KR101967427B1 - Heat-resistant styrene copolymer composition, heat-resistant styrene copolymer, and method for preparing the copolymer - Google Patents
Heat-resistant styrene copolymer composition, heat-resistant styrene copolymer, and method for preparing the copolymer Download PDFInfo
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- KR101967427B1 KR101967427B1 KR1020150106410A KR20150106410A KR101967427B1 KR 101967427 B1 KR101967427 B1 KR 101967427B1 KR 1020150106410 A KR1020150106410 A KR 1020150106410A KR 20150106410 A KR20150106410 A KR 20150106410A KR 101967427 B1 KR101967427 B1 KR 101967427B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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Abstract
The present invention relates to a heat-resistant styrenic copolymer composition, a heat-resistant styrenic copolymer and a process for producing the copolymer. The heat-resistant styrenic copolymer composition according to the present invention can improve the polymerization reactivity by containing a mercaptan-type compound having at least three functional groups and N-vinyl-2-pyrrolidone in a certain amount, A heat-resistant styrenic copolymer having improved polymerization conversion can be produced.
Description
The present invention relates to a heat-resistant styrenic copolymer composition, a heat-resistant styrenic copolymer, and a process for producing the copolymer, which have excellent polymerization and conversion while maintaining excellent mechanical and chemical properties.
Generally, the heat-resistant styrenic copolymer is excellent in moldability, rigidity and electrical characteristics, and can be used in a variety of industrial fields including office automation equipment such as computers, printers, copying machines, household electrical appliances such as televisions and audios, . ≪ / RTI > Particularly, heat-resistant styrenic copolymers which are resistant to external high temperatures by increasing the heat resistance are used for special applications such as housings for home appliances and automobile interior materials.
To obtain a styrenic copolymer having high heat resistance,? -Methylstyrene (AMS) is usually used. Although α-methylstyrene is relatively inexpensive and has excellent heat-resistant properties, the polymerization proceeds at a temperature lower than the polymerization temperature of the conventional heat-resistant styrenic copolymer due to a low ceiling temperature (Tc) . The low polymerization conversion rate is directly related to the deterioration of the productivity, which is a great obstacle to industrial application.
Therefore, in order to easily apply the heat-resistant styrenic copolymer to industry, it is necessary to improve the polymerization conversion ratio of the heat-resistant styrenic copolymer by complementing the disadvantage of low ceiling temperature of? -Methylstyrene, A technology that does not deteriorate the mechanical chemical properties of the thermostable styrenic copolymer, that is, a technique that only improves the polymerization conversion rate and inherently does not cause deformation of the heat resistant styrenic copolymer is required.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to provide a heat resistant styrenic copolymer having a high weight average molecular weight while maintaining excellent mechanical and chemical properties, Based copolymer composition.
Another object of the present invention is to provide a process for producing the heat-resistant styrenic copolymer.
Still another object of the present invention is to provide a heat-resistant styrenic copolymer produced from the heat-resistant styrenic copolymer composition.
In order to solve the above problems, the present invention provides a heat-resistant styrenic copolymer which comprises 0.07 to 0.2 parts by weight of a mercaptan-based compound per 100 parts by weight of a monomer mixture and the mercaptan-based compound has at least three functional groups Lt; / RTI >
And adding 0.07 to 0.2 part by weight of a mercaptan-based compound to 100 parts by weight of the monomer mixture to a polymerization solution containing a monomer mixture, wherein the mercaptan-based compound has at least three functional groups Based on the total weight of the styrene-based copolymer.
In addition, there is provided a heat-resistant styrenic copolymer produced from the heat-resistant styrenic copolymer composition.
The heat-resistant styrenic copolymer composition according to the present invention can improve the polymerization reactivity and improve the polymerization conversion rate by containing a mercaptan-type compound having at least three functional groups and N-vinyl-2-pyrrolidone at a certain ratio , A heat-resistant styrenic copolymer having a high weight-average molecular weight can be produced.
Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.
The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.
The present invention provides a heat-resistant styrenic copolymer composition capable of producing a heat-resistant styrenic copolymer having a high weight-average molecular weight and capable of improving polymerization conversion.
The heat-resistant styrenic copolymer has been widely applied to special applications such as automobile interior materials, home appliance housings, and the like. In order to obtain such a styrenic copolymer having high heat resistance, a-methylstyrene (AMS) is usually used. However, the? -Methylstyrene is significantly lower than the polymerization temperature of a conventional styrenic copolymer due to a low ceiling temperature There is a problem that the polymerization conversion is largely deteriorated since polymerization is carried out at a temperature. The low polymerization conversion rate is directly related to the deterioration of the productivity, which is a great obstacle to industrial application.
Therefore, in order to easily apply the heat-resistant styrenic copolymer to industry, there is a need to improve the polymerization conversion rate of? -Methylstyrene to increase the productivity, and at the same time, to provide a technique that does not deteriorate the mechanical and chemical properties inherent in the heat resistant styrenic copolymer .
Accordingly, the present invention provides a heat-resistant styrenic copolymer composition capable of producing a heat-resistant styrenic copolymer having a high weight average molecular weight with a high polymerization conversion.
The heat-resistant styrenic copolymer composition according to an embodiment of the present invention comprises 0.07 to 0.2 parts by weight of a mercaptan-based compound per 100 parts by weight of the monomer mixture, and the mercaptan-based compound has at least three functional groups .
In the present invention, the term " at least " represents a minimum value, for example, at least three may represent at least three or more than three.
The term " functional group " in the present invention may denote an atom or an atomic group in a molecule having reactivity under a specific condition, and may be represented generally by a functional atomic group, a functional group or a functional group.
The mercaptan compound may be a compound containing mercaptan or thiol, and the mercaptan may be a compound in which a hydrogen atom of an aliphatic hydrocarbon is substituted with a -SH group.
The mercaptan-based compound according to an embodiment of the present invention may be one having at least three functional groups as described above, and may be a copolymer of a heat-resistant styrenic copolymer finally formed by forming a branched polymerization structure to improve the polymerization conversion ratio The weight average molecular weight can be increased.
Specifically, the mercaptan-based compound may be one or more of trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate). As described above, the monomer mixture 100 0.07 to 0.2 part by weight based on 100 parts by weight of the thermostable styrenic copolymer composition. If the mercaptan-based compound is included in an amount outside the above range, the conversion of the heat-resistant styrenic copolymer from the heat-resistant styrenic copolymer composition can not be effectively improved, The weight average molecular weight of the copolymer can not be effectively increased.
The monomer mixture according to one embodiment of the present invention may contain alpha -methylstyrene, acrylonitrile and N-vinyl-2-pyrrolidone, and specifically, the monomer mixture may contain alpha -methylstyrene in an amount of 60 Wt% to 75 wt%; From 24% to 35% by weight of acrylonitrile; And 1 wt% to 5 wt% of N-vinyl-2-pyrrolidone.
The above-mentioned alpha-methylstyrene (AMS) is an alkylated styrene compound represented by the following general formula (1), and has excellent heat resistance and impact strength characteristics, and is a chemical intermediate or raw material for imparting heat resistance and impact strength in the production of resins and polymers It may be used as a material.
[Chemical Formula 1]
In the present invention, as described above,? -Methylstyrene has excellent heat resistance and impact strength, thereby imparting excellent heat resistance to the heat-resistant styrenic copolymer finally contained in the heat-resistant styrenic copolymer composition, It can serve to improve the strength. However, since α-methylstyrene has a very low ceiling temperature (Tc, 66 ° C.), when it is subjected to homopolymerization, it is required to carry out the polymerization for a long time at a low temperature. Also, the polymerized polymer is not only unstable, There is a problem that productivity is low. Therefore, the heat-resistant styrenic copolymer composition of the present invention contains acrylonitrile and N-vinyl-2-pyrrolidone described below together with the above-mentioned? -Methylstyrene to thereby further improve the mechanical and chemical properties, So that the polymerization can be performed more easily.
The term " ceiling temperature " in the present invention means an upper limit value of a temperature range that enables an exothermic reaction to proceed thermodynamically in a reversible reaction. When a substance is at a ceiling temperature, If the depolymerization rate is the same, the depolymerization rate is faster than the polymerization rate, and the polymerization is inhibited, so that the polymerization to the desired polymer can not easily occur.
The monomer mixture may contain 60% by weight to 75% by weight of the? -Methylstyrene as described above. If the? -Methylstyrene is contained in an amount of less than 60% by weight, the effect of improving the heat resistance may be insignificant. When the? -Methylstyrene is contained in an amount exceeding 75% by weight, the acrylonitrile and the N- The content of 2-pyrrolidone is decreased and the effect of improving the polymerization conversion is insignificant. As a result, a weight-average molecular weight reduction due to a low polymerization conversion ratio and a large amount of residual monomer may occur.
The acrylonitrile is a kind of unsaturated nitrile compound and has excellent reactivity and polymerizability, and may be widely used as a raw material for synthetic rubber and synthetic resin.
In the present invention, the acrylonitrile can be easily polymerized by complementing the low ceiling temperature of the? -Methylstyrene, and at the same time, the weight average molecular weight of the thermostable styrenic copolymer finally produced can be increased. Impact strength and chemical resistance of the resin.
The monomer mixture may comprise from 24% to 35% by weight of the acrylonitrile as described above. If the amount of the acrylonitrile is less than 24% by weight, the polymerization may be incomplete and unreacted monomers may be increased, and the finally produced thermostable styrenic copolymer may not have a sufficiently high weight average molecular weight, There is a possibility that the property is deteriorated. On the other hand, when the acrylonitrile is contained in an amount of more than 35% by weight, the content of? -Methylstyrene may be relatively decreased, which may cause a decrease in heat resistance.
N-vinyl-2-pyrrolidone is a compound represented by the following general formula (2), and has a characteristic of being able to easily form a polymer because of its excellent reactivity due to double bonds present in the molecule have.
(2)
In the present invention, the N-vinyl-2-pyrrolidone has excellent reactivity, so that the low ceiling temperature of? -Methylstyrene is supplemented together with the acrylonitrile to increase the polymerization temperature and increase the polymerization reactivity, It can play a role in making it happen. Thus, the polymerization conversion ratio can be increased without lowering the heat resistance of the heat-resistant styrenic copolymer finally produced.
The monomer mixture may contain 1 wt% to 5 wt% of the N-vinyl-2-pyrrolidone as described above. If the content of N-vinyl-2-pyrrolidone is less than 1% by weight, the effect of improving the polymerization reactivity is insignificant and the effect of improving the polymerization conversion of the heat-resistant styrenic copolymer finally produced may be insignificant. When the vinyl-2-pyrrolidone is contained in an amount of more than 5% by weight, the effect of improving the polymerization reactivity becomes greater and the polymerization conversion ratio of the heat-resistant styrenic copolymer finally produced can be greatly improved. However, (For example, an excessive increase in glass transition temperature) may result in a problem that the above characteristics are deteriorated. Further, the weight-average molecular weight of the heat-resistant styrenic copolymer produced is reduced, and N-vinyl-2-pyrrolidone is yellow, which may cause problems due to coloration.
The present invention also provides a process for producing the above heat-resistant styrenic copolymer.
The method according to an embodiment of the present invention includes the step of adding 0.07 part by weight to 0.2 part by weight of a mercaptan compound to 100 parts by weight of a monomer mixture to a polymerization solution containing a monomer mixture, followed by bulk polymerization do.
Step A is a step of adding a mercaptan-based compound to a monomer mixture to perform a bulk polymerization in order to produce a heat-resistant styrene-based copolymer composition.
The monomer mixture comprises 60 wt% to 75 wt% of [alpha] -methylstyrene; From 24% to 35% by weight of acrylonitrile; And 1 wt% to 5 wt% of N-vinyl-2-pyrrolidone.
The polymerization solution may optionally contain a reaction medium, wherein the reaction medium may be contained in an amount of 10 parts by weight or less based on 100 parts by weight of the monomer mixture.
The reaction medium is not particularly limited, but aromatic compounds such as ethylbenzene, benzene, toluene and xylene; Methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane and the like.
The mercaptan-based compound may have at least three functional groups, and may be specifically as described above.
In the production method according to an embodiment of the present invention, the polymerization initiator may be added together with the mercaptan-based compound before the massive polymerization is started, or after the addition of the mercaptan-based compound. In this case, the polymerization initiator may be an organic peroxide initiator containing a polyfunctional group. Specifically, the organic peroxide initiator containing a polyfunctional group may be 1,1-bis (tertiarybutylperoxy) cyclohexane (t- butylperoxy cyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (tertiary butylperoxy) Bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (tertiary butylperoxy) butane (2,2 -bis (t-butylperoxy) butane) and 2,2-bis (4,4-di-t-butylperoxycyclohexane) Or a combination thereof.
The amount of the polymerization initiator to be used is not particularly limited, but may be 0.1 part by weight to 0.2 part by weight based on 100 parts by weight of the monomer mixture.
The bulk polymerization is not particularly limited, but may be continuous bulk polymerization and may be carried out in a temperature range of 100 ° C to 120 ° C.
The manufacturing method according to an embodiment of the present invention may further include a devolatilizing process step after step A, wherein the devolatilization process is performed under a temperature range of 200 ° C. to 250 ° C. and a vacuum pressure of 25 torr or less .
In addition, the present invention provides a heat-resistant styrenic copolymer prepared from the heat-resistant styrenic copolymer composition.
The heat-resistant styrenic copolymer according to an embodiment of the present invention has a weight-average molecular weight (Mw) of 80,000 g / mol or more while exhibiting a polymerization conversion of 65% or more. At this time, the heat-resistant styrenic copolymer may be polymerized at a polymerization temperature of 112 ° C. Specifically, the heat-resistant styrenic copolymer may have a weight average molecular weight (Mw) of 80,000 g / mol to 100,000 g / mol and a polymerization conversion of 65% to 75%.
Herein, the weight average molecular weight is a relative value to a standard polystyrene sample through gel permeation chromatography (GPC) after dissolving the heat-resistant styrenic copolymer in tetrahydrofuran.
The polymerization conversion ratios are calculated as the ratio between the weight of the polymerized product after completion of polymerization and the weight of the polymerized product after dewatering and drying, respectively.
Meanwhile, the heat-resistant styrenic copolymer according to an embodiment of the present invention may be used as a base resin of a rubbery polymer to impart heat resistance to the rubbery polymer.
The rubbery polymer is not particularly limited, but may be, for example, acrylonitrile-butadiene-styrene copolymer (ABS) or acrylate-styrene-acrylonitrile copolymer (ASA).
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.
The weight parts of each material used in the following examples, comparative examples and comparative examples are shown based on 100 parts by weight of the monomer mixture, wherein the monomer mixture contains? -Methylstyrene, acrylonitrile and N-vinyl-2-pyrrolidone .
Example 1
3 parts by weight of toluene was added to a monomer mixture of 68% by weight of? -methylstyrene, 29% by weight of acrylonitrile and 3% by weight of N-vinyl-2-pyrrolidone to prepare a mixed solution, and trimethylolpropane tris Mercapto propionate) and 0.2 part by weight of 1,1-bis (tertiarybutylperoxy) cyclohexane were added, and the mixture was continuously introduced into a polymerization reactor, followed by bulk polymerization at 112 ° C. After the polymerization was completed, a devolatilization process was performed at a temperature of 250 ° C. and a vacuum pressure of 20 torr to remove unreacted monomers and toluene to prepare a heat resistant styrenic copolymer.
Example 2
A heat-resistant styrenic copolymer was prepared in the same manner as in Example 1, except that 70% by weight of? -methylstyrene was used and 1% by weight of N-vinyl-2-pyrrolidone was used.
Example 3
(trimethylolpropane tris (3-mercaptopropionate) was used in an amount of 0.07 weight%, and the weight ratio of acrylonitrile to acrylonitrile was 30 wt% and that of N-vinyl-2-pyrrolidone was 5 wt% Was used to prepare a heat-resistant styrenic copolymer.
Example 4
(3-mercaptopropionate) instead of trimethylolpropane tris (3-mercaptopropionate) was obtained by using 69% by weight of? -methylstyrene and 2% by weight of N-vinyl- Propionate) was used in an amount of 0.2 part by weight, and a heat-resistant styrenic copolymer was prepared in the same manner as in Example 1, except that the devolatilization process was carried out under a vacuum of 15 torr.
Example 5
(3-mercaptopropionate) instead of trimethylolpropane tris (3-mercaptopropionate) was obtained by using 69% by weight of? -methylstyrene and 2% by weight of N-vinyl- Propionate) was used in place of the styrenic copolymer used in Example 1, to thereby obtain a heat-resistant styrenic copolymer.
Comparative Example 1
except that n-vinyl-2-pyrrolidone and trimethylolpropane tris (3-mercaptopropionate) were not used in the case of using? -methylstyrene as 71% by weight and acrylonitrile as 29% by weight , A heat-resistant styrenic copolymer was prepared in the same manner as in Example 1 above.
Comparative Example 2
except that N-vinyl-2-pyrrolidone was not used, and the heat-resistant styrenic copolymer was obtained through the same procedure as in Example 1 except that? -methylstyrene was used in an amount of 71% by weight and acrylonitrile was used in an amount of 29% Lt; / RTI >
Comparative Example 3
A heat-resistant styrenic copolymer was prepared in the same manner as in Example 1, except that trimethylolpropane tris (3-mercaptopropionate) was not used.
Comparative Example 4
A heat-resistant styrenic copolymer was prepared in the same manner as in Example 3, except that 0.05 part by weight of trimethylolpropane tris (3-mercaptopropionate) was used.
Comparative Example 5
A heat-resistant styrenic copolymer was prepared in the same manner as in Example 4, except that 0.25 parts by weight of pentaerythritol tetra (3-mercaptopropionate) was used.
Comparative Example 6
A thermostable styrenic copolymer was obtained in the same manner as in Example 3 except that 65% by weight of? -methylstyrene, 29% by weight of acrylonitrile and 6% by weight of N-vinyl-2-pyrrolidone were used. .
Comparative Example 7
A heat-resistant styrenic copolymer was prepared in the same manner as in Example 2, except that acrylonitrile was used in an amount of 29.5% by weight and N-vinyl-2-pyrrolidone was used in an amount of 0.5% by weight.
Comparative Example 8
A heat-resistant styrenic copolymer was prepared in the same manner as in Example 1 except that 0.1 part by weight of n-dodecyl mercaptan was used instead of trimethylolpropane tris (3-mercaptopropionate).
Experimental Example
(Tg, 占 폚) and weight average molecular weight (Mw, 占 폚) of each of the copolymers were measured in order to compare the physical properties of the heat-resistant styrenic copolymers of Examples 1 to 5 and Comparative Examples 1 to 8, g / mol) and polymerization conversion (%) were measured. The results are shown in Table 1 below.
The glass transition temperature was measured by DSC (differential scanning calorimeter, TA Instrument).
The weight average molecular weight was determined by dissolving each copolymer in tetrahydrofuran and measuring the relative value for a standard polystyrene sample through gel permeation chromatography (GPC).
The polymerization conversion rate was obtained by measuring the total weight of the polymerized product before the devolatilization process after the completion of the polymerization and measuring the weight of the heat-resistant styrenic copolymer prepared after the devolatilization process.
As shown in Table 1, the heat-resistant styrenic copolymers of Examples 1 to 5 according to one embodiment of the present invention have a weight average molecular weight of 80,000 g / mol or more and a high polymerization conversion of 65% or more Respectively. On the other hand, the heat-resistant styrenic copolymers of Comparative Examples 1 to 8 exhibited a weight-average molecular weight of 80,000 g / mol or less overall.
Specifically, the heat-resistant styrenic copolymer of Example 1 and the heat-resistant styrenic copolymer of Comparative Example 1 using only? -Methylstyrene and acrylonitrile according to an embodiment of the present invention, N-vinyl-2-pyrrolidone Of the heat-resistant styrenic copolymer of Comparative Example 2 and the heat-resistant styrenic copolymer of Comparative Example 3 which did not use the mercaptan-type compound of Comparative Example 2, The weight average molecular weight was reduced to about 95% of the heat-resistant styrenic copolymer of Example 1, and the polymerization conversion rate was also about 91% to 98%.
In addition, in the case of the heat-resistant styrenic copolymer of Comparative Example 8 using a typical n-dodecylmercaptan not present in the present invention, the heat-resistant styrenic copolymer of Example 1 also had a reduced weight average molecular weight And showed a relatively low polymerization conversion rate.
The heat-resistant styrenic copolymer of Comparative Example 6 (6% by weight) and Comparative Example 7 (0.5% by weight), which were used in the content range of N-vinyl-2-pyrrolidone, 1) and Example 3 (5% by weight), respectively. As a result, it was found that the heat-resistant styrenic copolymer of Comparative Example 6 had a similar polymerization conversion to that of the heat-resistant styrenic copolymer of Example 3 But the weight average molecular weight was reduced to about 87%. The heat-resistant styrenic copolymer of Comparative Example 7 showed a weight-average molecular weight similar to that of the heat-resistant styrenic copolymer of Example 2, but the polymerization conversion was lowered.
In addition, the heat-resistant styrenic copolymer of Comparative Example 3 (0.05 part by weight) and Comparative Example 4 (0.25 part by weight) which used the mercaptan compound outside the content range of the present invention, Example 3 (0.07 part by weight) The heat-resistant styrenic copolymer of Comparative Example 4 showed a similar degree of polymerization conversion as the heat-resistant styrenic copolymer of Example 3, but the weight average molecular weight Was about 96%. The heat-resistant styrenic copolymer of Comparative Example 5 showed a slightly higher polymerization conversion than the heat-resistant styrenic copolymer of Example 4, but the gel in the copolymer was generated. It is generally known that gels present in the polymer can interfere with uniform melting of the polymer and degrade the processing performance of the polymer. Therefore, the heat-resistant styrenic copolymer of Comparative Example 5 is unsuitable for industrial application.
Claims (11)
Wherein the mercaptan-based compound has at least three functional groups
The monomer mixture comprises 60 wt% to 75 wt% of [alpha] -methylstyrene; From 24% to 35% by weight of acrylonitrile; And 1 wt% to 5 wt% of N-vinyl-2-pyrrolidone.
Wherein the mercaptan-based compound is at least one of trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate).
Wherein the mercaptan-based compound has at least three functional groups,
The monomer mixture comprises 60 wt% to 75 wt% of [alpha] -methylstyrene; From 24% to 35% by weight of acrylonitrile; And 1 wt% to 5 wt% of N-vinyl-2-pyrrolidone.
Wherein the mercaptan-based compound is at least one of trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate).
Wherein the mass polymerization is continuous mass polymerization.
Wherein the bulk polymerization is carried out in the presence of an organic peroxide initiator containing a polyfunctional group.
The polyfunctional group-containing organic peroxide initiator may be at least one selected from the group consisting of 1,1-bis (tertiarybutylperoxy) cyclohexane, 1,1-bis (tertiarybutylperoxy) -2-methylcyclohexane, Butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (tertiary butylperoxy) butane and 2,2-bis (4,4-ditertiarybutylperoxycyclohexane) Wherein the styrene-based copolymer is at least one selected from the group consisting of a styrene-based styrene copolymer and a styrene-based styrene copolymer.
Wherein the copolymer has a weight average molecular weight (Mw) of 80,000 g / mol or more.
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