KR20170043901A - Preparation method of heat-resistant styrene copolymer and heat-resistant styrene copolymer produced by the same - Google Patents
Preparation method of heat-resistant styrene copolymer and heat-resistant styrene copolymer produced by the same Download PDFInfo
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- KR20170043901A KR20170043901A KR1020150143555A KR20150143555A KR20170043901A KR 20170043901 A KR20170043901 A KR 20170043901A KR 1020150143555 A KR1020150143555 A KR 1020150143555A KR 20150143555 A KR20150143555 A KR 20150143555A KR 20170043901 A KR20170043901 A KR 20170043901A
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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
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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
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to a process for producing a heat-resistant styrenic copolymer having excellent heat resistance and a heat-resistant styrenic copolymer produced therefrom. In the production method, the second monomer mixture is further added to prepare a heat-resistant styrenic copolymer by the second polymerization step to improve the polymerization reactivity to improve the conversion and to produce a styrenic copolymer having excellent heat resistance .
Description
The present invention relates to a process for producing a heat-resistant styrenic copolymer having excellent heat resistance and a heat-resistant styrenic copolymer produced therefrom.
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 resistance characteristics, the polymerization proceeds at a temperature lower than the polymerization temperature of the existing heat-resistant styrenic copolymer due to a low ceiling temperature (Tc) There is a problem that the polymerization reaction must proceed and the polymerization conversion rate is greatly lowered, and also the molecular weight of the polymer produced is low and pyrolysis can easily occur.
Therefore, a manufacturing method through emulsion polymerization using a batch process which can easily control the polymerization reaction temperature and the polymerization reaction time has been mainly used. However, such emulsion polymerization requires a long polymerization reaction time due to a low reaction temperature and requires a high coagulation temperature condition. Since impurities such as an emulsifier and a flocculant are contained in the resin, they are easily decomposed into heat during extrusion and injection molding, And the like. In addition, the above emulsion polymerization is not carried out in the process of recovering unreacted monomers, so that the heat resistance may be lowered due to unreacted monomers remaining in the resin, and a large amount of acrylonitrile is contained in the unreacted monomers, However, there is a problem that the acrylonitrile remains as an insoluble gel and acts as a foreign substance damaging the appearance.
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.
The present invention has been conceived to solve the problems of the prior art, and an object of the present invention is to provide a production method capable of producing a heat-resistant styrenic copolymer having excellent heat resistance while improving polymerization conversion.
Another object of the present invention is to provide a heat-resistant styrenic copolymer produced by the above production process.
In order to solve the above problems, the present invention provides a process for producing a polymer, comprising: (1) preparing a polymer by first polymerizing a first monomer mixture comprising? -Methylstyrene and acrylonitrile; And a step (2) of introducing a second monomer mixture containing? -Methylstyrene and methacrylonitrile into the polymer and then polymerizing the second monomer (Step 2). The present invention also provides a method for producing a heat-resistant styrenic copolymer. .
Further, the present invention provides a heat-resistant styrenic copolymer produced by the above-mentioned production method.
The production method according to the present invention can improve the polymerization reactivity by improving the polymerization reactivity by preparing the heat-resistant styrenic copolymer by the second polymerization step by further adding the second monomer mixture, and at the same time, preparing the styrenic copolymer having excellent heat resistance .
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 production method capable of producing a heat-resistant styrenic copolymer having improved heat resistance and improved productivity with improved 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 The polymerization is carried out at a temperature, resulting in a problem that the conversion rate is significantly lowered. The low conversion rate is directly linked to the deterioration of productivity, which is a major obstacle to industrial application.
Therefore, in order to easily apply the heat-resistant styrenic copolymer to the industry, there is a need for a technique that improves the conversion of? -Methylstyrene to improve productivity and does not deteriorate the mechanical-chemical properties inherent in the heat-resistant styrenic copolymer.
Accordingly, the present invention provides a method for producing a heat-resistant styrenic copolymer capable of producing a heat-resistant styrenic copolymer having excellent heat resistance at a high conversion ratio.
According to an embodiment of the present invention, the method comprises: (1) preparing a polymer by first polymerizing a first monomer mixture comprising? -Methylstyrene and acrylonitrile; And a step (2) of introducing a second monomer mixture containing? -Methylstyrene and methacrylonitrile into the polymer and then performing a second polymerization.
Further, the production method is characterized in that the second monomer mixture is introduced at a point of time when the polymerization conversion rate of the first monomer mixture is 50% or more.
In addition, the production method according to an embodiment of the present invention may be performed by continuous bulk polymerization. For example, a continuous reactor in which at least two stirring vessels are connected in series is used to continuously feed materials to be polymerized, Or by polymerizing them.
Hereinafter, the manufacturing method according to an embodiment of the present invention will be described step by step.
Step 1 is a step for preparing a polymer by first polymerizing a first monomer mixture containing? -Methylstyrene and acrylonitrile.
Specifically, the first monomer mixture may contain 60 wt% to 75 wt% of? -Methylstyrene and 25 wt% to 40 wt% of acrylonitrile.
The above-mentioned alpha-methylstyrene (AMS) is an alkylated styrene compound represented by the following formula (1), which has excellent heat resistance characteristics and is used as a chemical intermediate or raw material for imparting heat resistance in the production of resins and polymers have.
[Chemical Formula 1]
As described above, the? -Methylstyrene has excellent heat resistance and can improve the heat resistance of the finally produced heat-resistant styrenic copolymer. 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, in the production method according to an embodiment of the present invention, acrylonitrile is first polymerized together with the? -Methylstyrene to prepare a polymer, and then a second monomer mixture comprising? -Methylstyrene and methacrylonitrile And the secondary polymerization was carried out to improve the mechanical and chemical properties and to improve the conversion and heat resistance.
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 first monomer mixture may contain 60 wt% to 75 wt% of? -Methylstyrene. 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 content of acrylonitrile, which will be described later, The effect of improving the conversion rate is insignificant, resulting in a decrease in the weight average molecular weight due to a low polymerization conversion rate and a large amount of residual monomers.
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.
The first monomer mixture may contain 25 wt% to 40 wt% of the acrylonitrile as described above. If the amount of the acrylonitrile is less than 25% 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 40% by weight, the content of? -Methylstyrene may be relatively decreased, which may cause a decrease in heat resistance.
The first polymerization may be carried out by continuously introducing the first monomer mixture into a polymerization reactor and mass-mixing the first monomer mixture. In this case, the first polymerization may be carried out by using a polymerization initiator and a reaction medium, if necessary, to perform bulk polymerization, and the polymerization initiator and the reaction medium are continuously introduced into the polymerization reactor simultaneously with the first monomer mixture Alternatively, the first monomer mixture may be sequentially introduced, and the polymerization initiator and the reaction medium may be continuously introduced. In addition, the polymerization initiator and the reaction medium may be added to the first monomer mixture before being added to the polymerization reactor, and the mixture may be continuously added to the polymerization reactor in a mixture state.
The polymerization initiator is not particularly limited, but may be used in an amount of 0.1 part by weight to 0.3 part by weight based on 100 parts by weight of the first monomer mixture. Specifically, the polymerization initiator may be an organic peroxide initiator containing a polyfunctional group and is not particularly limited. Examples thereof include 1,1-bis (tertiarybutylperoxy) cyclohexane, 1,1-bis (tertiarybutylperoxy) Bis (tertiary butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (tertiary butylperoxy) butane and 2,2-bis 4,4-ditertiary butyl peroxycyclohexane) propane.
The reaction medium may be used in an amount of 10 parts by weight or less based on 100 parts by weight of the first monomer mixture, but is not limited thereto. The reaction medium may be an aromatic compound such as ethylbenzene, benzene, toluene or xylene; Methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane, and the like, but is not limited thereto.
The primary polymerization may be performed at a temperature ranging from 100 ° C to 120 ° C for a reaction time of 4 hours to 6 hours, but is not limited thereto. At this time, the reaction time may be the same as the residence time in the polymerization reactor and may be controlled by controlling the flow rate of the first monomer mixture.
The step 2 is a step for preparing a heat-resistant styrenic copolymer at an improved conversion rate. The step 2 may be carried out by introducing a second monomer mixture into the polymerized product prepared in the step 1, followed by secondary polymerization.
The second monomer mixture may comprise? -Methylstyrene and methacrylonitrile, and? -Methylstyrene and methacrylonitrile in the second monomer mixture may have a weight ratio of 6.5: 3.5 to 8: 2 . In addition, the weight ratio of? -Methylstyrene in the second monomer mixture may be a weight ratio of 5% to 10% reduced relative to the weight ratio of? -Methylstyrene in the first monomer mixture. For example, when the total weight of the first monomer mixture is 10 and the weight ratio of? -Methylstyrene in the first monomer mixture is 8, the weight ratio of? -Methylstyrene in the second monomer mixture (total weight 10) 7.6. ≪ / RTI > If the weight ratio of? -Methylstyrene and methacrylonitrile in the second monomer mixture is out of the above range, the effect of improving the heat resistance and conversion may be insignificant.
The second polymerization may be carried out by adding the second monomer mixture to the polymerizate prepared in the step 1 and bulk mixing. The second monomer mixture may be added in an amount of 20 parts by weight or less based on 100 parts by weight of the first monomer mixture. Specifically, the second monomer mixture may be added in an amount of 10 parts by weight to 20 parts by weight.
In addition, the second monomer mixture may be added at a time when the polymerization conversion of the first monomer mixture is 50% or more as described above. If the second monomer mixture is added to the first monomer mixture at a polymerization conversion rate of less than 50%, secondary polymerization may cause a decrease in polymerization conversion.
Here, the polymerization conversion rate represents the degree of polymerization conversion of the first monomer mixture, that is, the degree of polymerization of? -Methylstyrene and acrylonitrile contained in the first monomer mixture to form a polymer. The weight and the weight of the polymer after dewatering and drying were measured and calculated as the ratio of the two weights.
The secondary polymerization may be performed under elevated temperature conditions relative to the primary polymerization. Specifically, it may be carried out under a temperature condition that is raised by 2 ° C to 10 ° C relative to the temperature at the time of the first polymerization.
The production method according to an embodiment of the present invention is characterized in that a second monomer mixture containing? -Methylstyrene and methacrylonitrile is introduced and subjected to second-order polymerization to form a thermostable styrenic copolymer finally produced by the methacrylonitrile Can be further improved. Further, the conversion rate can be further improved by further participating in the reaction of the unreacted? -Methylstyrene.
In addition, the manufacturing method according to an embodiment of the present invention may further include a devolatilizing process step after the step 2.
The devolatilization process is for recovering and removing impurities such as a weakly monomer, a reaction medium and the like, and is not particularly limited, and may be carried out under appropriate conditions to easily recover and remove the impurities. Specifically, it may be carried out at a temperature of 240 to 300 DEG C and a vacuum pressure of 30 torr or less.
Further, the present invention provides a heat-resistant styrenic copolymer produced by the above-mentioned production method.
The heat-resistant styrenic copolymer according to an embodiment of the present invention has a glass transition temperature of 126 캜 or higher.
The glass transition temperature was elevated from room temperature to 160 캜 at a rate of 20 캜 / min using a differential scanning calorimetry (DSC) Ta instrument Q10, and then the temperature was decreased to 40 캜 at 20 캜 / min. And the maximum temperature difference of the heat flow during the phase change was measured when the temperature was increased by 10 ° C / min.
On the other hand, the heat-resistant styrenic copolymer according to one embodiment of the present invention can 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.
Example 1
100 parts by weight of a first monomer mixture containing 70% by weight of? -methylstyrene and 30% by weight of acrylonitrile, 0.2 parts by weight of 1,1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane And 3 parts by weight of toluene were continuously introduced into a first polymerization reactor equipped with a stirrer, followed by primary polymerization at 110 占 폚. At this time, the feed flow rate was adjusted so that the residence time in the first polymerization reactor was 5 hours. Thereafter, the polymerizers of the first polymerization reactor were all transferred to the second polymerization reactor, and 20 parts by weight of the second monomer mixture was added at the time when the polymerization conversion conversion ratio of the first monomer mixture was 50%, followed by secondary polymerization Respectively. The second monomer mixture was prepared by mixing? -Methylstyrene and methacrylonitrile in a weight ratio of 6.5: 3.5. After completion of the polymerization, a devolatilization process was performed at a temperature of 250 ° C and a vacuum pressure of 30 torr to recover unreacted monomers and toluene, and a pellet-shaped heat resistant styrenic copolymer was produced through a discharge pump extruder.
Example 2
A heat-resistant styrenic copolymer in the form of pellets was prepared in the same manner as in Example 1 except that a first monomer mixture containing 72% by weight of? -methylstyrene and 28% by weight of acrylonitrile was used.
Example 3
The heat-resistant styrenic copolymer in the form of pellets was prepared in the same manner as in Example 1, except that 15 parts by weight of the second monomer mixture was used.
Comparative Example 1
100 parts by weight of a monomer mixture comprising 70% by weight of? -methylstyrene and 30% by weight of acrylonitrile, 0.2 part by weight of 1,1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane, 3 parts by weight were added, and the mixture was continuously charged into a polymerization reactor, followed by bulk polymerization at 110 占 폚. After completion of the polymerization, a devolatilization process was performed at a temperature of 250 ° C and a vacuum pressure of 30 torr to recover unreacted monomers and toluene, and a pellet-shaped heat resistant styrenic copolymer was prepared through a discharge pump extruder.
Comparative Example 2
except that a monomer mixture containing 70% by weight of? -methylstyrene, 25% by weight of acrylonitrile and 5% by weight of methacrylonitrile was used instead of the thermoplastic styrenic copolymer .
Comparative Example 3
A heat-resistant styrenic copolymer in the form of pellets was prepared in the same manner as in Example 1, except that styrene monomer was used instead of the second monomer mixture.
Comparative Example 4
A heat-resistant styrenic copolymer in the form of pellets was prepared in the same manner as in Example 1, except that? -Methylstyrene was used instead of the second monomer mixture.
Comparative Example 5
A heat-resistant styrenic copolymer in the form of pellets was prepared in the same manner as in Example 1 except that the second monomer mixture was added at a polymerization conversion rate of 40% of the first monomer mixture.
Experimental Example
(%) And the weight average molecular weight (Mw, g (g)) of each of the copolymers were measured in order to comparatively analyze the physical properties of the heat-resistant styrenic copolymers prepared in Examples 1 to 3 and Comparative Examples 1 to 5 / mol) and glass transition temperature (Tg, 占 폚) were measured. The results are shown in Table 1 below.
1) Conversion rate (%)
After the completion of the polymerization, the total weight of the polymerized product before the devolatilization process was measured, and the weight of the heat-resistant styrenic copolymer prepared after the devolatilization process was measured.
2) Weight average molecular weight (g / mol)
The weight average molecular weight was determined by dissolving each copolymer in tetrahydrofuran and relative value to standard polystyrene samples through gel permeation chromatography (GPC).
3) Glass transition temperature (占 폚)
The glass transition temperature was increased from room temperature to 160 ° C at a rate of 20 ° C / min using a differential scanning calorimetry (DSC) Ta instrument Q10, then the temperature was decreased to 20 ° C / min to 40 ° C, min, the maximum variation point of the heat flow was measured in the section where the phase change occurred.
The heat-resistant styrenic copolymers of Examples 1 to 3 according to one embodiment of the present invention, as shown in Table 1 above, exhibited an overall conversion rate as compared with the heat-resistant styrenic copolymers of Comparative Examples 1 to 5 And showed a high glass transition temperature.
Specifically, the conversion of the heat-resistant styrenic copolymer of Comparative Example 1 to the heat-resistant styrenic copolymer of Example 1 was 8% when the second polymerization was not carried out using the second monomer mixture, And the glass transition temperature decreased by 2%.
In addition, the heat-resistant styrenic copolymer of Comparative Example 2, which was a ternary copolymer produced by using methacrylonitrile, exhibited a glass transition temperature similar to that of the heat-resistant styrenic copolymer of Example 1, Which is about 75% of that of the thermostable styrenic copolymer.
The heat-resistant styrenic copolymer of Comparative Example 3 using the styrene monomer instead of the second monomer mixture showed a similar degree of conversion as compared with the heat-resistant styrenic copolymers of Examples 1 to 3. The glass transition temperature was 7% 8, and the heat-resistant styrenic copolymer of Comparative Example 4 using? -Methylstyrene had a glass transition temperature similar to that of the heat-resistant styrenic copolymers of Examples 1 to 3, but the conversion rate was 18% Respectively.
In the case of the heat-resistant styrenic copolymer of Comparative Example 5 in which the second monomer mixture was added and polymerized at a time outside the point of view of the present invention, the glass transition temperature of the heat-resistant styrenic copolymers of Examples 1 to 3 Was decreased.
Claims (13)
2) introducing a second monomer mixture containing? -Methylstyrene and methacrylonitrile into the polymerizable material, and subjecting the second monomer mixture to second-stage polymerization to produce a heat-resistant styrenic copolymer.
Wherein the second monomer mixture is introduced at a time when the polymerization conversion ratio of the first monomer mixture is 50% or more.
Wherein the second monomer mixture is added in an amount of 20 parts by weight or less based on 100 parts by weight of the first monomer mixture.
Wherein the second monomer mixture comprises? -Methylstyrene and methacrylonitrile in a weight ratio of 6.5: 3.5 to 8: 2.
Wherein the first monomer mixture comprises 60 wt% to 75 wt% of? -Methylstyrene and 25 wt% to 40 wt% of acrylonitrile.
Wherein the secondary polymerization is carried out under elevated temperature conditions relative to the primary polymerization.
Wherein the manufacturing method further comprises a devolatilization step after step 2).
Wherein the devolatilization step is carried out at a temperature of 240 ° C to 300 ° C and a vacuum pressure of 30 torr or less.
Wherein the production process is carried out by continuous bulk polymerization.
Wherein the first 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 glass transition temperature of 126 캜 or higher.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100193022B1 (en) * | 1995-12-26 | 1999-06-15 | 유현식 | Process for production of optical polymer resins having good heat resistance properties |
| KR20060074752A (en) | 2004-12-28 | 2006-07-03 | 주식회사 엘지화학 | Method for continuous preparing alpha methylstrylene-acrylonitrile copolymer resin having heat-resistance |
| KR20070101537A (en) * | 2006-04-11 | 2007-10-17 | 주식회사 엘지화학 | Preparation method of copolymer of aromatic vinyl monomer and vinylcyano compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100193022B1 (en) * | 1995-12-26 | 1999-06-15 | 유현식 | Process for production of optical polymer resins having good heat resistance properties |
| KR20060074752A (en) | 2004-12-28 | 2006-07-03 | 주식회사 엘지화학 | Method for continuous preparing alpha methylstrylene-acrylonitrile copolymer resin having heat-resistance |
| KR20070101537A (en) * | 2006-04-11 | 2007-10-17 | 주식회사 엘지화학 | Preparation method of copolymer of aromatic vinyl monomer and vinylcyano compound |
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