JP3269033B2 - Method for producing maleimide-based copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a maleimide copolymer having a high glass transition temperature, which is effective as a material for improving various properties such as heat resistance by being incorporated into a molding material or a thermoplastic resin. The present invention relates to a method for obtaining a maleimide copolymer by removing volatile components from a polymer composition containing a solvent, unreacted monomers, volatile by-products or volatile components such as impurities.

[0002]

2. Description of the Related Art A maleimide copolymer is known to be a thermoplastic resin having a high heat deformation temperature and a high thermal decomposition temperature. Generally, the heat resistance and the heat resistance of products using other thermoplastic resins are known. It is used to improve impact properties and moldability. The maleimide-based copolymer is usually produced by copolymerizing a maleimide-based monomer with another monomer copolymerizable therewith.

[0003] The properties of the maleimide-based copolymer depend on the ratio of the maleimide-based monomer units in the structure. If the ratio is low, the heat resistance is low, so that sufficient heat resistance may not be imparted to the resin composition. If the ratio is too high, the molding processability may deteriorate and the impact resistance may decrease. Copolymers having a relatively small proportion of maleimide-based monomer units are generally synthesized by an emulsion polymerization method or a suspension polymerization method. According to the emulsion polymerization method, since the maleimide-based copolymer having a high ratio of the maleimide-based monomer unit is hard to soften and is very difficult to recover from the emulsion, the ratio of the maleimide-based monomer unit is low. Copolymers have been produced. A copolymer obtained by such an emulsion polymerization method is not preferred because it has poor impact resistance due to the influence of a residual emulsifier and the like and is significantly colored during molding. In the suspension polymerization method, an aromatic vinyl monomer and a maleimide monomer are easily copolymerized alternately, and if a copolymer having a high ratio of the maleimide monomer unit is to be obtained, an inhomogeneous copolymerization may occur. Coalescence is easy to form. In the solution polymerization method and the bulk polymerization method, a copolymer in which the unreacted maleimide-based monomer is reduced by an aging reaction, or a composition distribution in each molecular weight category is narrow by a specific polymerization method, and the amount of unreacted maleimide-based monomer is small. Various studies have been made in order to obtain coalescence.

A maleimide copolymer is obtained in a solution state in solution polymerization or bulk polymerization, and in a dispersion state in emulsion polymerization or suspension polymerization. From these conditions, the solvent, unreacted monomer,
It is necessary to obtain a maleimide-based copolymer by separating volatile components such as volatile by-products or impurities. This is because if volatile components such as a solvent and unreacted monomer remain in the maleimide-based copolymer, deterioration of physical properties such as heat resistance and poor appearance of a molded product (silver streak) occur. This is because the physical properties of the product are significantly reduced.

For this reason, in the emulsion polymerization method and the suspension polymerization method,
A method of separating a polymer by coagulation, filtration, steam stripping, or the like has been adopted (Japanese Patent Application Laid-Open No. 62-1).
12612, 62-138510). On the other hand, in solution polymerization or bulk polymerization, the reaction solution after polymerization is placed in another solvent in which the solvent and unreacted monomer are dissolved but the maleimide-based copolymer to be recovered is not dissolved, and the unreacted monomer is removed. Or solvent by extraction (JP-A-58-162616).
After evaporating unreacted monomers and solvents using a flash evaporator, the polymer is extracted in a molten state (JP-A-61-276807, JP-A-3-205411).
JP-A No. 62-129334), and the like.

A method is known in which the reaction mixture after the polymerization is directly or directly heated or dried and then supplied to a vent-type extruder to pelletize the polymer while devolatilizing (Japanese Patent Laid-Open No. 59-1984). -126411, 59-580
06, 57-135814, 50-40688, 57-
49603, 50-40687, 63-147501 and JP-A-3-49925). Such a method is also used as a method for obtaining a maleimide-based copolymer (JP-A-2-51514, JP-A-63-1988).
-89806).

[0007]

The glass transition temperature is 17
Maleimide copolymers exceeding 0 ° C. generally have a high thermal decomposition temperature and excellent thermal stability, but have a remarkably high melt viscosity, so that at a higher temperature than general-purpose plastics such as polystyrene and polymethyl methacrylate. Need to be handled. In particular, in order to melt and transfer the polymer, it is necessary to lower the viscosity by heating the polymer to 300 ° C. or higher. Even if a polymer is excellent in thermal stability, it will be colored and thermally degraded if handled at a high temperature such that the viscosity becomes low.

In the conventional drying method using a flash evaporator, after the flash, the thermoplastic polymer is heated and melted and discharged by a gear pump or the like. Can not. In the method of extracting and removing with a solvent, the steps of washing, filtering and drying the thermoplastic polymer after the extraction are required, and the steps are complicated because a distillation separation step for recovering a large amount of the solvent is required. Become. In the method of supplying a reaction mixture with a large amount of volatile components directly to a vent type extruder, the thermoplastic polymer is strongly foamed due to gasification of the volatile components in the vent type extruder, and the vent is blocked by the foamed polymer. Troubles, making it difficult to operate continuously for a long time, or requiring large equipment due to the large amount of volatile components, or an extruder to remove a large amount of volatile components. The residence time in the polymer becomes longer and the polymer is altered or colored.

In other methods for removing volatile components, it takes a long time to raise the temperature of the polymer, the non-volatile component after removing the volatile components is transported as a high-viscosity fluid, The residence time causes the deterioration of the polymer and the generation of side reaction products. The present invention can efficiently remove volatile components from a maleimide-based copolymer composition containing a volatile component, such as a polymerization reaction solution, and
By not heating the maleimide-based copolymer with a high melt viscosity more than necessary, without causing physical property deterioration,
It is an object of the present invention to provide a method capable of obtaining a maleimide-based copolymer having a low residual volatile component content.

[0010]

Means for Solving the Problems The inventors of the present invention have studied various methods for removing volatile components, and as a result, have found that in order to efficiently remove volatile components from a maleimide-based copolymer composition containing volatile components. Is that the process is relatively simple, there is no need to use a large amount of solvent, and there is no need to heat the copolymer to a high temperature for a long time. Research was conducted on the belief that the method of treating the coalesced composition was appropriate. As a result, when the above-described copolymer composition is treated by operating a vent-type extruder under operating conditions that have not been conventionally performed at all, foaming of the maleimide-based copolymer accompanying the gasification of volatile components as described above. The present invention has been accomplished by finding that little or no occurrence occurs and that there is no need to extend the residence time of the copolymer in the extruder to remove a large amount of volatile components.

Accordingly, in order to solve the above-mentioned problems, the present invention is to treat a maleimide-based copolymer having a glass transition temperature of 170 ° C. or more and a polymer composition containing a volatile component with a vent-type screw extruder. A method for producing a maleimide-based copolymer in which volatile components are removed by:
A maleimide-based copolymer, wherein the extruder is operated at a screw rotation speed of 50 to 150 rpm, and water is injected from an injection port located ahead of a workpiece supply port of the extruder. And a method for producing the same. In addition, a maleimide copolymer having a glass transition temperature of 170 ° C. or higher and a polymer composition containing a volatile component is treated with a vent-type screw extruder to remove the volatile component, thereby producing a maleimide copolymer. A method wherein the polymer composition is heated to 150 to 300 ° C. and pressurized to 5 to 30 atm and then supplied to the extruder, and the extruder is operated at a screw rotation speed of 50 to 150 rpm. The present invention also provides a method for producing a maleimide-based copolymer characterized by the following.

In the present invention, the glass transition temperature of the maleimide-based copolymer is a value measured using a differential thermal balance. The volatile component amount is a value obtained by dissolving the maleimide copolymer in chloroform and quantifying the remaining volatile components by gas chromatography. The molecular weight retention at 280 ° C.
After heating the copolymer to 280 ° C. for 10 minutes under reduced pressure conditions (20 mmHg or less) using a differential thermobalance, the ratio of the molecular weight of the copolymer obtained by quenching to the molecular weight of the copolymer before the treatment is obtained. It is.

The maleimide-based copolymer having a glass transition temperature of 170 ° C. or more is produced, for example, by copolymerizing a maleimide-based monomer and another copolymerizable monomer. A maleimide copolymer having an aromatic vinyl monomer unit and a maleimide monomer unit as main components has heat resistance,
It is excellent in processability and impact resistance as well as in thermal stability. By changing the composition ratio of each monomer unit, copolymers having a glass transition temperature of 170 ° C or higher, preferably 180 ° C or higher can be easily obtained. Is preferred. Polymers having a glass transition temperature of less than 170 ° C. can have their volatile components removed by conventional devolatilization methods.

The maleimide copolymer is obtained by copolymerizing an aromatic vinyl monomer (a) and a maleimide monomer (b), or by copolymerizing the monomers (a), (b) and Or by copolymerizing other monomers (c). The aromatic vinyl monomer (a) is represented by the following formula:

[0015]

Embedded image [Wherein, R ² , R ³ and R ⁴ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁵ is an aryl group or a substituted aryl group. And styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene (o-, m-, p-
Methylstyrene is also called vinyltoluene), 1,3-
Alkyl styrenes such as dimethyl styrene, 2,4-dimethyl styrene, ethyl styrene and p-tertiary butyl styrene; α-methyl styrene, α-ethyl styrene, α
-Methyl-p-methylstyrene; vinylnaphthalene; o
Halogenated styrenes such as -chlorostyrene, m-chlorostyrene, p-chlorostyrene and 2,4-dibromostyrene; halogenated alkylstyrenes such as 2-methyl-4-chlorostyrene; divinylbenzene and the like. One or more of them can be used. From the viewpoint of the balance between productivity and physical properties, it is particularly desirable to use at least one selected from the group consisting of styrene, vinyltoluene and α-methylstyrene. Note that when an aliphatic vinyl monomer is used without using an aromatic vinyl monomer, the reactivity of the monomer is low,
Further, the obtained copolymer has low heat resistance and high hygroscopicity.

The maleimide monomer (b) has the following formula:

[0017]

Embedded image [In the formula, R ¹ is hydrogen or an alkyl group, a cycloalkyl group, a substituted alkyl group, an aryl group or a substituted aryl group having 1 to 15 carbon atoms. For example, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
N-isopropylmaleimide, N-butylmaleimide,
N-isobutylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, 2-hydroxyethylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and the like, and one or more of these may be used. Can be. In particular,
It is preferable to use one or both of phenylmaleimide and cyclohexylmaleimide since a copolymer which is easily available and has excellent heat resistance can be obtained.

In the maleimide-based copolymer, if necessary, other vinyl-based monomers (c) copolymerizable with the monomers (a) and (b) can be used. .
The monomer (c) is a compound having an ethylenically unsaturated bond other than the monomer (a) and the monomer (b), and improves, for example, impact resistance, solvent resistance, and compatibility. It is used for the purpose. Examples of the monomer (c) include unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile, and phenylacrylonitrile; and an alkyl group having 1 to 18 carbon atoms including a cycloalkyl group and a benzyl group ( (Meth) acrylic acid ester [for example, methyl (meth) acrylate, (meth)
Ethyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, (meth) ) 2-ethylhexyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate,
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like]; olefins such as ethylene, propylene, isobutylene and diisobutylene; dienes such as butadiene and isoprene; vinyl chloride; Vinyl halides such as vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl esters of saturated monocarboxylic acids such as vinyl acetate and vinyl propionate; allyl acetate and allyl propionate Allyl esters or methallyl esters of saturated aliphatic monocarboxylic acids such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diallyl phthalate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dimethacrylate of ethylene oxide or propylene oxide adduct of bisphenol A, ethylene oxide or propylene oxide of halogenated bisphenol A Multivalent (meth) such as di (meth) acrylate of adduct, tri (meth) acrylate of isocyanurate, and di or tri (meth) acrylate of ethylene oxide or propylene oxide adduct of isocyanurate
Acrylates; polyarylates such as triallyl isocyanurate; glycidyl (meth) acrylate, allyl glycidyl ether, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and half-esterified products thereof; One or two or more types are used depending on the conditions, and their types and amounts may be selected without departing from the object of the present invention.

The maleimide-based monomer (b) is a component for improving the heat resistance of the obtained copolymer, and the amount of the maleimide-based monomer (b) used depends on the amount of the aromatic vinyl-based monomer (a) and the amount of the maleimide-based monomer (b). Although it can be changed depending on the type and the ratio of the above), there is no particular problem as long as the obtained copolymer is used so that the glass transition temperature is 170 ° C. or higher. The amount of the monomer (c) to be used is preferably 0 to 20% by weight in a range where the glass transition temperature of the obtained copolymer is 170 ° C. or higher.

In the present invention, the volatile components are those having volatility such as, for example, solvents, unreacted monomers, volatile by-products or impurities. Here, the solvent may be any solvent that can be generally used in solution polymerization or the like, and examples thereof include aromatic solvents such as toluene, xylene, and ethylbenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; dimethyl sulfoxide; A polar solvent such as ethyl acetate;
Further, when a polymer is obtained by suspension polymerization or emulsion polymerization, water is used. The volatile by-product contained in the maleimide-based copolymer is a volatile low-molecular-weight substance generated during the reaction or a volatile impurity contained in the raw material.

According to the present invention, either a vent type single screw or twin screw or more screw extruder having one or more screws and one or more vents sequentially arranged along the axial direction on the side surface of the cylinder is effective. Can be used for FIG.
As shown in FIG. 1, the screw extruder 1 has a cylinder 10. The cylinder 10 is usually composed of a plurality of parts (barrels), and a vent port is provided on a side surface of the cylinder 10. The vent port has a rear vent 3 behind the supply section 2 of the raw polymer composition, and a plurality of, for example, 2 to 2 ports in front of the polymer outlet 4 after devolatilization.
5 forevents (3 forevents 5 in this figure)
a, 5b and 5c) are preferably provided, and the devolatilization rate is greatly improved by gradually lowering the exhaust pressure while the devolatilization from the polymer composition proceeds. If the number of forevents is one, the efficiency of removing volatile components may be significantly reduced, and even if six or more are used, the efficiency of removal may not be changed. The pressure of the rear vent 3 is 300
760 mmHg, and a vent 5 near the polymer outlet 4.
The pressure at c is preferably 600 mmHg or less,
g or less is more preferable. It is preferable to lower the pressure as the desolvation proceeds (as it approaches the outlet), because the efficiency of desolvation can be further increased. The pressure in each vent is evacuated to a predetermined pressure by using a vacuum pump. In FIG. 1, 6 is a screw drive unit, 7 is a heat exchanger,
Reference numeral 8 denotes a polymer composition storage tank.

The most important point in the present invention is the number of revolutions of the screw when devolatilizing with a screw extruder. 5
A polymer with little deterioration in physical properties can be obtained only by operating the screw at a rotational speed of 0 to 150 rpm. If the screw rotation speed is less than 50 rpm, the amount of volatile components remaining in the polymer will increase, and the appearance of the molded product will be easily deteriorated, and it will be easy to vent up, so that the polymer composition cannot be processed stably. On the other hand, when the rotation speed is higher than 150 rpm, the resin temperature rises due to remarkable heat generation which is considered to be characteristic of a polymer having a high melt viscosity, and the physical properties of the polymer deteriorate due to thermal deterioration.

Since the barrel temperature of the screw extruder varies depending on the barrel position, it cannot be determined unconditionally, but it can be operated in the range of 100 to 300 ° C. In particular, in a barrel near the extruder outlet where devolatilization from the maleimide-based copolymer has progressed, the resin temperature tends to increase due to shear heat generated by the maleimide-based copolymer, so the screw rotation speed is an important factor.

When a maleimide-based copolymer having a glass transition temperature of 170 ° C. or higher is produced by a bulk polymerization method or a solution polymerization method, the maleimide-based copolymer composition (here, a reaction mixture) contains the maleimide-based copolymer. If an attempt is made to increase the amount, the viscosity of the polymer composition increases, and special equipment is also required for removing heat generated during the polymerization, and it is difficult to transfer the extruder to the extruder. A polymer composition containing a volatile component is preferred. If the content of the volatile component of the polymer composition is below this range, the viscosity of the composition becomes too high, and handling may be difficult, and if it exceeds, the volatile component becomes too large and remains after desolvation, and remains. Volatile components may increase.

In order to devolatilize such a maleimide-based copolymer composition having a large amount of volatile components, as shown in FIG. It is transported and supplied by a gear pump or the like to a vent type screw extruder 1 maintained at atmospheric pressure or reduced pressure, and volatile components are removed through a vent port 3 located behind a supply port 2. Multiple vents 5 located in front
Preferably, the remaining volatile components are separated via a, 5b, 5c.

The heat exchanger 7 may be a screw extruder,
Further, a double tube type or a static mixer type heat exchanger may be used. The polymer composition heated to 150 to 300 ° C. by the heat exchanger 7 is subjected to
After the pressure is adjusted to 5 to 30 atm, a decrease in devolatilization efficiency due to lack of heat or the like is suppressed by being supplied to the screw extruder, and gas generated from volatile components generated in large quantities is supplied to the rear of the supply port. By removing through the vent hole located, vent-up at the fore vent and entrainment of the polymer are less likely to occur. The processing time in the vented screw extruder is preferably 0.5 to 30 minutes. Below this range, devolatilization will be insufficient, and the remaining volatile components may increase. Above this range, the resin may be easily deteriorated or deteriorated.

In the present invention, the inert liquid (resin and resin) is supplied from the injection port of the extruder, which is located forward of the supply port of the material to be processed.
It is important to inject water , which is a liquid that does not react , so that the residual volatile components can be further reduced without causing deterioration in the physical properties of the polymer. That is, by injecting water into the cylinder through the inlets 9a, 9b and 9c in the barrel in front of one or more forevent portions, mixing with the polymer composition by rotating a screw, and then separating the pressure under reduced pressure at the vent portion. Residual volatile components can be further reduced. The amount of water used is preferably 0.5 to 3% by weight based on the polymer.

Since the heat resistance of the resin is apt to be significantly reduced due to the remaining volatile components, the residual volatile components should be reduced in a maleimide copolymer having a glass transition temperature of 170 ° C. or higher, which is characterized by heat resistance. Is preferred. The devolatilization is performed when the amount of the volatile component remaining in the polymer is 1000 ppm.
It is preferable to set the following value, more preferably 5
It should be below 00 ppm. If the amount of the remaining volatile component is larger than that, heat resistance is inferior, and the appearance of the molded article is poor, and the physical properties of the molded article may be reduced. As described above, the maleimide monomer unit and the aromatic vinyl monomer unit are used as essential components (or main components), and the weight average molecular weight after devolatilization is 50,000 to 500,000. A maleimide-based copolymer excellent in heat stability, having a retention of a molecular weight of 90% or more and a volatile component amount of 1000 ppm or less when heated for one minute is obtained.

Thermal degradation is caused by a decrease in the degree of polymerization of the polymer, coloring,
It can be evaluated by a decrease in impact resistance. In the method of the present invention, while operating a vent-type screw extruder in a specific screw rotation speed range, water is injected to treat a maleimide-based copolymer having excellent heat resistance to perform heating and devolatilization. This method is characterized in that it is particularly effective in suppressing a decrease in the molecular weight of the polymer among thermal degradation.

After devolatilization, a maleimide-based copolymer having a weight-average molecular weight of less than 50,000 undesirably deteriorates impact resistance and is not preferable in physical properties. A maleimide copolymer having a weight-average molecular weight higher than 500,000 has a melt viscosity that is too high. On the contrary, the amount of residual volatile components tends to increase due to a decrease in devolatilization efficiency. If the screw rotation speed is increased or the barrel temperature is increased, thermal deterioration proceeds, causing coloration or a decrease in molecular weight, which tends to be undesirable in physical properties.

The maleimide-based copolymer obtained by the method of the present invention has excellent heat stability, and its molecular weight hardly decreases even after heating and holding at 280 ° C. for further 10 minutes. It has a retention of at least 90%, preferably at least 95%, in comparison. In the method of the present invention, it is important to remove volatile components of the maleimide-based copolymer under specific conditions to give an appropriate heat history to the maleimide-based copolymer. By this operation, it is possible to convert to a thermally stable maleimide-based copolymer without causing significant thermal degradation, so that the resulting maleimide copolymer no longer has such a heat-labile structure or component. Is not present and is presumed to be excellent in thermal stability. As a criterion for such thermal stability, the present inventors have introduced a new parameter of the molecular weight retention at 280 ° C.

A maleimide-based copolymer having excellent thermal stability exhibits excellent heat resistance and impact resistance even when molded alone, and when used as a blend with another thermoplastic resin composition. Also has the characteristic that the physical properties hardly fluctuate depending on the blending temperature and kneading conditions. The maleimide-based copolymer from which volatile components have been removed by the method of the present invention, when used in such a blend, has excellent heat resistance, good moldability and particularly excellent impact resistance, and is obtained. The advantage is that the physical properties of the resulting blend are stable.

The maleimide copolymer devolatilized by the method of the present invention has a low volatile component content without deterioration in physical properties. Therefore, when this polymer is used, heat resistance and impact resistance are reduced. It is excellent in balance of typical physical properties, and is useful for applications of improving heat resistance and rigidity by blending with these resins as a modifier for general-purpose plastics and engineering plastics.

[0034]

According to the present invention, a maleimide copolymer having a glass transition temperature of 170 ° C. or higher and a polymer composition containing a volatile component are supplied to a vent type screw extruder at a screw rotation speed of 50 to 150 rpm. Since the devolatilization is performed by operating the extruder and injecting water , a polymer with little deterioration in physical properties can be obtained.

[0035]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.
In the following, “parts” means “parts by weight”. (Production Example 1) A polymerization reaction tank equipped with a condenser, a stirrer and two dropping funnels was charged with 7.2 parts of styrene and 36.5 parts of toluene, the inside of the reaction tank was replaced with nitrogen, and the temperature was raised to 114 ° C.

The reaction was started by adding 0.01 part of t-butylperoxyisopropyl carbonate as a polymerization initiator into the reaction vessel, and 23.3 parts of N-phenylmaleimide and 15.1. 5 parts of a dropping liquid (1), and 17.5 parts of styrene and t-
Polymerization was carried out under reflux while dropping liquids (2) each consisting of 0.02 parts of butyl peroxyisopropyl carbonate were separately dropped at a uniform rate over 3.5 hours. After completion of the dropwise addition, the reaction mixture was further heated for 1.5 hours, so that 52.0 wt% of toluene and 5.1 w of styrene were added.
Thus, a maleimide-based copolymer composition (A) consisting of t% and 42.9% by weight of the maleimide-based copolymer was obtained. N-
Phenylmaleimide was less than 0.05 wt% and could not be detected. The resulting maleimide-based copolymer was composed of 54.3 wt% of N-phenylmaleimide units and 4 of styrene units.
It consisted of 5.7% by weight and had a glass transition temperature of 206 ° C.

(Production Example 2) Styrene 21.
1 part and 31.9 parts of methyl ethyl ketone were charged;
T-Butylperoxy-2- as a polymerization initiator in a reaction tank
0.04 part of ethylhexanoate was added;
Using a dropping solution (1) consisting of 19.1 parts of phenylmaleimide and 5.3 parts of methyl ethyl ketone; and
Using a dropping liquid (2) consisting of 22.6 parts of styrene and 0.04 part of t-butylperoxy-2-ethylhexanoate, the polymerization temperature was adjusted to 90 ° C, and after the dropwise addition, the temperature was increased to 60 ° C.
Styrene 2 in the same manner as in Production Example 1 except that
A maleimide-based copolymer composition (B) consisting of 2.5% by weight, 40.3% by weight of the maleimide-based copolymer and 37.2% by weight of methylelketone was obtained. In addition, N-phenylmaleimide was less than 0.05 wt% and could not be detected. The obtained copolymer was composed of 47.4 wt% of N-phenylmaleimide units and 52.6 wt% of styrene units, and had a glass transition temperature of 189 ° C.

(Production Example 3) Styrene 47.
0 parts and 28.0 parts of toluene were charged; 0.01 part of t-butylperoxyisopropyl carbonate was added as a polymerization initiator to the reaction tank; 11.9 parts of N-phenylmaleimide and 1.3 parts of toluene Was used, and 11.1 parts of styrene and t
-Butyl peroxyisopropyl carbonate 0.02
After completion of the dropping, the temperature was adjusted to 6
A maleimide copolymer consisting of 31.5 wt% of styrene, 30.0 wt% of toluene, 38.4 wt% of a maleimide copolymer and 0.1 wt% of N-phenylmaleimide was prepared in the same manner as in Production Example 1 except that the temperature was changed to 0 ° C. A polymer composition (C) was obtained. The obtained copolymer was composed of 30.7% by weight of N-phenylmaleimide unit and 69.3% by weight of styrene unit.
% And the glass transition temperature was 150 ° C.

The glass transition temperature of the above copolymer was measured using DSC-8230 manufactured by Rigaku Denki Co., Ltd. under a nitrogen stream.
It was determined by a midpoint method from a DSC curve measured at a heating rate of 5 ° C./min using α-alumina as a reference. (Example 1) A vent type screw extruder is a twin-screw co-engaging type extruder manufactured by Japan Steel Works, Ltd., having a screw diameter (D) of 65 mm and a cylinder length (L) of 260.
0 mm, L / D = 40, number of vents 4 (1 rear vent, 3 fore vents) were used. The maleimide-based copolymer composition (A) obtained in Production Example 1 was passed through a static mixer type heat exchanger circulating a 285 ° C. heat medium using a gear pump and heated to 240 ° C. After holding so that 20 kg / cm ² gave supplies the set screw extruder operating conditions shown in Table 1 maleimide copolymer (a-1). In addition, water was injected at a supply rate of 7 kg / h in each stage before the second and third vents.

(Examples 2 and 3 and Comparative Examples 1 and 2) The same operation as in Example 1 was repeated except that the temperature of the copolymer composition or the operating conditions of the screw extruder were changed as shown in Table 1. Maleimide copolymers (a-2) to (a-
3), (a-6) to (a-7) were obtained. The second and third
Water was injected at a feed rate of 7 kg / h in each stage before venting.

(Examples 4 and 5) The vent type screw extruder is a twin screw co-engaging type extruder manufactured by Nippon Steel Works, Ltd., having a screw diameter (D) of 120 mm and a cylinder length (L) of 5460 mm. , L / D = 45.5, the number of vents was 4 (rear vent 1, fore vent 3), and the same operation as in Example 1 was repeated, except that the maleimide copolymer (a- 4) and (a-5) were obtained. The water injection operation was performed at a supply rate of 60 kg / h in the same manner as in Example 1.

(Examples 6 and 7, Comparative Examples 3 and 4) Screw diameter (D) 44 mm, cylinder length (L) 1958 m
m, L / D = 45.5, using a vent type screw extruder with 4 vents (1 rear vent, 3 for vents), using the maleimide copolymer composition as (B),
Example 1 except for changing to (C) and as shown in Table 1.
By repeating the same operation as in the above, the maleimide polymer (b-
1), (b-2), (c-1), and (c-2) were obtained. The water injection operation was performed at a supply speed of 4 kg / h in the same manner as in Example 1.

Example 8 A maleimide polymer (a-8) was obtained by repeating the same operation as in Example 1 except that water was not injected.
In Table 1, Forevents 1, 2, and 3 represent the order of forevents from the polymer composition supply port.

[0044]

[Table 1]

The obtained maleimide copolymer (a-1)
To (a-5), (a-7), (a-8), (b-1),
Table 2 shows the analysis results of the volatile component amounts, the weight average molecular weight, the thermal degradation, the appearance, and the molecular weight retention of (b-2), (c-1) and (c-2). The amount of volatile components is obtained by dissolving the obtained maleimide-based copolymer in chloroform,
ST (styrene), PMI (N-phenylmaleimide)
Was quantified by gas chromatography.

The type and ratio of the monomer units in the copolymer structure were determined by infrared absorption spectrum, 1 H-NMR, and elemental analysis. The weight average molecular weight of the copolymer was represented by a value obtained by using tetrahydrofuran (THF) as an eluent and measuring the molecular weight measured by gel permeation chromatography (GPC) using standard polystyrene.

For the thermal deterioration, a test piece (thickness: 3 mm) of a maleimide copolymer obtained by injection molding with the cylinder temperature set to 280 ° C. was subjected to an Izod impact test based on JIS K7110, and the Izod impact value was measured. Indicated. The larger the value, the less the degree of thermal degradation. The appearance of the test piece was visually observed.

The molecular weight retention was measured at 280 ° C. under a reduced pressure (20 mmHg or less) using a differential thermobalance.
After heating for 1 minute, the copolymer was quenched and the molecular weight of the obtained copolymer was measured, and the ratio to the value before the treatment was determined.

[0049]

[Table 2]

As shown in Tables 1 and 2, the polymers obtained in the examples have a small amount of volatile components, and also have a small decrease in molecular weight and little coloring of the polymers. Further, the obtained polymer has a high molecular weight retention rate and excellent thermal stability. The polymer obtained in the comparative example was thermally degraded, had a low retention of molecular weight, or had a large amount of volatile components.

[0051]

According to the method of the present invention, a volatile component can be removed without heating a maleimide copolymer having a high melt viscosity more than necessary, so that a maleimide copolymer having a low residual volatile component content can be obtained. The polymer can be obtained efficiently without causing physical property deterioration. Further, the obtained maleimide-based copolymer has a high molecular weight retention at 280 ° C. and is excellent in thermal stability.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a vent type screw extruder used to carry out the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vent type screw extruder 2 Supply port 3 Rear vent 5a Fore vent 5b Fore vent 5c Fore vent 7 Heat exchanger

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-77904 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 6/00-6/28

Claims (4)

(57) [Claims] 1. A maleimide-based copolymer for removing a volatile component by treating a maleimide-based copolymer having a glass transition temperature of 170 ° C. or higher and a polymer composition containing a volatile component with a vent-type screw extruder. A method for producing a united product, wherein the extruder is operated at a screw rotation speed of 50 to 150 rpm, and water is injected from an injection port located forward of a workpiece supply port of the extruder. A method for producing a maleimide-based copolymer. 2. The glass transition temperature is 170 ° C. or higher.
Polymer set containing maleimide copolymer and volatile components
The product is treated with a vent-type screw extruder for volatility
A method for producing a maleimide-based copolymer from which components are removed.
Heating the polymer composition to 150-300 ° C. , and
Pressurized and supplied to the extruder from the 5～30Atm, before
The extruder was operated at a screw rotation speed of 50 to 150 rpm.
A method for producing a maleimide-based copolymer, which is operated . 3. A process according to claim 1 or 2, wherein the maleimide copolymer is a copolymer as an essential component a maleimide-based monomer unit and an aromatic vinyl monomer units. 4. A vent type screw extruder has a vent port behind a supply port of a workpiece and a plurality of vent ports ahead of the supply port, and is maintained at atmospheric pressure or reduced pressure. 20 to 80
The method according to any of the preceding claims, wherein a polymer composition containing wt% of volatile components is provided.