KR100527298B1 - Method for Preparing Acrylic Resin with Reduced Coagulation in the Suspension Polymerization - Google Patents
Method for Preparing Acrylic Resin with Reduced Coagulation in the Suspension Polymerization Download PDFInfo
- Publication number
- KR100527298B1 KR100527298B1 KR10-2002-0047684A KR20020047684A KR100527298B1 KR 100527298 B1 KR100527298 B1 KR 100527298B1 KR 20020047684 A KR20020047684 A KR 20020047684A KR 100527298 B1 KR100527298 B1 KR 100527298B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- mercetopropionate
- monomer
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 10
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 10
- 238000010557 suspension polymerization reaction Methods 0.000 title claims description 15
- 230000015271 coagulation Effects 0.000 title abstract description 3
- 238000005345 coagulation Methods 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- -1 t-butyl peroxy Chemical group 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 2
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical group CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002348 vinylic group Chemical group 0.000 claims description 2
- VZBZCLRLPBEOBO-UHFFFAOYSA-N carboxyoxy octan-3-yl carbonate Chemical compound CCCCCC(CC)OC(=O)OOC(O)=O VZBZCLRLPBEOBO-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- 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)
Abstract
본 발명의 응집현상이 감소된 아크릴계 수지의 제조방법은 80-100 중량%의 메틸 메타크릴레이트 및 0-20 중량%의 비닐계 모노머로 이루어진 단량체 혼합물, 개시제 및 분산안정제의 존재 하에 연쇄이동제로서 하기 화학식 1로 표시되는 알킬 3-머켑토프로피오네이트 및 n-도데실머캅탄이 조합된 혼합물을 사용하는 것을 특징으로 한다.The method for preparing an acrylic resin having reduced coagulation is according to the present invention as a chain transfer agent in the presence of a monomer mixture, an initiator and a dispersion stabilizer composed of 80-100% by weight of methyl methacrylate and 0-20% by weight of a vinyl monomer. It is characterized by using a mixture of an alkyl 3-mercetopropionate and n-dodecyl mercaptan represented by the formula (1).
[화학식 1][Formula 1]
(상기 식에서, R은 4 내지 18개의 탄소원자를 갖는 알킬기임).Wherein R is an alkyl group having 4 to 18 carbon atoms.
Description
발명의 분야Field of invention
본 발명은 현탁중합에 있어서 응집현상이 감소된 아크릴계 수지의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 PMMA 입자를 제조하기 위한 현탁중합에 있어서, 사슬이동제로서 n-도데실 머켑탄과 알킬 3-머켑토 프로피오네이트를 적절하게 조합하여 사용함으로써, 높은 전환율을 갖을 뿐만 아니라, 반응기내에 입자의 응집현상이 감소되는 아크릴계 수지의 제조방법에 관한 것이다. The present invention relates to a method for producing an acrylic resin having reduced aggregation in suspension polymerization. More specifically, the present invention, in suspension polymerization for producing PMMA particles, by using a suitable combination of n-dodecyl merethane and alkyl 3-merceto propionate as a chain transfer agent, not only has a high conversion rate, The present invention relates to a method for producing an acrylic resin in which agglomeration of particles in a reactor is reduced.
발명의 배경Background of the Invention
일반적으로 현탁중합은 단량체를 미세한 크기로 분산시켜 중합하는 공정으로서, 분산상 내에서는 단량체가 괴상중합 방식으로 중합되는 방법이다. 현탁중합의 특징은 고중합도 고분자 생성물을 쉽게 얻을 수 있으며 또한 유화중합에서와 같이 분산제나 유화제 등을 사용하지 않기 때문에 비교적 순도가 높은 화합물을 얻을 수 있는 장점이 있다. In general, suspension polymerization is a process of dispersing a monomer to a fine size and polymerizing. In the dispersed phase, a monomer is polymerized in a bulk polymerization manner. Suspension polymerization is characterized in that it is easy to obtain a high polymer product, and also because it does not use a dispersing agent or an emulsifier, as in emulsion polymerization, it is possible to obtain a relatively high purity compound.
그런데, 현탁중합의 경우 반응 도중에 약간의 입자의 응집현상이 일어나는 문제점이 있는데, 이러한 현상은 반응기 벽면에 수지가 달라붙는 코팅현상과 입자들끼리의 뭉침현상 등으로 구별된다. 이러한 응집현상은 매질과의 열전달을 어렵게 하거나 최종 생성물을 이송할 때 공정상의 문제점을 유발하며, 특히 생성물의 물성에 영향을 미칠 가능성이 존재하게 된다. By the way, in the case of suspension polymerization, there is a problem that some particles are agglomerated during the reaction, and this phenomenon is classified into a coating phenomenon in which a resin adheres to the reactor wall and agglomeration of particles. Such agglomeration may make it difficult to transfer heat to the medium or cause process problems when transferring the final product. In particular, there is a possibility of affecting the physical properties of the product.
특히 폴리메틸메타아크릴레이트(PMMA)와 같이 반응기 벽면에 달라붙는 경향이 강한 고분자의 경우 이러한 현상은 더욱 문제가 된다. This is especially problematic for polymers that tend to stick to the reactor wall, such as polymethylmethacrylate (PMMA).
유럽특허 제372,968호에서는 현탁중합 도중에 소량의 페놀을 투입해서 코팅함량을 감소시키는 방법을 개시하고 있다. 그러나 상기 방법은 고분자가 일부 변색되기 때문에, PMMA나 폴리스틸렌과 같은 투명 수지의 제조에는 적용하기가 곤란하다는 단점이 있다. EP 372,968 discloses a method of reducing the coating content by adding a small amount of phenol during suspension polymerization. However, the method has a disadvantage in that it is difficult to apply to the production of a transparent resin such as PMMA and polystyrene because the polymer is partially discolored.
그 외에도 버퍼용액을 사용하거나 다양한 분산제를 사용함으로서 코팅현상을 억제하기 위한 노력이 진행되고 있으나, 만족할만한 결과를 얻어내지 못하고 있다. In addition, efforts have been made to suppress the coating phenomenon by using a buffer solution or various dispersants, but have not obtained satisfactory results.
반응기 벽면에 달라붙는 코팅현상 이외에도 입자들끼리의 뭉침현상도 공정상에서 매우 심각한 결과를 초래하게 된다. 반응초기에는 전환율이 낮아서 큰 문제가 발생되지 않으나 반응 속도가 증가함에 따라 점도가 증가하게 되며 발열현상을 억제할 수 없는 젤 현상 등이 일어날 가능성이 있다. 이러한 현상을 억제하기 위한 방법으로 적절한 분산 안정제를 사용하거나 저온 및 고온개시제를 적절히 혼합해서 사용하는 등의 다양한 방법이 시도되고 있다. In addition to coating on the reactor walls, the agglomeration of particles together has very serious consequences in the process. In the initial stage of the reaction, a low conversion rate does not cause a big problem, but as the reaction rate increases, the viscosity increases and there is a possibility that a gel phenomenon that cannot suppress the exothermic phenomenon may occur. As a method for suppressing such a phenomenon, various methods have been tried, such as using an appropriate dispersion stabilizer or by mixing a low temperature and a high temperature initiator as appropriate.
한편 사슬이동제로서 보통 머켑탄 류의 화합물을 많이 사용하는데, n-도데실머켑탄의 경우 냄새가 거의 없으며 사슬이동 효과가 큰 장점이 있으나, t-도데실머켑탄에 비해 용매에 대한 사슬이동속도가 매우 높아서 투입량이 증가함에 따라 올리고머 생성이 가속화되어 입자들의 응집현상이 증가할 뿐만 아니라, 전환율이 급격히 감소되는 현상이 발생되어 공정상에서 어려움이 있다. 반면 t-도데실머켑탄을 사용하게 되면 최종 생성물에서 냄새 발생 가능성이 존재하므로 이 역시 사용에 제약이 따른다. On the other hand, as a chain transfer agent, a lot of methane compounds are usually used. In the case of n-dodecyl merethane, there is almost no smell and a great effect of chain transfer. However, the chain transfer rate of solvent is much higher than that of t-dodecyl merethane. As the input amount is increased, oligomer formation is accelerated to increase the aggregation phenomenon of the particles, and the conversion rate is rapidly decreased, which causes difficulties in the process. On the other hand, the use of t-dodecylmerethane results in the possibility of odor generation in the final product, which also limits its use.
따라서, 본 발명에서는 상기와 같은 문제점을 해결하기 위하여, 사슬이동제로서 n-도데실머켑탄과 알킬 3-머켑토프로피오네이트이 일정비율로 조합된 혼합물을 도입함으로서, 현탁중합에 있어서 높은 전환율을 갖을 뿐만 아니라, 반응기내에 입자의 응집현상을 억제할 수 있는 아크릴계 수지의 제조 방법을 개발하기에 이른 것이다. Therefore, in the present invention, in order to solve the above problems, by introducing a mixture of n-dodecylmerethane and alkyl 3-mertotopionate as a constant ratio as a chain transfer agent, not only has a high conversion in suspension polymerization. Rather, it is to develop a method for producing an acrylic resin that can suppress the aggregation phenomenon of particles in the reactor.
본 발명의 목적은 현탁중합에 있어서 입자의 응집현상을 억제된 아크릴계 수지의 제조 방법을 제공하기 위한 것이다.An object of the present invention is to provide a method for producing an acrylic resin with suppressed agglomeration of particles in suspension polymerization.
본 발명의 다른 목적은 현탁중합에 있어서 높은 전환율을 갖는 아크릴계 수지의 제조 방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing an acrylic resin having a high conversion rate in suspension polymerization.
본 발명의 상기 및 기타의 목적들은 하기에 설명되는 본 발명에 의하여 모두 달성될 수 있다. 이하 본 발명의 내용을 하기에 상세히 설명한다. The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.
본 발명의 응집현상이 감소된 아크릴계 수지의 제조방법은 80-100 중량%의 메틸 메타크릴레이트 및 0-20 중량%의 비닐계 모노머로 이루어진 단량체 혼합물, 개시제 및 분산안정제의 존재하에 연쇄이동제로서 하기 화학식 1로 표시되는 알킬 3-머켑토프로피오네이트 및 n-도데실머캅탄이 조합된 혼합물을 사용하는 것을 특징으로 한다.The method for preparing an acrylic resin having reduced coagulation is according to the present invention as a chain transfer agent in the presence of a monomer mixture, an initiator and a dispersion stabilizer composed of 80-100% by weight of methyl methacrylate and 0-20% by weight of a vinyl monomer. It is characterized by using a mixture of an alkyl 3-mercetopropionate and n-dodecyl mercaptan represented by the formula (1).
[화학식 1][Formula 1]
(상기 식에서, R은 4 내지 18개의 탄소원자를 갖는 알킬기임). Wherein R is an alkyl group having 4 to 18 carbon atoms.
이하, 본 발명의 내용에 대하여 상세히 설명한다. EMBODIMENT OF THE INVENTION Hereinafter, the content of this invention is demonstrated in detail.
본 발명에서 PMMA 수지를 제조하기 위한 현탁중합의 조성물은 단량체 외에 크게 세가지로 분류할 수 있다. 즉, 개시제, 분산안정제 및 사슬이동제로 구성되어 있다. Suspension polymerization composition for producing PMMA resin in the present invention can be classified into three types in addition to the monomer. That is, it consists of an initiator, a dispersion stabilizer, and a chain transfer agent.
라디칼 중합은 기존에 알려진 어떠한 방법 즉, 현탁중합, 에멀젼 중합 및 벌크중합등으로 가능하며, 회분식 중합 또는 연속식 중합법이 사용될 수 있다. 더욱 유리한 방법은 현탁중합이며, 여기서 단량체 또는 단량체 혼합물은 수용액상에서 중합 될 수 있다. The radical polymerization may be any method known in the art, that is, suspension polymerization, emulsion polymerization, bulk polymerization, and the like, and batch polymerization or continuous polymerization may be used. A more advantageous method is suspension polymerization, wherein the monomer or monomer mixture can be polymerized in aqueous solution.
단량체 혼합물Monomer mixture
본 발명의 단량체 혼합물은 80 내지 100 중량%의 메틸 메타아크릴레이트 및 0 내지 20%의 비닐계 모노머로 이루어진다. The monomer mixture of the present invention consists of 80 to 100% by weight methyl methacrylate and 0 to 20% vinylic monomers.
상기 비닐계 모노머의 구체적인 예로는 메틸 메타아크릴레이트, 메타크릴레이트, 아크릴레이트, 메타크릴산, 아크릴로니트릴 등이 있다. Specific examples of the vinyl monomers include methyl methacrylate, methacrylate, acrylate, methacrylic acid, acrylonitrile, and the like.
중합개시제Polymerization initiator
본 발명에서 중합개시제는 t-부틸 퍼옥시 네오데카노에이트, t-부틸 퍼옥시 피말레이트, t-부틸퍼옥시 2-에틸 헥사노에이트, 디이소프로필 퍼옥시디카보네이트, 디-2-에틸헥실 퍼옥시디카보네이트, 3,5,5-트리메틸 헥사노일 퍼옥사이드, 벤조일 퍼옥사이드, 라우로일 퍼옥사이드와 같은 유기과산화물; 및 아조비스이소부티로니트릴(이하, AIBN이라함) 등의 아조화합물을 단독 또는 1종 이상을 혼합하여 사용할 수 있다. 이중 벤조일 퍼옥사이드와 AIBN이 바람직하며, 더욱 바람직하게는 벤조일 퍼옥사이드를 사용하는 것이 가장 유리하다.In the present invention, the polymerization initiator is t-butyl peroxy neodecanoate, t-butyl peroxy pymaleate, t-butylperoxy 2-ethyl hexanoate, diisopropyl peroxydicarbonate, di-2-ethylhexyl perox Organic peroxides such as cidicarbonate, 3,5,5-trimethyl hexanoyl peroxide, benzoyl peroxide, lauroyl peroxide; And azo compounds such as azobisisobutyronitrile (hereinafter referred to as AIBN) may be used alone or in combination of one or more thereof. Of these, benzoyl peroxide and AIBN are preferred, and more preferably, benzoyl peroxide is most advantageous.
중합개시제는 상기 개시제를 단독으로 사용할 수 있으나, 반감기가 50 ℃에서 7시간 이하인 저온용 중합 개시제와 80 ℃에서 7시간 내지 8시간 정도인 중고온용 중합 개시제를 조합하여 사용하면 더욱 좋다. 일반적으로 총 조성물 100 중량부에 대하여 저온용 중합개시제는 0.5 내지 2.5 중량부, 중고온용 중합 개시제는 0.005 내지 0.15 중량부로 사용하는 것이 바람직하다. The polymerization initiator may be used alone, but it is better to use a combination of a low-temperature polymerization initiator having a half-life of 7 hours or less at 50 ° C and a high-temperature polymerization initiator having a high temperature of about 7 hours to 8 hours at 80 ° C. Generally, it is preferable to use 0.5 to 2.5 parts by weight of the low temperature polymerization initiator and 0.005 to 0.15 parts by weight of the high temperature polymerization initiator with respect to 100 parts by weight of the total composition.
본 발명에서는 아크릴 단량체 100 중량부에 대하여, 개시제 0.1 내지 5.0 중량부를 사용하는 것이 바람직하다. In this invention, it is preferable to use 0.1-5.0 weight part of initiators with respect to 100 weight part of acrylic monomers.
분산안정제Dispersion Stabilizer
분산안정제로는 일반적으로 유기분산제와 무기분산제가 있으며, 본 발명에서는 무기 분산제를 사용하는 것이 더 바람직하다. The dispersion stabilizer generally includes an organic dispersant and an inorganic dispersant, and in the present invention, it is more preferable to use an inorganic dispersant.
본 발명에 사용될 수 있는 무기분산제로는 알루미늄 히드록사이드, 페릭 히드록사이드, 티타늄 히드록사이드, 포스페이트계 화합물, 카보네이트계 화합물, 설페이트 화합물 등이 있다. 이중 특히 포스페이트 화합물, 더욱 바람직하게는 트리칼슘 포스페이트가 가장 바람직하다. Inorganic dispersants that can be used in the present invention include aluminum hydroxide, ferric hydroxide, titanium hydroxide, phosphate compounds, carbonate compounds, sulfate compounds and the like. Most particularly of these are phosphate compounds, more preferably tricalcium phosphate.
본 발명에서 무기 분산제는 일반적으로 수용액 상에 미세한 고체입자로 존재하는데, 이때 고체 입자의 농도는 보통 0.1 내지 50%, 바람직하게는 10 내지 40% 범위가 유리하다. In the present invention, the inorganic dispersant is generally present as fine solid particles on the aqueous solution, in which the concentration of the solid particles is usually in the range of 0.1 to 50%, preferably 10 to 40%.
분산안정제는 일반적으로 중합 후에 물로 여러 차례 세척을 함으로서 고분자 입자로부터 제거된다. Dispersion stabilizers are generally removed from polymer particles by washing several times with water after polymerization.
사슬이동제Chain transfer agent
중합체의 분자량은 적절한 사슬이동제를 이용하여 조절 가능하다. 본 발명에서 사용되는 사슬이동제는 하기 화학식 1로 표시되는 알킬 3-머켑토프로피오네이트와 n-도데실머캅탄이 조합된 혼합물을 사용하는 것을 특징으로 한다. The molecular weight of the polymer can be adjusted using an appropriate chain transfer agent. The chain transfer agent used in the present invention is characterized by using a mixture of an alkyl 3-mercetopropionate and n-dodecyl mercaptan represented by the following formula (1).
[화학식 1][Formula 1]
(상기 식에서, R은 4 내지 18개의 탄소원자를 갖는 알킬기임). Wherein R is an alkyl group having 4 to 18 carbon atoms.
본 발명에서 사슬이동제는 아크릴 단량체 100 중량부에 대하여, 0.02 내지 2 중량부 범위에서 사용될 수 있다. Chain transfer agent in the present invention can be used in the range of 0.02 to 2 parts by weight based on 100 parts by weight of the acrylic monomer.
또한 알킬 3-머켑토프로피오네이트와 n-도데실머캅탄의 적정 중량 비율은 0.1:1.0 내지 1.0:0.1의 범위이다. In addition, the appropriate weight ratio of alkyl 3-mercetopropionate and n-dodecyl mercaptan is in the range of 0.1: 1.0 to 1.0: 0.1.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다. The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예 Example
실시예 1Example 1
메틸 메타아크릴레이트 245 g(100 중량부), 메틸 아크릴레이트 6.12 g, 벤조일퍼옥사이드 1.2 g, 폴리옥시에틸렌 도데실 에테르포스페이트 0.37 g, n-도데실머켑탄 0.24 g(메틸 메타아크릴레이트 100 중량부를 기준으로 0.1 중량부) 및 2-에틸헥실 3-머켑토프로피오네이트 0.49 g(메틸 메타아크릴레이트 100 중량부를 기준으로 0.2 중량부)를 포함하는 모노머 용액을 트리칼슘포스페이트 1.2 g 이 포함된 순수용액 450 g을 포함하는 1ℓ4구 유리 반응기에 투입하였다. 투입 후 혼합물을 75 ℃로 승온 시킨후 3시간 동안 400 rpm에서 반응을 진행시킨 다음, 추가로 90 ℃에서 2시간 동안 반응을 더 진행시켰다. 반응 후 냉각시킨 다음, 세척 및 탈수과정을 3회 이상 반복해서 얻은 생성물을 80 ℃ 오븐에서 24 시간 동안 건조해서 최종 생성물을 얻었다. 응집체의 함량은 최종 생성물을 채번호 20(20 mesh)을 이용해서 여과 후 채 위에 남은 양을 측정하였으며, 측정 결과 반응 후 응집된 수지의 양은 약 3.1 g 이었다. 전환율은 최종 생성물 기준으로 85 %, 수지의 중량평균 분자량은 110,000 g/mol으로 분석되었다. 245 g of methyl methacrylate (100 parts by weight), 6.12 g of methyl acrylate, 1.2 g of benzoyl peroxide, 0.37 g of polyoxyethylene dodecyl ether phosphate, 0.24 g of n-dodecyl merketane (based on 100 parts by weight of methyl methacrylate) 0.1 parts by weight) and 0.49 g of 2-ethylhexyl 3-mercetopropionate (0.2 parts by weight based on 100 parts by weight of methyl methacrylate) were added to a pure solution containing 1.2 g of tricalcium phosphate. Into a 1 L four-neck glass reactor containing g. After the addition, the mixture was heated to 75 ° C. and then reacted at 400 rpm for 3 hours, and then further reacted at 90 ° C. for 2 hours. After the reaction was cooled, the product obtained by repeating the washing and dehydration three times or more was dried in an oven at 80 ℃ for 24 hours to obtain a final product. The amount of aggregate was measured by using the number 20 (20 mesh) of the final product was measured on the remaining amount after filtering, the amount of the aggregated resin after the reaction was about 3.1 g. The conversion was 85% based on the final product and the weight average molecular weight of the resin was 110,000 g / mol.
실시예 2Example 2
n-도데실머켑탄을 0.2 중량부, 2-에틸헥실 3-머켑토프로피오네이트를 0.35 중량부로 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that 0.2 part by weight of n-dodecylmerethane was used and 0.35 part by weight of 2-ethylhexyl 3-mercetopropionate.
실시예 3Example 3
n-도데실머켑탄을 0.3 중량부, 2-에틸헥실 3-머켑토프로피오네이트를 0.45 중량부로 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that 0.3 part by weight of n-dodecyl merethane was used and 0.45 part by weight of 2-ethylhexyl 3-mercetopropionate.
실시예 4Example 4
n-도데실머켑탄을 0.1 중량부, 2-에틸헥실 3-머켑토프로피오네이트 대신 이소프로필 3-머켑토프로피오네이트를 0.25 중량부로 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that 0.1 part by weight of n-dodecylmerethane was used and 0.25 part by weight of isopropyl 3-mercetopropionate instead of 2-ethylhexyl 3-mercetopropionate.
실시예 5Example 5
n-도데실머켑탄을 0.2 중량부, 2-에틸헥실 3-머켑토프로피오네이트 대신 이소프로필 3-머켑토프로피오네이트를 0.35 중량부로 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행되었다. It was carried out in the same manner as in Example 1, except that 0.2 part by weight of n-dodecyl merpentane and 0.35 part by weight of isopropyl 3-mertotopropionate instead of 2-ethylhexyl 3-mertotopropionate.
실시예 6Example 6
n-도데실머켑탄을 0.3 중량부, 2-에틸헥실 3-머켑토프로피오네이트 대신 이소프로필 3-머켑토프로피오네이트를 0.55 중량부로 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that 0.3 part by weight of n-dodecyl merethane was used and 0.55 part by weight of isopropyl 3-mercetopropionate instead of 2-ethylhexyl 3-mercetopropionate.
비교 실시예 1Comparative Example 1
n-도데실머켑탄만을 0.4 중량부로 사용한 것을 제외하고는 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that only n-dodecylmerethane was used at 0.4 part by weight.
비교 실시예 2Comparative Example 2
n-도데실머켑탄만을 0.6 중량부로 사용한 것을 제외하고는 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that only n-dodecylmerethane was used at 0.6 parts by weight.
비교 실시예 3Comparative Example 3
n-도데실머켑탄만을 0.8 중량부로 사용한 것을 제외하고는 실시예 1과 동일하게 수행되었다. The same procedure as in Example 1 was carried out except that only n-dodecylmerethane was used at 0.8 parts by weight.
상기 각 실시예 및 비교실시예에서 제조된 최종 생성물의 전환율, 분자량 및 생성된 응집체의 함량을 하기 표 1에 나타내었다. Conversion rate, molecular weight and content of the aggregates of the final product prepared in each of the above Examples and Comparative Examples are shown in Table 1 below.
NDM: n-도데실머켑탄 NDM: n-dodecyl merethane
EHM: 2-에틸헥실 3-머켑토프로피오네이트 EHM: 2-ethylhexyl 3-mercetopropionate
IPM: 이소프로필 3-머켑토프로피오네이트IPM: Isopropyl 3-merctopropionate
상기 표 1에 나타난 바와 같이, 사슬이동제로서 n-도데실머켑탄과 알킬 3-머켑토프로피오네이트를 혼합하여 사용한 실시예 1-6의 경우, 비교실시예에 비해 전환율이 우수한 것으로 나타났으며, 응집체의 양도 현저하게 저하된 것을 확인할 수 있었다. 반면, 사슬이동제로서 n-도데실머켑탄만을 사용한 비교실시에 1-3은 실시예에 비해 전환율이 떨어졌으며, 또한 응집체의 양도 높게 나타났다. As shown in Table 1, Example 1-6 using a mixture of n-dodecyl merethane and alkyl 3-mertotopropionate as a chain transfer agent, the conversion was found to be superior to the comparative example, It was confirmed that the amount of aggregate was also significantly reduced. On the other hand, in Comparative Examples 1-3 using only n-dodecyl merethane as a chain transfer agent, the conversion was lower than that of the Example, and the amount of aggregates was also high.
본 발명은 현탁중합에 있어서 사슬이동제로서 n-도데실머켑탄에 알킬 3-머켑토프로피오네이트를 도입함으로서, 입자의 응집현상을 억제할 뿐만 아니라, 우수한 전환율을 나타내는 아크릴계 수지의 제조방법을 제공하는 효과를 갖는다. The present invention provides a method for producing an acrylic resin that exhibits excellent conversion as well as suppressing aggregation of particles by introducing an alkyl 3-mertotopropionate into n-dodecylmerethane as a chain transfer agent in suspension polymerization. Has an effect.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2002-0047684A KR100527298B1 (en) | 2002-08-13 | 2002-08-13 | Method for Preparing Acrylic Resin with Reduced Coagulation in the Suspension Polymerization |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2002-0047684A KR100527298B1 (en) | 2002-08-13 | 2002-08-13 | Method for Preparing Acrylic Resin with Reduced Coagulation in the Suspension Polymerization |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20040015852A KR20040015852A (en) | 2004-02-21 |
KR100527298B1 true KR100527298B1 (en) | 2005-11-09 |
Family
ID=37321944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR10-2002-0047684A Expired - Fee Related KR100527298B1 (en) | 2002-08-13 | 2002-08-13 | Method for Preparing Acrylic Resin with Reduced Coagulation in the Suspension Polymerization |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100527298B1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100725934B1 (en) * | 2005-12-06 | 2007-06-11 | 엘지엠엠에이 주식회사 | Manufacturing method of acrylic resin with excellent thermal stability and easy molecular weight control |
KR100890172B1 (en) * | 2006-12-18 | 2009-03-25 | 엘지엠엠에이 주식회사 | Coating |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0178115A2 (en) * | 1984-10-02 | 1986-04-16 | Sumitomo Chemical Company, Limited | Process for the production of heat resistant methacrylic resin |
US4593081A (en) * | 1985-04-25 | 1986-06-03 | Phillips Petroleum Company | Chain-transfer agents for emulsion polymerization and polymer products produced therewith |
US6111042A (en) * | 1997-09-24 | 2000-08-29 | Nof Corporation | Polyfunctional peroxides, vinyl monomer polymerization initiators comprising the same and process for polymerization vinyl monomers employing the same |
-
2002
- 2002-08-13 KR KR10-2002-0047684A patent/KR100527298B1/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0178115A2 (en) * | 1984-10-02 | 1986-04-16 | Sumitomo Chemical Company, Limited | Process for the production of heat resistant methacrylic resin |
US4593081A (en) * | 1985-04-25 | 1986-06-03 | Phillips Petroleum Company | Chain-transfer agents for emulsion polymerization and polymer products produced therewith |
US6111042A (en) * | 1997-09-24 | 2000-08-29 | Nof Corporation | Polyfunctional peroxides, vinyl monomer polymerization initiators comprising the same and process for polymerization vinyl monomers employing the same |
Also Published As
Publication number | Publication date |
---|---|
KR20040015852A (en) | 2004-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4052661B2 (en) | Improved polymer formation method | |
JP6240637B2 (en) | Styrenated phenol ethoxylates in emulsion polymerization. | |
US6150468A (en) | Water soluble amphiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization | |
KR101056958B1 (en) | Method for preparing vinyl chloride polymer by additional addition of water soluble initiator | |
KR100527298B1 (en) | Method for Preparing Acrylic Resin with Reduced Coagulation in the Suspension Polymerization | |
KR102310659B1 (en) | Secondary suspending agent for suspension polymerisation reaction | |
CN1788025A (en) | Dosing of peroxide to a suspension process wherein styrene is polymerized | |
JP4070260B2 (en) | Method for producing acrylic-based polymer beads | |
JP2002506478A (en) | Improved acid-catalyzed polymerization method | |
US5344901A (en) | Process for preparing acrylic polymers in suspension | |
US5155190A (en) | Process for producing poly methyl methacrylate/N-substituted maleimide optical resin | |
JPS6028282B2 (en) | Dispersion stabilizer for suspension polymerization of vinyl compounds | |
JPH0125483B2 (en) | ||
JP3149487B2 (en) | Method for producing methacrylic resin particles | |
CN111484580B (en) | Physical cross-linking agent, high oil absorption material and preparation method thereof | |
JPH0368883B2 (en) | ||
JPS61123613A (en) | Manufacture of low molecular weight vinyl halide/ vinyl ester copolymer by aqueous polymerization | |
JPH11181003A (en) | Method for producing polymer fine particles | |
EP1290036A1 (en) | Water soluble ampiphilic heteroarm star polymers and their use as emulsion stabilizers in emulsion polymerization | |
CN112390905B (en) | Methyl methacrylate polymer and preparation method and application thereof | |
JPH07145214A (en) | Manufacturing method of heat-resistant methacrylic resin | |
KR100231260B1 (en) | Process for producing styrene resin composition with excellent processability | |
JP3492243B2 (en) | Method for producing polymer fine particles | |
JPH0735406B2 (en) | Method for producing composite polymer particles | |
JP3668692B2 (en) | Method for producing alkali-soluble polymer aqueous dispersion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 20020813 |
|
PA0201 | Request for examination | ||
PG1501 | Laying open of application | ||
E902 | Notification of reason for refusal | ||
PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20041116 Patent event code: PE09021S01D |
|
AMND | Amendment | ||
E601 | Decision to refuse application | ||
PE0601 | Decision on rejection of patent |
Patent event date: 20050801 Comment text: Decision to Refuse Application Patent event code: PE06012S01D Patent event date: 20041116 Comment text: Notification of reason for refusal Patent event code: PE06011S01I |
|
J201 | Request for trial against refusal decision | ||
PJ0201 | Trial against decision of rejection |
Patent event date: 20050901 Comment text: Request for Trial against Decision on Refusal Patent event code: PJ02012R01D Patent event date: 20050801 Comment text: Decision to Refuse Application Patent event code: PJ02011S01I Appeal kind category: Appeal against decision to decline refusal Decision date: 20051101 Appeal identifier: 2005101005888 Request date: 20050901 |
|
AMND | Amendment | ||
PB0901 | Examination by re-examination before a trial |
Comment text: Amendment to Specification, etc. Patent event date: 20050930 Patent event code: PB09011R02I Comment text: Request for Trial against Decision on Refusal Patent event date: 20050901 Patent event code: PB09011R01I Comment text: Amendment to Specification, etc. Patent event date: 20050516 Patent event code: PB09011R02I |
|
B701 | Decision to grant | ||
PB0701 | Decision of registration after re-examination before a trial |
Patent event date: 20051101 Comment text: Decision to Grant Registration Patent event code: PB07012S01D Patent event date: 20051014 Comment text: Transfer of Trial File for Re-examination before a Trial Patent event code: PB07011S01I |
|
GRNT | Written decision to grant | ||
PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20051102 Patent event code: PR07011E01D |
|
PR1002 | Payment of registration fee |
Payment date: 20051103 End annual number: 3 Start annual number: 1 |
|
PG1601 | Publication of registration | ||
PR1001 | Payment of annual fee |
Payment date: 20081001 Start annual number: 4 End annual number: 4 |
|
PR1001 | Payment of annual fee |
Payment date: 20090917 Start annual number: 5 End annual number: 5 |
|
PR1001 | Payment of annual fee |
Payment date: 20100929 Start annual number: 6 End annual number: 6 |
|
PR1001 | Payment of annual fee |
Payment date: 20111025 Start annual number: 7 End annual number: 7 |
|
FPAY | Annual fee payment |
Payment date: 20121002 Year of fee payment: 8 |
|
PR1001 | Payment of annual fee |
Payment date: 20121002 Start annual number: 8 End annual number: 8 |
|
FPAY | Annual fee payment |
Payment date: 20130913 Year of fee payment: 9 |
|
PR1001 | Payment of annual fee |
Payment date: 20130913 Start annual number: 9 End annual number: 9 |
|
FPAY | Annual fee payment |
Payment date: 20140917 Year of fee payment: 10 |
|
PR1001 | Payment of annual fee |
Payment date: 20140917 Start annual number: 10 End annual number: 10 |
|
LAPS | Lapse due to unpaid annual fee | ||
PC1903 | Unpaid annual fee |
Termination category: Default of registration fee Termination date: 20161009 |