KR101723628B1 - -- 4 Maleimide--alkyl styrene based heat-resistant tetra-polymer having good flowability and manufacturing methods thereof - Google Patents

Abstract

More particularly, the present invention relates to a maleimide-? -Alkylstyrene-based high heat resistant quaternary block copolymer having excellent fluidity and a method for producing the same. More specifically, the present invention relates to a maleimide- -Methylstyrene monomer, 10 to 70% by weight of an alkylstyrene monomer, 5 to 50% by weight of an unsaturated nitrile monomer, and 3 to 50% by weight of an aromatic vinyl monomer is prepared by simultaneously charging a polyfunctional mercaptan and a polyfunctional vinyl compound The present invention relates to a method for producing a heat-resistant, block copolymer resin having excellent fluidity.
The present invention is a heat-resistant resin having a weight-average molecular weight of 80,000 to 200,000 and a glass transition temperature of 150 to 200 ° C, which is excellent in fluidity and has a branched structure introduced without degradation of mechanical properties and heat resistance Lt; RTI ID = 0.0 > flowability.

Description

TECHNICAL FIELD The present invention relates to a maleimide-α-alkyl styrene based heat-resistant tetra-polymer having excellent fluidity and a method for producing the same.

More particularly, the present invention relates to a maleimide-? -Alkylstyrene-based high heat resistant quaternary block copolymer having excellent flowability and a method of producing the same. More specifically, the present invention relates to a maleimide- Heat-resistant quaternary copolymer which is composed of a compound, an aromatic vinyl compound, and an unsaturated nitrile compound and has high fluidity and can introduce a branch structure without deteriorating the mechanical properties and heat resistance without generating a gel And a manufacturing method thereof.

Conventional heat-resistant copolymers can be classified differently according to the constituent components and the polymerization process. First, based on the constituents, the copolymer is largely classified into a maleimide-based copolymer and an? -Alkylstyrene-based copolymer, It can be classified into emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization.

The maleimide-based copolymer generally adopts only the solution polymerization process due to the technical problems of the polymerization. It contains a large amount of maleimide and exhibits a high heat distortion temperature and a high thermal decomposition temperature. Thus, when mixed with various thermoplastic resins The heat resistance of the applied thermoplastic resin is greatly improved and the processability is excellent. However, since the maleimide content is high, the melt viscosity is considerably high, which requires a high processing temperature in processing. In general, the heat resistance and the impact resistance are in inverse proportion to each other. In the case of the maleimide-based heat resistant copolymer, the thermal resistance is too high, so that the impact resistance is drastically lowered as the applied amount increases in the thermoplastic resin , And a large amount of expensive maleimide is contained at the same time, so that the polymerized heat-resistant copolymer has a disadvantage that the price is not competitive.

On the other hand, the α-alkylstyrene-based copolymer is mainly composed of bulk polymerization and emulsion polymerization, and in the case of the α-alkylstyrene-based copolymer, the α-alkylstyrene content is low and the melt viscosity is low, And is excellent in color of thermoplastic resin applied when blended with various thermoplastic resins, has excellent impact resistance, and has a relatively low cost. However, it has the disadvantage that it is difficult to manifest the most important heat resistance. Also, the emulsion polymerized? -Alkyl styrenic copolymer has a high? -Alkylstyrene content and thus has an advantage of being able to exhibit heat resistance (heat resistance) at a level of 135 占 폚. However, since the melt viscosity is higher than that of heat resistance, Due to the nature of the polymerization process, most of the low molecular weight emulsifier and various additives applied to the final product remain, and thus the color of the thermoplastic resin applied to the thermoplastic resin is poor and the appearance defect due to gas generation during processing is disadvantageous.

Japanese Patent Publication JP 1982-98536 discloses a maleimide-aromatic vinyl monomer copolymer prepared by solution polymerization. However, since the heat resistance and the melt viscosity are too high, the processing temperature is high, the natural color is poor and the coloring property is bad, and ABS (Acrylonitrile-Butadiene-Styrene copolymer: hereinafter abbreviated as ABS resin) and AS (Acrylonitrile- When the resin is kneaded with the resin, the difference in melt viscosity is large and the kneading property is deteriorated. The solution-polymerized N-substituted maleimide-aromatic vinyl monomer copolymer proposed in Japanese Patent No. JP 1983-162616 requires a solvent recovery apparatus and a separate solvent tank, which are applied in polymerization, and is not practical because of high production cost. In the case of the solution-polymerized N-substituted maleimide-aromatic vinyl monomer copolymer proposed in Japanese Patent Registration JP 2003-41080, a method of precipitating the final polymerized product synthesized by solution polymerization in methanol is adopted, and a large amount of methanol solvent Which is inefficient in terms of manufacturing cost. The α-alkylstyrene-N-substituted maleimide-unsaturated nitrile-aromatic vinyl monomer copolymer proposed in Japanese Patent Publication JP 1985-147414 is susceptible to formation of heterogeneous copolymers having different compositions due to adoption of suspension polymerization, In addition, filtration equipment is required, and other large amounts of additives such as suspending agents remain in the polymer product, which has a disadvantageous effect on physical properties. The N-substituted maleimide-unsaturated nitrile-maleic anhydride copolymer according to Japanese Patent Registration Nos. JP 1987-280249 and JP 1990-189361 is a solution polymerized product and thus has a high production cost due to its low practicality and high melt viscosity, In particular, there is a problem that the blendability is lowered when blended with ABS. The bulk polymerized α-alkylstyrene-unsaturated nitrile copolymers disclosed in US Pat. Nos. US 4874829 and US 6593424 are good in processability, but they have α-alkylstyrene as a main component, and their heat resistance is remarkably low. Substituted maleimide-unsaturated nitrile-aromatic vinyl monomer copolymer according to US Patent No. 5478903, US 5565537 and solution polymerized N-substituted maleimide-aromatic vinyl monomer copolymer as disclosed in Japanese Patent Application JP 2004-307760, JP 200554097, The aromatic vinyl monomer copolymer adopts a solution polymerization process, which results in a considerably high production cost, an excessively high heat resistance and a high melt viscosity, a high processing temperature, and a poor kneading ability due to processability and difference in melting point when blended with other thermoplastic resins There is a problem that the impact resistance is reduced.

In Korean Patent No. 10-0915114, in order to solve the above-mentioned problems, it has excellent thermal stability and heat resistance at a high temperature and has a low melt viscosity, so that it has excellent productivity, formability and formability when blended with other thermoplastic resins Heat-shrinkable copolyesters which are excellent in kneading properties and capable of exhibiting higher heat resistance and can be produced at low cost and high efficiency, and a manufacturing process thereof. In the above-mentioned invention, the N-substituted maleimide compound and the? -Alkylstyrene are used together. However, by using low cost maleimide, the production cost is lowered and the continuous melt polymerization is advantageously used for high productivity and low cost production And the lack of heat resistance due to the reduced maleimide content was compensated for by an appropriate amount of? -Alkylstyrene. In addition, by applying unsaturated nitrile which acts as a solvent for the solid-type maleimide, which is excellent in chemical resistance, it is possible to apply continuous bulk polymerization by homogenizing the polymerization system, and an aromatic vinyl monomer having excellent processability and colorability is applied The melt viscosity of the polymer product is remarkably lowered and the kneading property with other thermoplastic resin is maximized.

In addition, the present inventors have found that when the maleimide-alpha-alkylstyrene heat-resistant quaternary copolymer is prepared in the Korean Patent Publication No. 10-2011-0063947, the N-substituted maleimide monomer is dissolved in the unsaturated nitrile monomer, A method for preparing the same, and a process for producing the same, which disclose a heat-resistant templating copolymer having improved heat resistance characteristics by reducing the content of oligomers due to side reactions in the final product.

Generally, when the heat-resistant copolymer has the same weight-average molecular weight, the melt viscosity increases as the glass transition temperature rises, and as a result, the flowability is lowered and the productivity and workability are deteriorated. In order to improve the workability, it is possible to increase the fluidity by a method such as adding a plasticizer, but there is a disadvantage that the heat resistance is remarkably lowered, and when the molecular weight is reduced to improve the fluidity, the mechanical strength and the chemical resistance are lowered. It is generally known that the flow characteristics of the resin are closely related to the chemical structure of the resin, and in the case of the olefin resin, the flow structure is superior to the linear structure in the case where the structure of the resin is branched at the same weight average molecular weight . Recently, many methods for improving the workability while maintaining the mechanical properties have been studied. Among them, a method of converting the rheological properties through introducing a branch structure having a sufficient length into one resin is widely used.

US Patent Nos. 6,608,141, 6,433,092 and 5,191,040, and Korean Patent No. 10-0762884 disclose a method of using a polyfunctional initiator for producing a resin having a branched structure as described above. However, when a multifunctional initiator is used alone, the efficiency of branch structure formation on the radical decomposition mechanism of the initiator drops sharply. Considering the polymerization rate, introduction of a sufficient length of branch structure is not easy to control the content of the initiator and adversely affects the color.

U.S. Patent Nos. 5,489,652, 5,059,667, and Korean Patent No. 10-0474830 disclose the use of a bifunctional or multifunctional vinyl compound. However, due to the short molecular structure, these compounds cause cross-linking effect during the production of resin to cause gelation. The generated gel contaminates the inner wall of the reactor and adversely affects the productivity. Due to the local crosslinking structure inside the resin, The surface of the product is poor. Korean Patent No. 10-0749665 is characterized in that a vinyl compound is copolymerized using a polyfunctional initiator. However, when a multifunctional vinyl compound is copolymerized by using a polyfunctional initiator, a certain level of branch structure can be introduced. However, when a sufficient amount of the molecular weight regulator is not used, a gel may be generated. When the content of the multifunctional vinyl compound is increased It is difficult to control the polymerization rate and the molecular weight.

U.S. Patent No. 4,918,159 discloses a method for producing a styrene resin using a multifunctional mercaptan. However, in the case of the suspension polymerization using the multifunctional mercaptan alone, the reactivity is lowered, and the polymerization system is unstable as the polymerization reaction proceeds, thus causing a problem in the polymerization reaction control. Korean Patent Publication No. 10-2006-0074513 discloses a method for producing a methacrylic resin by using a multifunctional mercaptan. However, it is difficult to introduce a sufficient branch structure due to the chain transfer reactivity and the input amount limit of the mercaptan itself by using the multifunctional mercapto group alone.

Korean Patent Laid-Open Publication No. 10-2011-0061757 discloses a method of simultaneously polymerizing an aromatic vinyl compound and a vinyl cyanide compound by introducing a multifunctional initiator, a monofunctional mercaptan, a multifunctional vinyl compound and a multifunctional mercaptan, Discloses a method for producing a thermoplastic resin having excellent fluidity and physical properties by forming a branched structure of sufficient length without causing gelation due to crosslinking while maintaining an excellent and stable polymerization rate.

However, there is a continuing need for a new method for solving the problem that the heat resistance copolymer containing the N-substituted maleimide compound and the? -Alkylstyrene compound is deteriorated in flowability and productivity and processability.

A problem to be solved by the invention is to provide a resin composition having excellent flowability by imparting high fluidity in the production of a maleimide-? -Alkylstyrene-based high heat resistance quartz block copolymer having excellent thermal stability and kneading property at high temperature .

Another object of the present invention is to provide a high heat resistant quaternary block copolymer resin composition excellent in fluidity and excellent in fluidity without deteriorating mechanical properties and heat resistance.

It is still another object of the present invention to provide a method for producing a high heat resistant quaternary block copolymer resin composition suitable for a continuous bulk polymerization process and free from gelation.

These and other objects of the present invention can be achieved by the present invention described below

In order to solve the above problems, the present invention provides a method for producing a heat resistant mass copolymer comprising an N-substituted maleimide compound, an? -Alkylstyrene compound, an aromatic vinyl compound and an unsaturated nitrile compound excellent in heat resistance and fluidity Wherein the polyfunctional mercaptan and the polyfunctional vinyl compound are introduced.

In one aspect, the present invention relates to a process for the production of a copolymer comprising an N-substituted maleimide, an a-alkylstyrene, an unsaturated nitrile, and an aromatic vinyl compound and having a glass transition temperature of 160 캜 or higher, preferably 165 캜 or higher, Has a glass transition temperature of 170 DEG C or higher, a weight average molecular weight of 80,000 to 200,000, an MI index of 8 or more measured at 240 DEG C and 21.6 kg, and substantially no gel.

When the absolute molecular weight and the intrinsic viscosity of a massive block copolymer having excellent flowability and heat resistance produced according to the present invention are calculated graphically, the slope thereof exhibits a characteristic that the Mark-Houwink exponent α is 0.55 to 0.67.

Hereinafter, the present invention will be described in detail.

In the present invention, the N-substituted maleimide monomer is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, -Butyl maleimide, N-isobutyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide, N-methoxyphenylmaleimide, N-methoxyphenylmaleimide, Or a mixture thereof, and the like can be used, more preferably N-phenylmaleimide. In the present invention, the N-substituted maleimide monomer can prevent the increase of the melt viscosity and Brittleness while preventing the decrease of the heat resistance and thermal stability of the quaternary copolymer, And 5-60% by weight, more preferably 10-55% by weight, and even more preferably 15-50% by weight, in order to maintain kneadability and facilitate heat generation control.

 In the present invention, the? -Alkylstyrene monomer may be? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, or a mixture thereof, more preferably? -Methylstyrene. In the present invention, the? -Alkylstyrene monomer prevents the decrease in the heat resistance characteristics when the content of the? -Alkylstyrene copolymer is low, and the instability of the polymerization rate, which may occur when the content is high, , More preferably 20-60% by weight, and even more preferably 25-55% by weight, in order to prevent the deterioration of the heat resistance of the thermosetting resin composition.

In the present invention, the unsaturated nitrile monomer may be a vinyl cyan compound such as acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, or a mixture thereof And more preferably acrylonitrile. In the present invention, the unsaturated nitrile monomer is used in an amount of 5 wt% or more so as to maintain an appropriate polymerization rate in the mass of the block copolymer and to prevent the non-uniform polymerization from proceeding due to the lowering of the solubility of the N-substituted maleimide monomer It is preferably used in an amount of 50% by weight or less, more preferably 10-45% by weight, more preferably 10-45% by weight in order to control the heat generation during the polymerization and to maintain the color tone of the quaternary copolymer. Preferably from 15 to 40% by weight.

In the present invention, examples of the aromatic vinyl monomer include styrene-based monomers such as styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, Or a mixture thereof, and more preferably styrene. In the present invention, the aromatic vinyl monomers are preferably used in an amount of 3 to 3 to maintain the melt viscosity in the siloxane copolymer so that the final product has good processability, formability and kneading property when blended with other resins, It is preferably used in an amount of 50% by weight or less, more preferably 5-45% by weight, and even more preferably 10-40% by weight in order to prevent the deterioration of heat resistance.

In the preferred embodiment of the present invention, the high-temperature-resistant heat-resistant copolymer is composed of 15 to 50 parts by weight of the N-substituted maleimide monomer, 25 to 55 parts by weight of the? -Alkylstyrene monomer, 15 to 40 parts by weight of the unsaturated nitrile monomer, To 40 parts by weight of a monomer mixture, and has an MI of 8 or more measured at 240 DEG C and 21.6 kg.

In the present invention, a multifunctional mercaptan is a compound having three or more-SH groups as a mercaptan having three or more valences, preferably a trifunctional and tetravalent mercaptan. The effect of improving the fluidity due to the branching effect is small and the possibility of forming a gel is high, which is not preferable. Examples of trifunctional mercaptans include trimethypropane tri (3-mercaptopropionate), trimethylolpropane tri (3-mercaptoacetate), trimethylolpropane tri (4-mercaptobutanate), tri Methylol propane tri (5-mercaptopentanate), trimethylol propane tri (6-mercaptohexanoate), and the like can be used. Examples of the 4-valent functional mercaptans include pentaerythritol tetrakis (2-mercaptoacetate), tentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercaptobutanate) Pentaerythritol tetrakis (5-mercaptopentanate), pentaerythritol tetrakis (6-mercaptohexanate), and the like. In the present invention, the multifunctional mercaptan may be used alone or in combination of two or more. The content of the polyfunctional mercaptan is suitably 0.001 to 0.3 parts by weight, more preferably 0.01 to 0.1 parts by weight, per 100 parts by weight of the mixture for preparing a quaternary copolymer. When the content of the multifunctional mercaptan is less than 0.001 part by weight, it is difficult to obtain the branching structure effect, and the polymerization rate and molecular weight increase due to the introduction of the multifunctional vinyl compound can not be efficiently controlled and it is not suitable for preventing gel formation. , There is a problem that the gel content is drastically increased due to the high crosslinking density.

In the present invention, the polyfunctional vinyl compound is a compound having three or more unsaturated hydrocarbons, and examples of the trifunctional vinyl compound include pentaerythritol triacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate Acrylate and the like can be used. As the tetrafunctional vinyl compound, di (trimethylol propane) tetraacrylate, pentaerythritol tetraacrylate and the like can be used. As the pentafunctional vinyl compound, dipentaerythritol pentaacrylate, and as the hexafunctional vinyl compound, dipentaerythritol hexaacrylate and the like can be used. In the present invention, the polyfunctional vinyl compound may be used alone or in combination of two or more. On the other hand, it is difficult to precisely control the structure of the resin when a bifunctional vinyl compound is used to produce a styrene resin having a branched structure, so that it is difficult to obtain a branch structure having desired characteristics and it is difficult to control the balance of physical properties.

The content of the polyfunctional vinyl compound is suitably 0.001 to 0.2 parts by weight, more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of the mixture of the aromatic vinyl compound and the vinyl cyanide compound. When the total content of the polyfunctional vinyl compound is less than 0.001 part by weight, the effect of chain entanglement due to the branch structure is not sufficiently exhibited. When the content of the polyfunctional vinyl compound exceeds 0.2 parts by weight, the molecular weight increases sharply or the cross- And the inner wall of the reactor is contaminated and the surface of the final product is not smooth.

In the production of the heat resistant quaternary copolymer of the present invention, a monofunctional mercaptan can be further used so as to prevent the molecular weight of the copolymer from becoming excessively large by controlling the molecular weight of the copolymer. The monofunctional mercaptans that can be used in the present invention are n-butylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and the like, which can be used alone or in a mixture of two or more have. In a preferred embodiment, the monofunctional mercaptan is used in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the monomer mixture.

In the production of the heat-resistant quaternary copolymer of the present invention, it is also preferable to use an initiator which has an appropriate reaction rate and can prevent gel formation. It is preferred to use a monofunctional initiator, a polyfunctional initiator, or a mixture thereof, and preferably to use a monofunctional initiator for the stability of the reaction.

The monofunctional initiator that can be used in the present invention is a monomer mixture comprising a group consisting of azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate ≪ / RTI > may be used.

The content of the initiator is suitably 0.001 to 1 part by weight, more preferably 0.02 to 0.5 part by weight based on 100 parts by weight of the mixture for preparing a quaternary copolymer. If the content of the initiator is less than 0.001 part by weight, the effect as an initiator is not exhibited and it is not suitable for preventing gel formation. When the amount exceeds 1.0 part by weight, there is a problem in controlling the polymerization rate and controlling the molecular weight .

In the present invention, the weight average molecular weight of the maleimide-? -Alkylstyrene-based high heat resistant quaternium block copolymer having excellent flowability is preferably 80,000 to 200,000, more preferably 80,000 to 150,000. When the weight average molecular weight is less than 80,000, the molecular weight is too low to lower the mechanical properties, and when the weight average molecular weight is 200,000 or more, the melt viscosity increases sharply and the working may be difficult.

In the present invention, the quaternary copolymerization is a bulk polymerization in which polymerization is carried out in a monomer mixture. The bulk polymerization may be carried out using an inert organic solvent. Any organic solvent may be used as long as the organic solvent used for the polymerization is inert to the reaction and is capable of dissolving both the raw monomer and the polymerization product. Examples of such an organic solvent include aromatic hydrocarbons such as various alcohols, petroleum ether, ethylbenzene and toluene, and halides such as carbon tetrachloride, chloroform, and ketones such as methyl ethyl ketone. They may be used alone or in a mixture of two or more. The amount of the organic solvent to be used can be appropriately adjusted in consideration of the viscosity reduction effect in the reaction system and the like, but the organic solvent ratio is suitably in the range of 5 to 30% by weight with respect to the monomer and the organic solvent mixture. When the amount is less than 5% by weight, the viscosity of the reactor is rapidly increased, which is not preferable. When the amount exceeds 30% by weight, the effective reaction volume of the reactor is decreased and the devolatilizing mechanism and the recovering device are complicated and large.

In addition to bulk polymerization, the present invention can be produced by known polymerization methods such as solution polymerization and suspension polymerization. However, bulk polymerization is most suitable for increasing efficiency of introduction of productivity and branch structure and for more effective copolymerization reaction.

The present invention will be further illustrated by the following examples, which are to be construed as illustrative examples only and are not intended to limit or limit the scope of protection of the present invention.

INDUSTRIAL APPLICABILITY As described above, the present invention relates to a maleimide- &agr; -alkylstyrene-based high heat resistant quaternary copolymer and a method for producing the same, wherein the gel is obtained by simultaneously using a multifunctional mercaptan and a multifunctional vinyl compound Heat-resistant quaternary block copolymer having excellent fluidity through a branched structure introduced without degradation of mechanical properties and heat resistance.

Example 1

Into a stirring reactor having a reactor capacity of 100 L, 23 wt% of N-phenylmaleimide, 40 wt% of alpha -methylstyrene, 17 wt% of styrene, 20 wt% of acrylonitrile and 100 wt parts of t- 0.20 part of butyrate, 0.25 part of t-dodecyl mercaptan (TDM) which is a monofunctional mercaptan, 0.05 part of trimethylolpropane tris (3-mercaptopropionate) (TMPTM) 0.03 parts by weight of trimethylolpropane trimethacrylate (TMPTMA) as a functional vinyl compound, and 15 parts by weight of toluene were uniformly mixed, and then the mixture was introduced into a reactor. The polymerization reaction solution was prepared by maintaining the polymerization reaction at 60% while maintaining the reaction temperature at 95 ° C. The unreacted monomers and the solvent were removed while maintaining the polymerization solution at 230 ° C. and a vacuum pressure of 20 torr, Alpha-alkylstyrene-based high heat-resistant, high-heat-resistant block copolymer having excellent fluidity, and the results are shown in Table 1 below.

Example 2

Into a stirring reactor having a reactor capacity of 100 L, 23 g of n-phenylmaleimide, 40 wt% of? -Methylstyrene, 17 wt% of styrene, 20 wt of acrylonitrile and 100 g of a monofunctional mercaptan , 0.30 part by weight of dodecylmercaptan (TDM) was added, and 0.05 part by weight of trimethylolpropane tris (3-mercaptopropionate) (TMPTM), which is a multifunctional mercaptan, and 0.05 part by weight of dipentaerythritol Maleic anhydride copolymer having excellent flowability was prepared and the physical properties thereof were measured in the same manner as in Example 1 except that 0.02 part by weight of pentaacrylate (DPTPA) was added, The results are shown in Fig.

Example 3

Into a stirring reactor having a reactor capacity of 100 L, 23% by weight of N-phenylmaleimide, 40% by weight of? -Methylstyrene, 17% by weight of styrene, 20% by weight of acrylonitrile and 100% by weight of monofunctional mercaptan and 0.03 part by weight of pentaerythritoltetrakis (3-mercaptopropionate) (PETMP), which is a multifunctional mercaptan, were added to the flask and 0.25 parts by weight of t-dodecyl mercaptan (TDM) A maleimide-? -Alkylstyrene-based high heat-resisting, high heat-resistant block copolymer having excellent flowability was prepared and measured for its physical properties in the same manner as in Example 1, except that 0.03 parts by weight of trimethylolpropane trimethacrylate (TMPTMA) The results are shown in Table 1 below.

Example 4

Into a stirring reactor having a reactor capacity of 100 L, 23% by weight of N-phenylmaleimide, 40% by weight of? -Methylstyrene, 17% by weight of styrene, 20% by weight of acrylonitrile and 100% by weight of monofunctional mercaptan 0.30 part by weight of t-dodecylmercaptan (TDM) was added and 0.03 part by weight of pentaerythritol tetrakis (3-mercaptopropionate) (PETMP), which is a multifunctional mercaptan, A maleimide-? -Alkylstyrene-based high heat-resistant, block copolymer having excellent flowability was prepared in the same manner as in Example 1, except that 0.02 part by weight of dipentaerythritol pentaacrylate (DPTPA) was added. The results are shown in Table 1 below.

Comparative Example 1

In the same manner as in Example 1 except that 0.22 parts by weight of t-dodecyl mercaptan (TDM) which is a monofunctional mercaptan in Example 1 was added and no multifunctional mercaptan or multifunctional vinyl compound was used, The results are shown in Table 1 below. ≪ tb >< TABLE >

Comparative Example 2

Except that 0.20 parts by weight of t-dodecyl mercaptan (TDM), which is a monofunctional mercaptan, was added in Example 1, and the multifunctional vinyl compound was not used at all. The physical properties were measured and the results are shown in Table 1 below.

Comparative Example 3

In Example 1, 0.18 parts by weight of t-dodecyl mercaptan (TDM), which is a monofunctional mercaptan, was added and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP), which is a multifunctional mercaptan, A resin was prepared in the same manner as in Example 1 except that no added polyfunctional vinyl compound was used and the properties were measured and the results are shown in Table 1 below.

Comparative Example 4

A resin was prepared in the same manner as in Example 1, except that 0.27 parts by weight of t-dodecyl mercaptan (TDM), which is a monofunctional mercaptan, was used in Example 1 and no multifunctional mercaptan was used , And physical properties were measured, and the results are shown in Table 1 below.

Comparative Example 5

In Example 1, 0.33 part by weight of t-dodecyl mercaptan (TDM), which is a monofunctional mercaptan, was added and 0.02 part by weight of dipentaerythritol pentaacrylate (DPTPA), which is a multifunctional vinyl compound, A resin was prepared in the same manner as in Example 1 except that no capstan was used, and physical properties were measured, and the results are shown in Table 1 below.

Comparative Example 6

0.38 parts by weight of t-dodecyl mercaptan (TDM), which is a monofunctional mercaptan, was added in Example 1 and 0.05 part by weight of dipentaerythritol pentaacrylate (DPTPA), which is a polyfunctional vinyl compound, was added, A resin was prepared in the same manner as in Example 1 except that no capstan was used, and physical properties were measured, and the results are shown in Table 1 below.

How to measure property

(1) Weight average molecular weight: Measured using Gel Permeation Chromatography (GPC) instrument

(2) Mark-Houwink exponent α: GPC-low angle light scattering was analyzed and the result was measured.

(3) Flowability: Measured under conditions of 240 占 폚 and 21.6 kg.

(4) Gel contents (%): The sample was dissolved in acetone and centrifuged to separate the insoluble matter. After the weight was measured, the weight% with respect to the weight of the initial sample was calculated.

[Table 1]

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims,

Claims (16)

A monomer mixture composed of an N-substituted maleimide monomer, an? -Alkylstyrene monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer is used as a monofunctional initiator together with a monofunctional mercaptan, a polyfunctional mercaptan, and a polyfunctional vinyl compound Wherein the polymer is polymerized in bulk. The composition according to claim 1, wherein the monomer mixture comprises 5-60 parts by weight of an N-substituted maleimide monomer, 10-70 parts by weight of an? -Alkylstyrene monomer, 5-50 parts by weight of an unsaturated nitrile monomer, 3-50 parts by weight of an aromatic vinyl monomer, Resistant resin. The composition according to claim 1, wherein the monomer mixture comprises 15 to 50 parts by weight of an N-substituted maleimide monomer, 25 to 55 parts by weight of an? -Alkylstyrene monomer, 15 to 40 parts by weight of an unsaturated nitrile monomer, and 10 to 40 parts by weight of an aromatic vinyl monomer ≪ / RTI > wherein the monomer mixture is a mixture of monomers. 4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein 0.001 to 0.3 parts by weight of a multifunctional mercaptan, 0.001 to 0.5 parts by weight of a monofunctional mercaptan, and 0.001 to 0.5 parts by weight of a multifunctional vinyl compound To 0.2 part by weight of a thermosetting resin. 4. The process according to any one of claims 1 to 3, wherein the monomer mixture is selected from the group consisting of azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate Wherein the polymerization initiator is polymerized using a monofunctional initiator compound selected from the group consisting of at least one polymerizable monomer. 4. The process according to any one of claims 1 to 3, wherein the multifunctional mercaptan is selected from the group consisting of trimethylolpropane tri (3-mercaptopropionate), trimethylolpropane tri (3-mercaptoacetate) (4-mercaptobutanoate), trimethylolpropane tri (5-mercaptopentanate), trimethylolpropane tri (6-mercaptohexanoate), pentaerythritol tetrakis Pentaerythritol tetrakis (4-mercaptobutanoate), pentaerythritol tetrakis (5-mercaptopentanate), pentaerythritol (4-mercaptobutanoate) And tetrakis (6-mercaptohexanate). ≪ / RTI > The polyfunctional vinyl compound according to any one of claims 1 to 3, wherein the polyfunctional vinyl compound is selected from the group consisting of pentaerythritol triacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, di (trimethylol propane ) Tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof. 4. The process of any one of claims 1 to 3 wherein the N-substituted maleimide monomer is selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N - isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-naphthylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N- Benzylmaleimide, and benzylmaleimide. The heat-resistant resin composition according to any one of claims 1 to 3, wherein the? -Alkylstyrene monomer is at least one selected from the group consisting of? -Methylstyrene,? -Ethylstyrene and methyl? -Methylstyrene ≪ / RTI > The aromatic vinyl monomer according to any one of claims 1 to 3, wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene, vinyl toluene, t-butyl styrene, halogen substituted styrene, 1,3-dimethyl styrene, Wherein the heat-resistant resin is at least one selected from the group consisting of polyvinyl chloride and polyvinyl chloride. 4. The composition of any one of claims 1 to 3, wherein the unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, alpha -chloroacrylonitrile, Wherein the heat-resistant resin is selected from the group consisting of: 4. The method according to any one of claims 1 to 3, wherein the bulk polymerization further comprises 5-30% by weight of a solvent based on 100 parts by weight of the monomer mixture. Characterized in that it comprises an N-substituted maleimide, an? -Alkylstyrene, an unsaturated nitrile compound and an aromatic vinyl compound and has an MI index of 8 or more measured at 240 占 폚 and 21.6 kg and substantially no gel. Block copolymers. 14. The method of claim 13, wherein the copolymer comprises 5 to 60 parts by weight of N-substituted maleimide, 10 to 70 parts by weight of? -Alkylstyrene, 5 to 50 parts by weight of an unsaturated nitrile compound and 3 to 50 parts by weight of an aromatic vinyl compound Heat-resistant block copolymer. 14. The method according to claim 13, further comprising: 15 to 50 parts by weight of N-substituted maleimide, 25 to 55 parts by weight of? -Alkylstyrene, 15 to 40 parts by weight of an unsaturated nitrile compound and 10 to 40 parts by weight of an aromatic vinyl compound. Block copolymers. The heat-resistant block copolymer according to any one of claims 13 to 15, wherein the copolymer has a weight average molecular weight of 80,000 to 200,000 and a glass transition temperature of 160 ° C or higher.