KR100193022B1 - Manufacturing method of photopolymer resin excellent in heat resistance - Google Patents
Manufacturing method of photopolymer resin excellent in heat resistance Download PDFInfo
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- KR100193022B1 KR100193022B1 KR1019950056521A KR19950056521A KR100193022B1 KR 100193022 B1 KR100193022 B1 KR 100193022B1 KR 1019950056521 A KR1019950056521 A KR 1019950056521A KR 19950056521 A KR19950056521 A KR 19950056521A KR 100193022 B1 KR100193022 B1 KR 100193022B1
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- 229920005989 resin Polymers 0.000 title claims description 17
- 239000011347 resin Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 53
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003999 initiator Substances 0.000 claims abstract description 38
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 11
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 8
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 7
- -1 peroxide compound Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 11
- 230000007423 decrease Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- QKNQPCLQRXMWJO-UHFFFAOYSA-N 1-(tert-butyldiazenyl)cyclohexane-1-carbonitrile Chemical compound CC(C)(C)N=NC1(C#N)CCCCC1 QKNQPCLQRXMWJO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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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
-
- 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
- C08F2/18—Suspension polymerisation
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
본 발명은 고분자 사슬내에 알파메틸스티렌의 함량이 높아 열변형온도가 높고 고 열안정성이 양호한 알파메틸스티렌과 아크릴로니트릴 공중합체 수지의 제조방법에 관한 것으로서, 전체 아크릴로니트릴과 알파메틸스티렌 단량체 투입량 100 중량부에 대하여 알파메틸스티렌 65-78중량부, 아크릴로니트릴 35-22중량부 및 중합개시제를 사용하여 10-40시간 동안 현탁중합하여 공중합체 수지를 제조함에 있어서, 중합초기에 개시제를 전체 투입되는 개시제 총량에 대하여 50-100중량% 투입하고, 단량체를 공비조성 이상에서 중합 진행시킨 다음, 중합 전환율이 30-70% 진행된 시점에서 아크릴로니트릴 전환율이 70-90%가 될 때까지 전체 단량체 투입량의 0.1-5중량%정도 연속 투입하고, 나머지 개시제 50-0중량%를 투입하여 중합을 진행시키거나 또는 중합 전환율이 30-70% 진행된 시점에서 아크릴로니트릴을 전체 단량체 투입량의 0.1-5중량% 정도 투입하고, 나머지 개시제 50-0중량%를 분할 투입한 후 전환율이 70-90% 진행된 시점에서 아크릴로니트릴을 투입 단량체의 0.5-4중량% 분할 투입하여 중합을 완료시킴을 특징으로 한다.The present invention relates to a method for preparing alphamethylstyrene and acrylonitrile copolymer resin having high heat deformation temperature and high thermal stability due to high content of alphamethylstyrene in the polymer chain, and the total amount of acrylonitrile and alphamethylstyrene monomers. Suspension polymerization for 10-40 hours using alpha methyl styrene 65-78 parts by weight, acrylonitrile 35-22 parts by weight and a polymerization initiator with respect to 100 parts by weight of the initiator to prepare the copolymer resin, 50-100% by weight relative to the total amount of initiator added, and the monomer was polymerized at the azeotropic composition or higher, and then the total monomer until the acrylonitrile conversion was 70-90% at the time when the polymerization conversion was 30-70%. 0.1-5% by weight of the input is continuously added, and 50-0% by weight of the remaining initiator is added to proceed with the polymerization or the polymerization conversion rate is 30-7. At the time of 0% progress, acrylonitrile was added in an amount of 0.1-5% by weight of the total monomer input amount, and 50-0% by weight of the remaining initiator was added in portions, and acrylonitrile was added at the point of conversion of 70-90%. 0.5-4% by weight of the split is characterized in that the polymerization is completed.
Description
본 발명은 내열성이 우수한 공중합체 수지의 제조방법에 관한 것으로서, 더욱 상세하게로는 고분자 사슬내에 알파메틸스티렌의 함량이 높아 열변형 온도가 높고 열안정성이 양호한 알파메틸스티렌과 아크릴로니트릴 공중합체 수지의 제조방법에 관한 것이다.The present invention relates to a method for preparing a copolymer resin having excellent heat resistance, and more particularly, to an alpha methyl styrene and acrylonitrile copolymer resin having a high content of alpha methyl styrene in a polymer chain and a high heat deformation temperature and good thermal stability. It relates to a manufacturing method of.
내열성을 가지는 알파메틸스티렌과 아크릴로니트릴 공중합체 수지(이하 내열 SAN 수지라고 칭함)를 제조하는데 있어서, 일반적으로는 전체 공중합체 수지 100 중량부에 대해 알파메틸스티렌을 65-78 중량부 투입하고 아크릴로니트릴 35-22 중량부 투입하여 제조하는데, 이와 같은 함량으로 제조되는 내열 SAN수지는 내열도와 충격강도가 우수하여 유화, 현탁, 과상중합 등의 기존 산업화된 중합방법에 의해 제조될 수 있다.In preparing alpha-methyl styrene and acrylonitrile copolymer resin (hereinafter referred to as heat-resistant SAN resin) having heat resistance, 65-78 parts by weight of alpha-methyl styrene is generally added to 100 parts by weight of the total copolymer resin. It is prepared by adding 35-22 parts by weight of ronitrile, and the heat-resistant SAN resin prepared in such a content is excellent in heat resistance and impact strength and can be produced by conventional industrial polymerization methods such as emulsification, suspension, and superphase polymerization.
그런데, 일반적으로 현탁중합으로 내열 SAN수지를 제조시에는 열변형 온도를 높이기 위하여 알파메틸스티렌과 아크릴로니트릴의 투입량, 중합온도, 개시제 종류 및 양, 단량체의 투입방법 등의 중합조건들을 변화시키는데, 이러한 조건들은 내열 SAN수지의 열변형온도, 열 안정성에 크게 영향을 미친다.However, in general, in preparing a heat-resistant SAN resin by suspension polymerization, in order to increase the heat deformation temperature, the polymerization conditions such as the amount of alphamethylstyrene and acrylonitrile, the polymerization temperature, the type and amount of the initiator, and the method of the monomer are changed. These conditions greatly affect the thermal deformation temperature and thermal stability of the heat resistant SAN resin.
따라서 내열 SAN수지의 현탁중합에 있어서 열변형 온도를 높이기 위한 방법으로서, 분자량을 높이고 공중합체의 잔류단량체의 양을 감소시키는 방법이 검토되었다. 그러나 이러한 방법에 의해서 얻어진 공중합체의 경우에는 분자량은 높으나 성형시 분자량의 저하가 일어나서 성형물의 경우 열변형 온도와 충격강도가 저하되는 문제가 생기는데, 이것은 알파메틸스티렌과 아크릴로니트릴의 공중합체의 경우에는 해중합성이 있기 때문에 중합완료시 고분자량의 중합체를 얻음에도 불구하여 성형시에 분자량의 저하가 일어나 열변형온도를 저하시키기 때문이다.Therefore, as a method for increasing the heat deformation temperature in suspension polymerization of heat-resistant SAN resin, a method of increasing the molecular weight and reducing the amount of residual monomers in the copolymer has been studied. However, the copolymer obtained by this method has a high molecular weight, but the molecular weight decreases during molding, resulting in a problem that the thermal deformation temperature and impact strength of the molded product are lowered. This is the case of the copolymer of alphamethylstyrene and acrylonitrile. This is because, due to depolymerization, the molecular weight decreases during molding to lower the heat deformation temperature despite obtaining a high molecular weight polymer upon completion of polymerization.
일본공개특허 소61-4709호에서는 이러한 문제점을 개선하고자 특정의 아조계 개시제를 투입하고, 중합온도를 조절하여 현탁중합하는 방법을 제시하고 있으며, 일본공개특허 소62-13413호에서는 10시간 반감기 온도가 서로 다른 두가지의 개시제를 혼용하여 현탁중합을 진행하되 중합온도를 2단계로 하는 방법을 사용함으로써 이를 개선하였다.Japanese Patent Laid-Open No. 61-4709 discloses a method of adding a specific azo initiator and suspending polymerization by adjusting a polymerization temperature to improve such a problem, and Japanese Patent Laid-Open No. 62-13413 discloses a 10-hour half-life temperature. Was improved by using a method in which the suspension polymerization was carried out using a mixture of two different initiators, but the polymerization temperature was used in two stages.
본 발명에서는 상기 기술들을 더 보완하여 내열 SAN수지의 물성을 결정하는데 있어 중요한 부분을 차지하는 내열 SAN수지의 중합방법을 개량함으로써 최종제품인 내열 ABS수지 제품의 열변형온도와 열안정성을 개선하는 것을 그 목적으로 한다.The present invention further improves the heat deformation temperature and thermal stability of the heat-resistant ABS resin product as a final product by improving the polymerization method of the heat-resistant SAN resin, which is an important part in determining the properties of the heat-resistant SAN resin by further supplementing the above techniques. It is done.
즉, 본 발명은 α-메틸스티렌과 아크릴로니트릴을 현탁중합하여 내열성이 우수한 공중합체를 제조함에 있어서, 개시제로는 10시간 반감기온도가 80-100℃인 아조계 또는 과산화물계 화합물을 전체 투입 단량체 100 중량부에 대해 0.2-1.0 중량부 투입하고, α-메틸스티렌, 아크릴로니트릴 단량체 및 개시제를 분할투입하여 10-40시간 중합함을 특징으로 한다.That is, according to the present invention, in preparing a copolymer having excellent heat resistance by suspending and polymerizing α-methylstyrene and acrylonitrile, an initiator or a peroxide-based compound having a half-life temperature of 80 to 100 ° C. for 10 hours is used as an initiator. 0.2-1.0 parts by weight based on 100 parts by weight, and the? -Methyl styrene, acrylonitrile monomer and initiator are separately added and polymerized for 10-40 hours.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 내열 SAN수지내의 알파메틸스티렌의 함량은 65-78중량부, 아크릴로니트릴의 함량은 35-22중량부로서, 만일 알파메틸스티렌의 함량이 65 중량부 미만인 경우에는 공중합체의 열변형온도가 낮아지고 내열 SAN 공중합체의 특징이 없어지며 몰비로 계산할 때 수지내의 아크릴로니트릴 함량이 알파메틸스티렌보다 많아져서 아크릴로니트릴의 연속쇄가 다량 생성되어 착색을 일으키기가 쉬우므로 좋지 않으며, 또한 알파메틸스티렌의 함량이 78중량부를 초과하게 되면 수지내의 착색현상은 일어나지 않지만 중합속도가 급격히 저하되어 잔존단량체가 많아져서 제조된 공중합체 수지의 열변형온도가 낮아져서 열 안정이 우수한 내열 ABS제품에 적용하기 어렵게 된다.The content of alpha methyl styrene in the heat-resistant SAN resin of the present invention is 65-78 parts by weight, the content of acrylonitrile is 35-22 parts by weight, if the content of alpha methyl styrene is less than 65 parts by weight of the thermal deformation of the copolymer It is not good because the temperature is lowered, the characteristics of the heat-resistant SAN copolymer are lost, and the content of acrylonitrile in the resin is higher than that of alphamethylstyrene as calculated in the molar ratio, so that a large amount of continuous chains of acrylonitrile are generated, which is easy to cause coloring. When the content of alpha methyl styrene exceeds 78 parts by weight, coloration in the resin does not occur, but the polymerization rate decreases rapidly, and the residual monomer increases, which is applied to heat-resistant ABS products having excellent thermal stability as the heat deformation temperature of the copolymer resin is lowered. It becomes difficult to do it.
이 때 상기와 같은 알파메틸스티렌 65-78중량부 중 3-15중량부를 연속 또는 수차에 걸쳐 중합계에 분할 투입시키면 효과적으로 내열 SAN수지의 연쇄조성을 조절할 수 있으나, 대신 내열 SAN수지 고분자슬내의 알파메틸스티렌 함량이 높은 내열 SAN수지를 얻기가 어렵게 된다.In this case, if 3-15 parts by weight of the above-mentioned 65-78 parts by weight of alpha methyl styrene is continuously added to the polymerization system in a continuous or aberration manner, it is possible to effectively control the chain composition of the heat-resistant SAN resin, but instead the alpha methyl in the heat-resistant SAN resin polymer chain. It is difficult to obtain a heat resistant SAN resin having a high styrene content.
따라서 고분자사슬내의 알파메틸스티렌 함량을 높이면서도 내열변형온도를 높게하고 열안정성이 우수한 내열 SAN수지를 얻기 위해서는 단량체 공비조성 이상의 알파메틸스티렌 함량을 유지시켜 주면서 보다 많은 알파메틸스티렌이 중합계에 참여할 수 있도록 하고 고분자사슬내 알파메틸스티렌 함량을 높여 내열변형온도를 높게하고 열안정성이 우수한 내열 SAN수지를 제조해야 한다.Therefore, in order to increase the heat deflection temperature and improve the heat stability of the high molecular methyl styrene in the polymer chain, while maintaining the alpha methyl styrene content above the monomer azeotropic composition, more alpha methyl styrene can participate in the polymerization system. It is necessary to manufacture heat resistant SAN resin with high heat stability and high heat stability by increasing alphamethylstyrene content in the polymer chain.
일반적으로 아크릴로니트릴은 수용성이 있는 단량체이기 때문에 중합초기에 이미 투입한 순수 중량부에 대하여 5중량부 정도 용해되어 있으므로 투입한 단량체의 조성과 중합계내의 단량체 조성은 차이가 나며 실제로 중합개시점에서 단량체 유적(MONOMER DROPLET)내의 아크릴로니트릴 함량은 상대적으로 감소하여 진행한다.In general, acrylonitrile is a water-soluble monomer, so it is dissolved about 5 parts by weight with respect to the pure weight part already added at the beginning of the polymerization, so the composition of the added monomer and the monomer composition in the polymerization system are different. The acrylonitrile content in MONOMER DROPLET proceeds with a relative decrease.
이를 고려하여 본 발명에서는 초기중합에서 단량체를 단량체 공비조성 이상에서 중합 진행시키고 중합이 진행되면서 알파메틸스티렌과 아크릴로니트릴 전체 투입량 중 1-10 중량%를 적정비율로 혼합하여 개시제와 함께 연속 또는 수차에 걸쳐 중합계내에 분할 투입하는데, 이 때 알파메틸스티렌 조성은 단량체 공비조성 이상에서 중합을 진행시킬 때 중합후반부에서 중합속도가 급격히 감소하여 적정전환을 이상까지 중합을 진행시키기 어렵기 때문에 아크릴로니트릴 단량체의 투입량 중 일부를 단독 혹은 소량의 개시제와 함께 연속 또는 수차에 걸쳐 종합계내에 분할 투입하여 중합을 진행한다.In consideration of this, in the present invention, in the initial polymerization, the monomer is polymerized at the monomer azeotropic composition or higher, and as the polymerization proceeds, 1-10% by weight of the total amount of alphamethylstyrene and acrylonitrile are mixed at an appropriate ratio to continuously or aberration with the initiator. In this case, the alphamethylstyrene composition is acrylonitrile because the polymerization rate decreases rapidly in the latter part of the polymerization when the polymerization proceeds above the monomer azeotropic composition, so that it is difficult to proceed the polymerization to the ideal conversion. Some of the monomers are added alone or in small amounts together with a small amount of initiator in a series or several times in the synthesis to proceed polymerization.
즉, 초기중합에서 단량체를 공비조성 이상에서 중합을 진행시킨 다음, 중합 전환율이 30-70% 진행된 시점에서 아크릴로니트릴을 중합 전환율이 70-90%가 될 때까지 전체 아크릴로니트릴과 알파메틸스티렌 단량체 투입량의 0.1-5중량% 정도로 연속 투입하여 중합을 진행시키거나 또는 중합 전환율이 30-70% 진행된 시점에서 아크릴로니트릴을 전체 아크릴로니트릴과 알파메틸스티렌 단량체 투입량의 0.1-5중량% 정도 투입한 후 전환율이 70-90% 진행된 시점에서 아크릴로니트릴을 투입 단량체의 0.5-4중량% 정도 분할 투입하여 중합을 진행시킨다.In other words, in the initial polymerization, the monomer was polymerized at the azeotropic composition or higher, and then the acrylonitrile was polymerized at the point of polymerization conversion of 30-70% until the polymerization conversion was 70-90%. 0.1-5% by weight of the monomer is continuously added to advance the polymerization, or when the polymerization conversion rate is 30-70%, acrylonitrile is added in the amount of 0.1-5% by weight of the total amount of acrylonitrile and alphamethylstyrene monomer. After the conversion rate is 70-90%, acrylonitrile is added at a rate of 0.5-4% by weight based on the monomers to proceed with polymerization.
또한 본 발명에서 이용되는 개시제로는 10시간 반감기 온도가 80-100℃인 아조계 또는 과산화물계의 개시제를 사용하는데, 아조계로는 1-t-부틸아조-1-시아노사이클로헥산, 2-t-부틸아조시아노프로판, 1,1-사이클로헥실카보니트릴 등을 사용할 수 있으며 과산화물개시제로는 t-부틸퍼옥시벤조에이트, t-부틸퍼옥시아세테이트, 1,1-(t-부틸퍼옥시)-3,3,5-트리메틸사이클로헥산, 1,1-디(t-부틸퍼옥시)-사이클로헥산, t-부틸퍼옥시스테아릴카바메이트 등을 사용할 수 있다.In addition, the initiator used in the present invention uses an azo or peroxide initiator having a half-life temperature of 80-100 ° C. for 10 hours. As the azo system, 1-t-butylazo-1-cyanocyclohexane, 2-t Butyl azocyanopropane, 1,1-cyclohexylcarbonitrile, etc. may be used, and as peroxide initiators, t-butylperoxybenzoate, t-butylperoxyacetate, 1,1- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) -cyclohexane, t-butylperoxy stearyl carbamate, etc. can be used.
상기와 같은 개시제를 전체 투입 단량체 100 중량부에 대해 0.2-1.0 중량부 투입하고, 중합온도 80-100℃에서 10-40시간 동안 중합을 진행하는 것이 바람직한데, 만일 상기 개시제 양이 0.2중량부 미만이거나 중합온도가 80℃미만이 되면 반응성이 현저히 저하되어 원하는 전환율까지 중합을 진행시키기가 곤란하게 되는 문제가 생기며, 또한 개시제가 1.0 중량부를 초과하여 과량 투입되거나 중합온도가 100℃를 초과하게 되면 반응성은 향상되기만 반응속도의 급격한 증가로 인하여 분산력이 파괴되어 중합진행이 곤란하게 되고 중합이 진행되더라도 분자량 저하로 인하여 기계적 물성이 저하되기 때문에 적용이 어렵게 되는 문제가 생긴다.0.2-1.0 parts by weight of the initiator is added to 100 parts by weight of the total monomer, and the polymerization is preferably carried out at a polymerization temperature of 80-100 ° C for 10-40 hours, if the amount of the initiator is less than 0.2 parts by weight. Or when the polymerization temperature is lower than 80 ° C., the reactivity is remarkably lowered, making it difficult to proceed the polymerization to the desired conversion rate, and when the initiator is added in excess of 1.0 parts by weight or the polymerization temperature is higher than 100 ° C. Is improved, but the dispersion force is destroyed due to the rapid increase in the reaction rate, making it difficult to proceed with the polymerization, and even when the polymerization proceeds, the mechanical properties are degraded due to the molecular weight decrease, thereby making it difficult to apply.
또한 상기의 개시제 투입시에는 전체 투입 개시제 총량에 대하여 50-100중량%의 개시제를 중합초기에 투입하고, 전환율이 30-70% 진행된 시점에서 나머지 개시제 0-50중량%를 투입하여 중합을 진행해야 하는데, 이와같은 중합개시제의 분할 투입 중에서 전환율이 30-70% 진행된 시점에서 투입시에는 개시제 단독으로 투입하지 않고, 알파메틸스티렌과 아크릴로니트릴의 일부에 용해시켜 투입해야 한다.In addition, when the initiator is added, 50-100% by weight of the initiator should be added to the initial stage of polymerization based on the total amount of the total initiator, and when the conversion rate is 30-70%, 0-50% by weight of the remaining initiator should be added to proceed with the polymerization. However, when the conversion rate is 30-70% in the divided addition of such a polymerization initiator, it should be added by dissolving in a part of alphamethylstyrene and acrylonitrile instead of adding the initiator alone.
본 발명에서는 이밖에 현탁안정제를 사용하는데, 현탁안정제로는 폴리비닐알콜, 폴리비닐피놀리돈, 메틸셀룰로오스, 메틸헥실셀룰로오스 등과 같은 유기화합물과 인산마그네슘, 탄산칼슘, 제3인산칼슘, 탄산마그네슘 등의 무기현탁 안정제 중에서 선택된 1종의 화합물 또는 그 이상을 병용하여 중합특성에 맞게 적용하여 사용한다. 현탁안정제의 투입량은 전체 투입단량체 100 중량부에 대해 0.1-1.0중량부인 것이 바람직하다.In the present invention, a suspension stabilizer is used, and as the suspension stabilizer, organic compounds such as polyvinyl alcohol, polyvinyl pinolidon, methyl cellulose, methylhexyl cellulose, magnesium phosphate, calcium carbonate, tricalcium phosphate, magnesium carbonate, etc. One or more compounds selected from inorganic suspension stabilizers may be used in combination to suit the polymerization properties. The amount of the suspension stabilizer is preferably 0.1-1.0 parts by weight based on 100 parts by weight of the total monomer.
이하 본 발명을 실시예 및 비교예를 통해 설명한다.Hereinafter, the present invention will be described through Examples and Comparative Examples.
[실시예 1]Example 1
압력에 견딜수 있는 교반기와 베플이 부착된 반응기에 이온교환수 100중량부, 제3인산칼슘 0.5중량부, 도데실벤젠슬폰산소다 0.01중량부, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸사이클로헥산 0.3 중량부, 알파메틸스티렌 70 중량부, 아크릴로니트릴 24 중량부를 투입한 후 반응기 상부를 충분히 질소로 치환한 다음 반응기를 완전히 밀폐하고 충분히 교반력을 부여하였다. 분산성을 확인한 후 반응기 내부의 온도를 100℃로 승온하여 반응을 개시하였다.100 parts by weight of ion-exchanged water, 0.5 parts by weight of tricalcium phosphate, 0.01 parts by weight of sodium dodecylbenzenesulfonic acid, 1,1-di (t-butylperoxy)-in a reactor equipped with a pressure-resistant stirrer and a baffle After adding 0.3 part by weight of 3,3,5-trimethylcyclohexane, 70 parts by weight of alphamethylstyrene, and 24 parts by weight of acrylonitrile, the upper part of the reactor was sufficiently replaced with nitrogen, and the reactor was completely sealed, and sufficient stirring power was given. After confirming the dispersibility, the reaction was initiated by raising the temperature in the reactor to 100 ℃.
고분자 전환율이 40% 진행된 시점에서 알파메틸스티렌 3 중량부, 아크릴로니트릴 2 중량부, 개시제 0.2 중량부를 혼합하여 반응기내부로 투입하여 중합을 진행시킨 후 고분자 전환율이 80%가 되는 시점에서 아크릴로니트릴 1 중량부를 반응기내로 투입하여 총 15시간 동안 반응을 실시하여 중합을 완료시켰다. 생성된 중합물을 염산으로 중화후 수세, 탈수, 건조하여 내열 SAN비드를 제조하였으며, 물성을 측정하여 그 결과를 다음표 1에 나타냈다.At the time when the polymer conversion was 40%, 3 parts by weight of alphamethylstyrene, 2 parts by weight of acrylonitrile, and 0.2 parts by weight of initiator were mixed, and the polymerization was carried out by introducing into the reactor. 1 part by weight was introduced into the reactor to carry out the reaction for a total of 15 hours to complete the polymerization. The resulting polymer was neutralized with hydrochloric acid, washed with water, dehydrated and dried to prepare a heat resistant SAN bead, and the physical properties were measured and the results are shown in Table 1 below.
[실시예 2]Example 2
중합초기에 알파메틸스티렌 73 중량부, 아크릴로니트릴 24 중량부와 개시제인 1,1-디-(t-부틸퍼옥시)-3,3,5-트리메틸사이클로 헥산을 0.4 중량부 투입하고, 고분자 전환율이 40%진행된 시점에서 아크릴로니트릴 2 중량부와 개시제 0.1 중량부를 투입하고 전환율이 80%진행되었을 때 아크릴로니트릴 1 중량부를 반응기 내부로 투입하는 것을 제외하고는 실시예 1과 동일하게 실시하였으며, 그 결과를 다음 표 1에 나타내었다.In the initial stage of polymerization, 73 parts by weight of alphamethylstyrene, 24 parts by weight of acrylonitrile and 0.4 part by weight of 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane as an initiator were added to the polymer. The conversion was carried out in the same manner as in Example 1 except that 2 parts by weight of acrylonitrile and 0.1 part by weight of the initiator were added at the time of 40% conversion, and 1 part by weight of acrylonitrile was introduced into the reactor when the conversion was 80%. The results are shown in Table 1 below.
[실시예 3]Example 3
중합초기에 알파메틸스티렌 70 중량부, 아크릴로니트릴 25 중량부, 개시제를 0.3 투입하고, 고분자 전환율이 40%진행된 시점에서 알파메틸스티렌 3 중량부와 아크릴로니트릴 2 중량부를 혼합하여 반응기 내부로 연속적으로 고분자 전환율 80%에 이르는 시점까지 투입하는 것을 제외하고는 실시예1과 동일하게 실시하였으며, 그 결과를 다음 표 1에 나타내었다.In the initial stage of polymerization, 70 parts by weight of alpha methyl styrene, 25 parts by weight of acrylonitrile and 0.3 initiator were added, and 3 parts by weight of alpha methyl styrene and 2 parts by weight of acrylonitrile were mixed continuously at the time when the polymer conversion was 40%. Was carried out in the same manner as in Example 1 except that until the time to reach the polymer conversion rate of 80%, the results are shown in Table 1 below.
[비교예 1]Comparative Example 1
중합초기에 알파메틸스티렌 73 중량부, 아크릴로니트릴 27 중량부, 개시제를 0.5 중량부 투입한 후, 고분자 전환율 95% 이상 진행시키는 것을 제외하고는 실시예1과 동일하게 실시하였으며, 그 결과를 다음 표 1에 나타내었다.In the initial stage of polymerization, 73 parts by weight of alphamethylstyrene, 27 parts by weight of acrylonitrile and 0.5 parts by weight of an initiator were added, and then the polymerization conversion was carried out in the same manner as in Example 1 except that the conversion was 95% or more. Table 1 shows.
[비교예 2]Comparative Example 2
중합초기에 알파메틸스티렌 70 중량부, 아크릴로니트릴 27 중량부, 개시제를 0.3 중량부 투입하고, 고분자 전환율이 40%진행된 시점에서 알파메틸스티렌 3 중량부와 개시제0.2 중량부를 투입하는 것을 제외하고는 실시예1과 동일하게 실시하였으며, 그 결과를 다음 표 1에 나타내었다.In the initial stage of polymerization, 70 parts by weight of alpha methyl styrene, 27 parts by weight of acrylonitrile and 0.3 parts by weight of initiator were added, and 3 parts by weight of alpha methyl styrene and 0.2 parts by weight of initiator were added at the time when the polymer conversion was 40%. It carried out similarly to Example 1, and the result is shown in following Table 1.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100387960B1 (en) * | 2000-12-04 | 2003-06-18 | 구희철 | foodstuffs sludge process structure for a sink |
| KR101213259B1 (en) | 2009-10-20 | 2012-12-18 | 주식회사 엘지화학 | A method for preparing heat resistant thermoplastic resin having high impact strength and good color properties |
| KR20170043901A (en) * | 2015-10-14 | 2017-04-24 | 주식회사 엘지화학 | Preparation method of heat-resistant styrene copolymer and heat-resistant styrene copolymer produced by the same |
| KR101757965B1 (en) * | 2014-12-09 | 2017-07-14 | 주식회사 엘지화학 | Method for producing heat resistance san resin, heat resistance san resin, and heat resistance abs resin |
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| KR20200070651A (en) | 2018-12-10 | 2020-06-18 | 주식회사 엘지화학 | Method for preparing thermoplastic copolymer, thermoplastic copolymer produced by the method and thermoplastic resin composition comprising the copolymer |
| WO2021101101A1 (en) * | 2019-11-21 | 2021-05-27 | 주식회사 엘지화학 | Method for preparing copolymer, copolymer prepared thereby, and thermoplastic resin composition comprising same |
| US11427659B2 (en) | 2017-09-29 | 2022-08-30 | Lg Chem, Ltd. | Method of preparing acrylonitrile-based polymer for producing carbon fiber |
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- 1995-12-26 KR KR1019950056521A patent/KR100193022B1/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100387960B1 (en) * | 2000-12-04 | 2003-06-18 | 구희철 | foodstuffs sludge process structure for a sink |
| KR101213259B1 (en) | 2009-10-20 | 2012-12-18 | 주식회사 엘지화학 | A method for preparing heat resistant thermoplastic resin having high impact strength and good color properties |
| KR101770879B1 (en) * | 2014-10-10 | 2017-08-23 | 주식회사 엘지화학 | Method for preparing heat resistance SAN resin, and method for preparing heat resistance resin having white color property and heat resistance |
| KR101757965B1 (en) * | 2014-12-09 | 2017-07-14 | 주식회사 엘지화학 | Method for producing heat resistance san resin, heat resistance san resin, and heat resistance abs resin |
| KR20170043901A (en) * | 2015-10-14 | 2017-04-24 | 주식회사 엘지화학 | Preparation method of heat-resistant styrene copolymer and heat-resistant styrene copolymer produced by the same |
| KR102015091B1 (en) * | 2015-10-14 | 2019-08-27 | 주식회사 엘지화학 | Preparation method of heat-resistant styrene copolymer and heat-resistant styrene copolymer produced by the same |
| US11427659B2 (en) | 2017-09-29 | 2022-08-30 | Lg Chem, Ltd. | Method of preparing acrylonitrile-based polymer for producing carbon fiber |
| KR20200070651A (en) | 2018-12-10 | 2020-06-18 | 주식회사 엘지화학 | Method for preparing thermoplastic copolymer, thermoplastic copolymer produced by the method and thermoplastic resin composition comprising the copolymer |
| US11603421B2 (en) | 2018-12-10 | 2023-03-14 | Lg Chem, Ltd. | Method for preparing thermoplastic copolymer, thermoplastic copolymer prepared therefrom, and thermoplastic resin composition including the same |
| WO2021101101A1 (en) * | 2019-11-21 | 2021-05-27 | 주식회사 엘지화학 | Method for preparing copolymer, copolymer prepared thereby, and thermoplastic resin composition comprising same |
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| KR970042630A (en) | 1997-07-24 |
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