KR20170062792A - Method for preparing high temperature copolymer - Google Patents
Method for preparing high temperature copolymer Download PDFInfo
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- KR20170062792A KR20170062792A KR1020150168412A KR20150168412A KR20170062792A KR 20170062792 A KR20170062792 A KR 20170062792A KR 1020150168412 A KR1020150168412 A KR 1020150168412A KR 20150168412 A KR20150168412 A KR 20150168412A KR 20170062792 A KR20170062792 A KR 20170062792A
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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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- 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
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
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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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a method for producing a heat-resistant copolymer, and more particularly, to a method for producing a heat-resistant copolymer by reversible iodine chain transfer polymerization (RITP) of an aromatic vinyl monomer and a vinyl cyan monomer, A first polymerization step of polymerizing all of the vinyl monomers and a part of the vinyl cyan monomer in the presence of a compound containing iodine, an initiator, and a redox-based catalyst; And (ii) a second polymerization step of continuously polymerizing the residual vinyl cyan monomer, initiator and redox catalyst at a polymerization conversion rate of 20 to 40% in the first polymerization step, wherein the aromatic vinyl monomer Wherein the content of? -Alkylstyrene is 50% by weight or more.
According to the present invention, it is possible to provide a process for producing a heat-resistant copolymer which is excellent in polymerization conversion and polymerization stability and has a reduced molecular weight and polydispersity index and is excellent in flowability and glass transition temperature without generating an unpleasant odor during processing .
Description
More particularly, the present invention relates to a process for producing a heat-resistant copolymer, which is free from unpleasant odor during processing, has excellent polymerization conversion and polymerization stability, and has a reduced molecular weight and polydispersity index, To a process for producing a heat-resistant copolymer.
Styrene-acrylonitrile (hereinafter referred to as SAN) resin, which is a copolymer resin made by polymerizing styrene (SM) and acrylonitrile (AN), has excellent transparency, chemical resistance and rigidity, , Automobile parts, and the like.
In addition, SAN resin is used for reinforcement of heat resistance by applying to acrylonitrile-butadiene-styrene (ABS) resin which is excellent in processability and impact resistance but low in heat resistance.
In order to impart high heat resistance, a method of introducing a-methylstyrene (AMS) monomer into a SAN resin and emulsion polymerization using an excess amount of a mercaptan-based molecular weight modifier as a method for improving fluidity for processability has been proposed, The use of a mercapane-based molecular weight modifier can achieve a molecular weight advantageous for processing and an efficiency of a polymerization reaction. However, in the case of a mercaptan-based molecular weight modifier containing a -SH group, an excess amount of the mercaptan- , There is a present industrial and environmental disadvantage which emphasizes the reduction of TVOCs. In addition, the polymerization inhibition effect is induced by the radical inhibition effect, and the glass transition temperature is lowered due to the generation of a large amount of oligomer, there is a problem. Further, there arises a problem of lowering the heat distortion temperature (HDT) of the material such as the heat resistant ABS resin.
Therefore, there is still a need for a heat-resistant copolymer capable of reducing the odor during processing while securing the heat resistance and fluidity of the prior art.
In order to solve the problems of the prior art as described above, the present invention relates to a thermosetting resin composition which does not cause an unpleasant odor during processing, has excellent polymerization conversion and polymerization stability, has a reduced molecular weight and polydispersity index, And a method for producing the copolymer.
These and other objects of the present disclosure can be achieved by all of the present invention described below.
In order to achieve the above object, the present invention relates to a method for producing a heat-resistant copolymer by reversible iodine transfer polymerization (hereinafter referred to as RITP) of an aromatic vinyl monomer and a vinyl cyan monomer, A first polymerization step of polymerizing the whole amount of the aromatic vinyl monomer and a part of the vinyl cyan monomer in the presence of an iodine-containing compound, an initiator, and a redox-based catalyst; And (ii) a second polymerization step of continuously polymerizing the residual vinyl cyan monomer, initiator and redox catalyst at a polymerization conversion rate of 20 to 40% in the first polymerization step, wherein the aromatic vinyl monomer Wherein the content of? -Alkylstyrene is 50% by weight or more.
As described above, the present invention is based on the finding that, by using RITP to maintain the polymerization conversion and polymerization stability and to decrease the molecular weight and the polydispersity index, the fluidity and the glass transition temperature are improved and the unpleasant odor is not generated during processing There is an effect of providing a process for producing a heat-resistant copolymer.
Hereinafter, the present invention will be described in detail.
The method for producing a heat-resistant copolymer according to the present invention is a process for producing a heat-resistant copolymer comprising an aromatic vinyl monomer and a vinyl cyan monomer, wherein the aromatic vinyl monomer and the vinyl cyan monomer are partially or entirely mixed with iodine A first polymerization step of polymerizing in the presence of a compound, an initiator, and a redox-based catalyst; And (ii) a second polymerization step of polymerizing and polymerizing residual vinyl cyan monomer, initiator, and redox catalyst at a polymerization conversion rate of 20 to 40% in the first polymerization step, wherein the aromatic vinyl monomer is alkyl styrene is contained in an amount of 50% by weight or more. In this case, unpleasant odor is not generated during processing, the polymerization conversion and polymerization stability are excellent, and the molecular weight and polydispersity index are reduced, A heat-resistant copolymer having an excellent glass transition temperature can be produced.
The heat-resistant copolymer may be produced, for example, by mixing (i) 65 to 85 parts by weight of an aromatic vinyl monomer and 10 to 20 parts by weight of the vinyl cyan monomer with 100 parts by weight of an aromatic vinyl monomer and a vinyl cyan monomer, 0.05 to 0.9 parts by weight of one compound, 0.05 to 0.5 parts by weight of an initiator, and 0.01 to 1 part by weight of a redox-based catalyst; And (ii) 5 to 15 parts by weight of a vinyl cyan monomer, 0.001 to 0.5 part by weight of an initiator and 0.005 to 0.2 part by weight of a redox-based catalyst at a polymerization conversion rate of 20 to 40% in the first polymerization step And the aromatic vinyl monomer may contain not less than 50% by weight of? -Alkylstyrene.
The polymerization reaction may be carried out in a light-shielded reactor or a dark room. In this case, the compound containing iodine is inhibited from being decomposed by ultraviolet rays.
The amount of water used in the polymerization reaction of the present invention is not particularly limited when it is used in the art as polymerized water, but it may be, for example, 50 to 1000 parts by weight, 100 to 500 parts by weight based on 100 parts by weight of total monomers, 100 to 200 parts by weight.
The polymerization conversion rate in the first polymerization step (ii) may be from 20 to 40%, for example, from 25 to 40%, or from 30 to 35%, and the weight average molecular weight and polydispersity index may be decreased within this range The effect of increasing the fluidity and the glass transition temperature is excellent.
In the (ii) secondary polymerization step, the administration of the vinyl cyan monomer, the initiator, and the redox-based catalyst may be, for example, continuous administration, and may be a continuous administration for 2 to 5 hours.
The aromatic vinyl monomer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, o-ethylstyrene, p-ethylstyrene and 2,4-dimethylstyrene, -Methylstyrene and? -Ethylstyrene as essential components.
The vinyl cyan monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
The compound containing an iodine may be, for example, an iodine, a potassium iodide, a sodium iodide, a lithium iodide, a bromoiodide, an iodine monochloride, a magnesium iodide, a phosphorus triiodide, , And in this case, molecular weight and polydispersity index can be reduced while maintaining the polymerization conversion ratio and polymerization stability.
The compound containing iodine may be contained in an amount of 0.1 to 0.7 parts by weight, or 0.1 to 0.5 parts by weight, for example. Within this range, the molecular weight and the polydispersity index are decreased, and the effect of improving the glass transition temperature is excellent.
The initiator may be at least one selected from the group consisting of cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyronitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide and benzoyl peroxide have.
The redox-based catalyst may be at least one selected from the group consisting of ferrous sulfate, dextrose, sodium pyrophosphate, sodium ethylenediamine tetraacetate, sodium formaldehyde sulfoxylate and sodium sulfite.
In the first polymerization step (i), the redox-based catalyst may include, for example, 0.01 to 0.1 parts by weight of dextrose, 0.01 to 0.2 parts by weight of sodium pyrophosphate, and 0.0003 to 0.003 parts by weight of ferrous sulfate.
In the second polymerization step (ii), the redox-based catalyst may include, for example, 0.005 to 0.15 parts by weight of dextrose, 0.01 to 0.1 parts by weight of sodium pyrophosphate, and 0.0001 to 0.003 parts by weight of ferrous sulfate.
The first polymerization step (i) may include, for example, 0.01 to 1 part by weight of a molecular weight regulator, 0.01 to 1 part by weight of an electrolyte, 0.5 to 5 parts by weight of an emulsifier, 0.05 to 0.5 parts by weight of a molecular weight modifier, 0.05 to 0.5 parts by weight of an electrolyte, And 1 to 3 parts by weight of an emulsifier.
The molecular weight adjuster may be at least one selected from the group consisting of n-dodecylmercaptan, tertiary dodecylmercaptan, n-tetradecylmercaptan and tertiary tetradecylmercaptan.
The electrolyte may include, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , Na 2 S 2 O 7 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4 .
The second polymerization step (ii) may include, for example, 0.01 to 1 part by weight, or 0.1 to 0.5 part by weight of an emulsifier.
In the (i) first polymerization step and (ii) the second polymerization step, the emulsifying agent is selected from, for example, alkylaryl sulfonates, alkaline methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid May be at least one selected from the group consisting of
The (i) first polymerization step can be carried out at a reaction temperature of 45 to 55 ° C, for example. Within this range, the polymerization conversion ratio and the polymerization stability are excellent.
The second polymerization step (ii) can be polymerized at a reaction temperature of 65 to 75 占 폚, for example. Within this range, polymerization conversion and polymerization stability are excellent.
After (ii) the second polymerization step, for example, the reaction temperature can be raised to 75 to 85 ° C and then the reaction can be terminated.
The heat-resistant copolymer may have a weight average molecular weight of 200,000 g / mol or less, 190,000 g / mol or 105,000-190,000 g / mol, for example, and the glass transition temperature is elevated within this range.
The heat-resistant copolymer may have a polydispersity index (PDI) of 3.5 or less, or 1.0 to 3.5, for example. The molecular weight distribution is uniformized within this range, and low molecular weight polymers such as oligomers are reduced, There is an effect of rising.
The heat-resistant copolymer may have a glass transition temperature of 132 ° C or more, 135 ° C or more, or 135 to 150 ° C, and has an excellent heat resistance within this range.
The heat-resistant copolymer may have residual mercaptan content of 500 ppm or less, 300 ppm or less, or 0 to 250 ppm in TVOCs, and an unpleasant odor is not generated during processing within this range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
[Example]
Example One
≪ Preparation of Heat-resistant SAN Copolymer Latex >
140 parts by weight of ion-exchanged water, 70 parts by weight of? -Methylstyrene, 4.5 parts by weight of styrene, 15 parts by weight of acrylonitrile, 0.1 part by weight of iodine, 2.0 parts by weight of a fatty acid potassium salt as an emulsifier, 0.1 part by weight of sodium phosphate as an electrolyte, 0.1 part by weight of tertiary dodecylmercaptan as a molecular weight regulator, 0.1 part by weight of t-butyl hydroperoxide as an initiator, 0.035 part by weight of dextrose as a redox catalyst, 0.08 part by weight of sodium pyrophosphate And 0.0006 parts by weight of ferrous sulfate, and the mixture was reacted at a reaction temperature of 50 ° C until a polymerization conversion rate of 30%. Then, 10 parts by weight of ion-exchanged water, 10.5 parts by weight of acrylonitrile, 0.2% by weight of oleic acid potassium salt 0.025 part by weight of t-butyl hydroperoxide, 0.009 part by weight of dextrose, 0.02 part by weight of sodium pyrophosphate and 0.00015 part by weight of ferrous sulfate were continuously emulsified for 2 hours The temperature was raised to 80 ° C and the reaction was terminated at a polymerization conversion of 98%. All reactions were carried out in a reactor that did not emit light. The reaction-completed latex was agglomerated with 2 parts by weight of an aqueous solution of calcium chloride, and after dehydration, dried powder was obtained.
≪ Production of heat-resistant resin &
70 parts by weight of the dried heat-resistant SAN copolymer powder and 30 parts by weight of acrylonitrile-butadiene-styrene (DP271) resin powder of LG Chemical Co. were mixed in a mixer, pelletized using an extruder, Dried and then injection molded to prepare a physical specimen.
Example 2
Except that 0.2 part by weight of iodine in Example 1 and 0.05 part by weight of t-butyl hydroperoxide added in the second polymerization step were added.
Example 3
Except that 0.5 part by weight of iodine in Example 1 and 0.1 part by weight of t-butyl hydroperoxide added in the second polymerization step were added.
Example 4
The procedure of Example 1 was repeated except that 0.5 part by weight of iodine was added in Example 1 and tertiary dodecyl mercaptan was not added as a molecular weight regulator.
Reference Example
The procedure of Example 1 was repeated except that 1.0 part by weight of iodine was used in Example 1.
Comparative Example One
The procedure of Example 1 was repeated, except that 0.5 part by weight of tertiary dodecylmercaptan was used as the molecular weight modifier in Example 1 and no iodine was added.
Comparative Example 2
Example 1 was repeated except that 1.0 part by weight of tertiary dodecyl mercaptan was used as the molecular weight modifier and no iodine was added.
Comparative Example 3
The procedure of Example 1 was repeated, except that the acrylonitrile, initiator and redox catalyst continuously added to the second polymerization stage in Example 1 were added at the start of the reaction.
Comparative Example 4
The procedure of Example 1 was repeated, except that the redox catalyst was not added to the second polymerization stage in Example 1.
[Test Example]
The heat-resistant SAN copolymers prepared in Examples 1 to 4, Reference Examples and Comparative Examples 1 to 4 and the heat-resistant resins prepared therefrom were measured by the following methods, and the results are shown in Table 1 below.
Polymerization Conversion (%): 1.5 g of the prepared latex was dried in a hot air drier at 150 캜 for 15 minutes, and the weight was measured to determine the total solid content (TSC,%).
[Equation 1]
* Mw (weight average molecular weight: g / mol): The sample was dissolved in THF (tetrahydrofuran) and measured by GPC.
* PDI (Polydispersity Indix): The value obtained by dividing the weight average molecular weight by the number average molecular weight. The smaller the value, the more uniform the molecular weight distribution.
Tg (glass transition temperature; 占 폚): Measured using a DSC 1 star system (Mettler toledo).
* TDDM detection (ppm): measured by py-GC analysis.
Melt Index (g / 5 min): Measured at 220 캜 under a load of 10 Kg for 5 minutes in accordance with ASTM D1238.
Residual oligomer (%): Determined by GC analysis.
One
2
3
One
2
3
4
(hr)
Conversion Rate
Detection amount
Impossible
Impossible
Impossible
Impossible
Oligomer
Impossible
Impossible
Impossible
As shown in Table 1, Examples 1 to 4 according to the production method of the present invention had a lowered weight average molecular weight and polydispersity index, resulting in excellent workability, increased glass transition temperature and excellent heat resistance, Was significantly reduced, so that there was no unpleasant smell during processing. The heat resistant resin prepared from the heat resistant SAN resin produced by the production method of the present invention had an effect of increasing the melt index.
Further, in the reference example in which an excessive amount of iodine was contained, the glass transition temperature was greatly lowered.
On the other hand, in Comparative Examples 1 and 2 in which the content of a general molecular weight modifier used in emulsion polymerization was used, a large amount of TDDM was detected and a large amount of unpleasant odor was generated during the processing. Particularly, in Comparative Example 2, The glass transition temperature was lowered.
In Comparative Example 3 in which acrylonitrile and additives were not added at the second polymerization stage and polymerization was added at the beginning of polymerization and Comparative Example 4 in which the redox catalyst was not added in the second polymerization stage, And the polymerization conversion rate was extremely low, so that the melt index and the residual oligomer content could not be measured. Likewise, in Reference Example and Comparative Example 2, the polymerization conversion was low and the latex could not be obtained as a powder by aggregating the latex, so that the melt index and the residual oligomer content could not be measured.
Claims (19)
(i) a first polymerization step of polymerizing the whole amount of the aromatic vinyl monomer and a part of the vinyl cyan monomer in the presence of an iodine-containing compound, an initiator, and a redox-based catalyst; And
(ii) a second polymerization step of polymerizing residual vinyl cyan monomer, initiator and redox-based catalyst at a polymerization conversion rate of 20 to 40% in the first polymerization step,
Wherein the aromatic vinyl monomer comprises? -Alkylstyrene in an amount of 50% by weight or more.
The method for producing the heat-resistant copolymer is characterized in that, based on 100 parts by weight of the following aromatic vinyl monomers and vinyl cyan monomers,
(i) 65 to 85 parts by weight of an aromatic vinyl monomer, 10 to 20 parts by weight of the vinyl cyan monomer, 0.05 to 0.9 part by weight of a compound containing iodine, 0.05 to 0.5 part by weight of an initiator, 0.01 to 1 part by weight of a redox catalyst A first polymerization step of polymerizing in the presence of a solvent; And
(ii) 5 to 15 parts by weight of a vinyl cyan monomer, 0.001 to 0.5 part by weight of an initiator and 0.005 to 0.2 part by weight of a redox-based catalyst at a polymerization conversion rate of 20 to 40% in the first polymerization step, Wherein the aromatic vinyl monomer has a content of? -Alkylstyrene of 50% by weight or more.
Wherein the polymerization reaction is carried out in a light-shielded reactor or in a dark room.
Wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, o-ethylstyrene, p-ethylstyrene and 2,4-dimethylstyrene, - < / RTI > ethylstyrene as essential components.
Wherein the vinyl cyan monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
The compound containing iodine may be at least one selected from the group consisting of iodine, potassium iodide, sodium iodide, lithium iodide, bromoiodide, iodine monochloride, magnesium iodide, phosphorus triiodide, And at least one selected from the group consisting of iodide.
The initiator is at least one selected from the group consisting of cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyronitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide and benzoyl peroxide. By weight based on the total weight of the copolymer.
Wherein the redox-based catalyst is at least one selected from the group consisting of ferrous sulfate, dextrose, sodium pyrophosphate, sodium ethylenediamine tetraacetate, sodium formaldehyde sulfoxylate and sodium sulfite. Gt;
(I) the first polymerization step comprises polymerizing 0.01 to 1 part by weight of a molecular weight regulator, 0.01 to 1 part by weight of an electrolyte and 0.5 to 5 parts by weight of an emulsifier.
Wherein the molecular weight modifier is at least one selected from the group consisting of n-dodecylmercaptan, tertiary dodecylmercaptan, n-tetradecylmercaptan and tertiary tetradecylmercaptan.
The electrolyte is KCl, NaCl, KHCO 3, NaHCO 3, K 2 CO 3, Na 2 CO 3, KHSO 3, NaHSO 3, Na 2 S 2 O 7, K 4 P 2 O 7, K 3 PO 4, Na 3 PO 4 , K 2 HPO 4, and Na 2 HPO 4 .
(Ii) the second polymerization step comprises polymerizing 0.01 to 1 part by weight of an emulsifier.
Wherein the emulsifier is at least one selected from the group consisting of alkylaryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid.
Wherein the first polymerization step (i) is carried out at a reaction temperature of 45 to 55 占 폚.
Wherein the second polymerization step (ii) is carried out at a reaction temperature of 65 to 75 占 폚.
Wherein the heat-resistant copolymer has a weight average molecular weight of 200,000 g / mol or less.
Wherein the heat-resistant copolymer has a polydispersity index (PDI) of 3.5 or less.
Wherein the heat-resistant copolymer has a glass transition temperature of 132 DEG C or higher.
Wherein the heat-resistant copolymer has a residual mercaptan content of 500 ppm or less in TVOCs.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018217017A2 (en) | 2017-05-22 | 2018-11-29 | 주식회사 엘지화학 | Cylindrical battery comprising anti-rust gasket |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040054108A1 (en) * | 2002-07-23 | 2004-03-18 | Mestach Dirk Emiel Paula | Method for polymerizing ethylenically unsaturated monomers by degenerative iodine transfer |
| KR20090094653A (en) * | 2008-03-03 | 2009-09-08 | 인하대학교 산학협력단 | Preparation method of low Molecular Weight of VinylPolymer by Reverse Iodine Transfer Polymerization-Emulsion Polymerization |
| JP2014084411A (en) * | 2012-10-24 | 2014-05-12 | Canon Inc | Method for producing polymer particle |
| KR20150037459A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Manufacturing method of SAN copolymer having good heat resistance |
| KR20150068114A (en) | 2013-12-11 | 2015-06-19 | 주식회사 엘지화학 | Method for preparing heat-resistant san resin, and heat-resistant san resin |
-
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- 2015-11-30 KR KR1020150168412A patent/KR102009315B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040054108A1 (en) * | 2002-07-23 | 2004-03-18 | Mestach Dirk Emiel Paula | Method for polymerizing ethylenically unsaturated monomers by degenerative iodine transfer |
| KR20090094653A (en) * | 2008-03-03 | 2009-09-08 | 인하대학교 산학협력단 | Preparation method of low Molecular Weight of VinylPolymer by Reverse Iodine Transfer Polymerization-Emulsion Polymerization |
| JP2014084411A (en) * | 2012-10-24 | 2014-05-12 | Canon Inc | Method for producing polymer particle |
| KR20150037459A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Manufacturing method of SAN copolymer having good heat resistance |
| KR20150068114A (en) | 2013-12-11 | 2015-06-19 | 주식회사 엘지화학 | Method for preparing heat-resistant san resin, and heat-resistant san resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018217017A2 (en) | 2017-05-22 | 2018-11-29 | 주식회사 엘지화학 | Cylindrical battery comprising anti-rust gasket |
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