 0.25 kg of 2,4-diphenyl-4-methyl-1-pentene, 3.4 kg of liquid polybutadiene, 0.8 kg of Sumilizer GA-80 as a radical scavenger, and 0.7 kg of Sumilizer TP-D A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 2 except that. The resin temperature during devolatilization was 348 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 6 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 5 except that 3.4 kg of liquid polybutadiene was added after completion of the polymerization reaction. The resin temperature during devolatilization was 348 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 7 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 5 except that 3.4 kg of liquid polybutadiene was added after completion of the imidization reaction. The resin temperature during devolatilization was 348 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 8 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 5 except that Sumilizer GA-80 was changed to 1.5 kg as a radical scavenger. The resin temperature during devolatilization was 348 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 9 In an autoclave equipped with a stirrer, 53 kg of styrene, 11.2 kg of methyl ethyl ketone, 0.25 kg of 2,4-diphenyl-4-methyl-1-pentene, liquid polybutadiene (poly oil 110 manufactured by Nippon Zeon Co., Ltd., number average molecular weight 1600, (Viscosity 800 mPa · s) 3.4 kg and the inside of the system was sufficiently replaced with nitrogen gas, and then the internal temperature of the can was raised to 92 ° C. A solution prepared by dissolving 47 kg of maleic anhydride and 0.16 kg of t-butylperoxy-2-ethylhexanoate in 126 kg of methyl ethyl ketone in a separate container was added over 4 hours at a uniform addition rate. After the addition, the temperature was raised to 120 ° C., and the mixture was further reacted for 1 hour, and then 1.2 molar equivalents of aniline with respect to the maleic anhydride group and 0.02 molar equivalents of triethylamine with respect to the maleic anhydride group were added. . Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After adding 1.5 kg of Sumilizer GA-80 as a radical scavenger to the imidization reaction liquid after completion of the imidization reaction, the imidization reaction liquid after completion of the reaction is put into a vent type screw type extruder to remove volatile components. Thus, a pellet-like maleimide copolymer composition was obtained. The resin temperature during devolatilization was 357 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 10 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 8 except that 2,4-diphenyl-4-methyl-1-pentene was changed to 0.05 kg. The resin temperature during devolatilization was 351 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 11 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 8 except that 2,4-diphenyl-4-methyl-1-pentene was changed to 0.02 kg. The resin temperature during devolatilization was 357 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 12 In an autoclave equipped with a stirrer, 63 kg of styrene, 11.2 kg of methyl ethyl ketone, 0.25 kg of 2,4-diphenyl-4-methyl-1-pentene, liquid polybutadiene (poly oil 110 manufactured by ZEON Corporation, number average molecular weight 1600, (Viscosity 800 mPa · s) 3.4 kg and the inside of the system was sufficiently replaced with nitrogen gas, and then the internal temperature of the can was raised to 92 ° C. A solution prepared by dissolving 37 kg of maleic anhydride and 0.16 kg of t-butylperoxy-2-ethylhexanoate in 126 kg of methyl ethyl ketone in a separate container was added over 6 hours at a uniform addition rate. After the addition, the temperature was raised to 120 ° C., and the mixture was further reacted for 1 hour, and then 1.2 molar equivalents of aniline with respect to the maleic anhydride group and 0.02 molar equivalents of triethylamine with respect to the maleic anhydride group were added. . Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After adding 0.8 kg of Sumilizer GA-80 and 0.7 kg of Sumizer TP-D as radical scavengers to the imidation reaction liquid after completion of the imidization reaction, the imidization reaction liquid after completion of the reaction is vent type screw type extrusion The volatile matter was removed, and a pellet-like maleimide copolymer composition was obtained. The resin temperature during devolatilization was 340 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 13 In an autoclave equipped with a stirrer, 66 kg of styrene, 11.2 kg of methyl ethyl ketone, 0.44 kg of 2,4-diphenyl-4-methyl-1-pentene, liquid polybutadiene (poly oil 110 manufactured by Nippon Zeon Co., Ltd., number average molecular weight 1600, (Viscosity 800 mPa · s) 3.4 kg and the inside of the system was sufficiently replaced with nitrogen gas, and then the internal temperature of the can was raised to 92 ° C. A solution prepared by dissolving 34 kg of maleic anhydride and 0.16 kg of t-butylperoxy-2-ethylhexanoate in 126 kg of methyl ethyl ketone in a separate container was added at a uniform addition rate over 8 hours. After the addition, the temperature was raised to 120 ° C., and the mixture was further reacted for 1 hour, and then 1.2 molar equivalents of aniline with respect to the maleic anhydride group and 0.02 molar equivalents of triethylamine with respect to the maleic anhydride group were added. . Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After adding 0.8 kg of Sumilizer GA-80 and 0.7 kg of Sumizer TP-D as radical scavengers to the imidation reaction liquid after completion of the imidization reaction, the imidization reaction liquid after completion of the reaction is vent type screw type extrusion The volatile matter was removed, and a pellet-like maleimide copolymer composition was obtained. The resin temperature during devolatilization was 320 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 14 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 5 except that the liquid polybutadiene was changed to 6.3 kg. The resin temperature during devolatilization was 320 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Example 15 As a radical scavenger, a pellet-like maleimide copolymer composition was obtained in the same manner as in Example 5 except that Sumilizer GA-80 was changed to 2.5 kg. The resin temperature during devolatilization was 350 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Comparative Example 1 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 1 except that liquid polybutadiene was not added. The resin temperature during devolatilization was 358 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Comparative Example 2 In an autoclave equipped with a stirrer, 48 kg of styrene, 137 kg of methyl ethyl ketone, 0.3 kg of 2,4-diphenyl-4-methyl-1-pentene, 0.06 kg of liquid polybutadiene (poly oil 110 manufactured by Nippon Zeon Co., Ltd.), maleic anhydride 52 kg, t-butyl peroxy-2-ethylhexanoate 0.16 kg was added. After sufficiently replacing the inside of the system with nitrogen gas, the internal temperature of the can was raised to 92 ° C. and reacted for 3 hours. Thereafter, the temperature was raised to 120 ° C., and the reaction was further continued for 1 hour. Thereafter, 1.2 molar equivalents of aniline with respect to maleic anhydride groups and 0.02 molar equivalents of triethylamine with respect to maleic anhydride groups were added. Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After adding 0.05 kg of Sumilizer GA-80 as a radical scavenger to the imidization reaction solution after completion of the reaction, it is put into a vent type screw type extruder to remove volatile matter, and a pellet-like maleimide copolymer composition I got a thing. The resin temperature during devolatilization was 370 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Comparative Example 3 A pellet-shaped maleimide copolymer composition was obtained in the same manner as in Example 3 except that the liquid polybutadiene was changed to 10 kg and the radical scavenger was changed to 0.05 kg. The resin temperature during devolatilization was 305 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Comparative Example 4 In an autoclave equipped with a stirrer, 73 kg of styrene, 11.2 kg of methyl ethyl ketone, 0.3 kg of 2,4-diphenyl-4-methyl-1-pentene, 0.03 kg of liquid polybutadiene (poly oil 110 manufactured by Nippon Zeon Co., Ltd.), system After the inside was sufficiently replaced with nitrogen gas, the internal temperature of the can was raised to 92 ° C. A solution prepared by dissolving 27 kg of maleic anhydride and 0.16 kg of t-butylperoxy-2-ethylhexanoate in 126 kg of methyl ethyl ketone in a separate container was added over 9 hours at a uniform addition rate. After the addition, the temperature was raised to 120 ° C., and the reaction was further continued for 1 hour. Thereafter, 1.2 molar equivalents of aniline with respect to maleic anhydride groups and 0.02 molar equivalents of triethylamine with respect to maleic anhydride groups were added. Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After adding 0.02 kg of Sumilizer GA-80 as a radical scavenger to the imidization reaction solution after completion of the reaction, it is put into a vent type screw type extruder to remove volatile matter and pellet-shaped maleimide copolymer A composition was obtained. The resin temperature during devolatilization was 305 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Comparative Example 5 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 2 except that the liquid polybutadiene was changed to 0.005 kg and the radical scavenger was changed to 0.05 kg. The resin temperature during devolatilization was 355 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

Comparative Example 6 A pellet-like maleimide copolymer composition was obtained in the same manner as in Example 1 except that 2,4-diphenyl-4-methyl-1-pentene was not added. The resin temperature during devolatilization was 365 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

  Comparative Example 7 A pellet-like maleimide copolymer was obtained in the same manner as in Example 1 except that 2,4-diphenyl-4-methyl-1-pentene was changed to 1.5 kg. The resin temperature during devolatilization was 295 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

  Comparative Example 8 In an autoclave equipped with a stirrer, 60.0 kg of styrene, 11.2 kg of methyl ethyl ketone, 0.16 kg of 2,4-diphenyl-4-methyl-1-pentene, solid polybutadiene rubber (UBEPOL-BR22H manufactured by Ube Industries) Was added to completely dissolve the rubber to prepare a rubber styrene solution. In a separate autoclave equipped with a stirrer, a total amount of styrene solution of rubber, 11.2 kg of methyl ethyl ketone, 0.3 kg of 2,4-diphenyl-4-methyl-1-pentene was charged, and the inside of the system was sufficiently replaced with nitrogen gas. The internal temperature of the can was raised to 92 ° C. A solution prepared by dissolving 40 kg of maleic anhydride and 0.16 kg of t-butylperoxy-2-ethylhexanoate in 126 kg of methyl ethyl ketone was added to a separate container at a uniform addition rate over 5 hours. After the addition, the temperature was raised to 120 ° C., and the mixture was further reacted for 1 hour, and then 1.2 molar equivalents of aniline with respect to the maleic anhydride group and 0.02 molar equivalents of triethylamine with respect to the maleic anhydride group were added. . Thereafter, the internal temperature of the can was raised to 155 ° C. and reacted for 5 hours. After completion of the reaction, the imidization reaction liquid was charged into a vent type screw extruder to remove volatile matter, thereby obtaining a pellet-like maleimide copolymer composition. The resin temperature during devolatilization was 371 ° C., and the degree of vacuum was 2000 Pa. The analysis results of the obtained maleimide copolymer composition are shown in Table 1.

  In all the maleimide copolymer compositions of Examples and Comparative Examples, maleic anhydride monomer units could not be confirmed (ND).

The measuring method of each physical property value is as follows.
(1) Measurement of residual amount of maleimide monomer, residual amount of aromatic vinyl monomer, and other residual amount of volatile matter The measurement was performed under the following measurement conditions.
Device name: Agilent 6890 series (manufactured by Agilent)
Column: Capillary column (dimethylpolysiloxane, cross-linked type)
Temperature: Oven: 50 ° C, inlet: 200 ° C, detector: 250 ° C
Detector: FID
Procedure: 0.50 g of sample and 0.001 g of n-octane were weighed and dissolved in methyl ethyl ketone to make 25.0 g as a whole, and n-octane was measured as an internal standard.
(2) Measurement of maleimide monomer unit and maleic anhydride unit in maleimide copolymer composition / Maleimide monomer unit NMR was measured under the following measurement conditions, and the intensity of imide carbonyl carbon signal near 175 ppm Thus, the maleimide monomer unit in the maleimide copolymer composition was determined.
Device name: AVANCE-300 (manufactured by BRUKER)
Measurement nuclide: C13
Measurement temperature: 110 ° C
Sample concentration: 10 parts by mass Solvent used: DMSO-d6
Integration number: 10,000 times / maleic anhydride monomer unit The neutralization titration method was used.
(3) Glass transition temperature It measured with DSC (differential scanning calorimetry) apparatus according to JIS K-7121.
(4) Weight average molecular weight device name: SYSTEM-21 Shodex (Showa Denko)
Column: 3 series PL gel MIXED-B Temperature: 40 ° C
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: produced using standard polystyrene (PS) (manufactured by PL), and the weight average molecular weight was expressed in terms of PS.
(5) Yellowness The yellowness of the maleimide copolymer composition was determined by the following method.
Apparatus: SZ-II Sigma 80 colorimetric color difference meter (manufactured by Nippon Denshoku)
Temperature: 23 ° C ± 2 ° C
Solvent: Tetrahydrofuran Measurement mode: Permeation method

Claims (13)

Maleimide copolymer 100 comprising 55-35 parts by weight of aromatic vinyl monomer units, 45-65 parts by weight of maleimide monomer units, and 0-10 parts by weight of monomer units copolymerizable with these monomers. A maleimide copolymer composition in which 0.01 to 4 parts by mass of liquid polydiene is added to parts by mass and the content of maleimide monomer is 0.1 to 300 ppm. The maleimide copolymer composition according to claim 1, wherein the liquid polydiene has a number average molecular weight of 500 to 10,000 and a viscosity of 500 to 5000 mPa · s. The maleimide copolymer composition according to claim 1 or 2, wherein the maleimide copolymer has a glass transition temperature of 180 to 230 ° C and a weight average molecular weight of 60000 to 200000. The maleimide copolymer composition according to any one of claims 1 to 3, wherein the volatile component other than the maleimide monomer is 0.1 to 1000 ppm and the yellowness is less than 5. The maleimide copolymer composition according to any one of claims 1 to 4, wherein the liquid polydiene is polybutadiene. To 100 parts by mass of a maleimide copolymer prepared by maleimidizing a copolymer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride with a primary amine, 0.01 to 4 parts by mass of a liquid polydiene and The manufacturing method of the maleimide-type copolymer composition which adds 0.01-2 mass parts of radical scavengers. The method for producing a maleimide copolymer composition according to claim 6, wherein the liquid polydiene is polybutadiene. The method for producing a maleimide copolymer composition according to claim 6 or 7, wherein a radical scavenger having a 1% heat loss temperature of more than 290 ° C is used. The manufacturing method of the maleimide-type copolymer composition as described in any one of Claims 6-8 which uses 2 or more types of radical scavengers together. The maleimidation is carried out using 1.0 to 1.4 molar equivalents of aniline in the presence of 0.01 to 0.10 molar equivalents of triethylamine with respect to the unsaturated dicarboxylic anhydride group. A method for producing the maleimide copolymer composition according to claim 1. After blending a liquid polydiene and a radical scavenger with the maleimide copolymer, the volatile components are devolatilized using a vent type screw type extruder at a temperature of less than 360 ° C. and a reduced pressure of 4000 Pa or less. The manufacturing method of the maleimide-type copolymer composition as described in any one of Claims 6-10. The molded object formed by shape | molding the maleimide-type copolymer as described in any one of Claims 1-5. The molded object formed by shape | molding the maleimide-type copolymer composition obtained by the manufacturing method as described in any one of Claims 6-11.