KR970009240B1 - Method for block copolymer of alkylene oxide with vinyl or diene monomers by anionic polymerization - Google Patents
Method for block copolymer of alkylene oxide with vinyl or diene monomers by anionic polymerization Download PDFInfo
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- KR970009240B1 KR970009240B1 KR1019930023777A KR930023777A KR970009240B1 KR 970009240 B1 KR970009240 B1 KR 970009240B1 KR 1019930023777 A KR1019930023777 A KR 1019930023777A KR 930023777 A KR930023777 A KR 930023777A KR 970009240 B1 KR970009240 B1 KR 970009240B1
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- monomer
- vinyl
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- butyl
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- 239000000178 monomer Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 21
- 150000001993 dienes Chemical class 0.000 title claims description 16
- 229920002554 vinyl polymer Polymers 0.000 title claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims description 14
- 125000002947 alkylene group Chemical group 0.000 title claims description 5
- 229920001400 block copolymer Polymers 0.000 title description 16
- 238000010539 anionic addition polymerization reaction Methods 0.000 title description 8
- 229920000642 polymer Polymers 0.000 claims description 25
- -1 alkali metal alkoxide Chemical class 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002924 oxiranes Chemical class 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012454 non-polar solvent Substances 0.000 claims description 9
- 238000012661 block copolymerization Methods 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000002798 polar solvent Substances 0.000 description 7
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000010550 living polymerization reaction Methods 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- HQDYNFWTFJFEPR-UHFFFAOYSA-N 1,2,3,3a-tetrahydropyrene Chemical compound C1=C2CCCC(C=C3)C2=C2C3=CC=CC2=C1 HQDYNFWTFJFEPR-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08F2438/00—Living radical polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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)
- Graft Or Block Polymers (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 음이온 중합에 의하여 비극성 용매중에서 알킬렌옥사이드와 비닐계 또는 디엔계 다량체와의 블록 공중합체를 제조하는 방법에 관한 것이다.The present invention relates to a process for producing block copolymers of alkylene oxides and vinyl or diene multimers in nonpolar solvents by anionic polymerization.
종래, 폴리알킬렌옥사이드의 중합은 통상 알칼리금속의 알콕사이드 계통의 개시제를 사용하고, 테트리히드로푸란(THF)이나 디그림(Diglyme)을 용매로 사용하는 음이온 중합 반응에 의하여 수행하여 왔다[Journal of Polymer Science : Part A : Polymer chemistry, 제26권, 2031페이지 참조]. 또 다른 합성방법은 디메틸 술폭사이드(DMSO)를 칼륨 tert-부톡사이드와 반응시켜 담실(Dimsyl) 음이온을 제조한후, 에틸렌 옥사이드를 DMSO 중에서 중압하는 것이다[Journal of Polymer Science : Part A-1, 제7권, 569페이지 참조].Conventionally, polymerization of polyalkylene oxides has been generally carried out by an anionic polymerization reaction using an alkali metal alkoxide initiator and using tetrahydrofuran (THF) or Diglyme as a solvent [Journal of Polymer Science: Part A: Polymer chemistry, Vol. 26, p. 2031]. Another synthetic method is to prepare dimethyl sulfide by reacting dimethyl sulfoxide (DMSO) with potassium tert-butoxide, and then pressurize ethylene oxide in DMSO [Journal of Polymer Science: Part A-1, agent 7, pp. 569].
이와같은 종래의 중합 방법에서는 극성 용매를 반드시 사용하여야 하는데, 사용된 극성 용매는 독성이 강하여 여러 가지 안전 상의 문제를 초래한다. 또한, 극성 용매의 사용으로 인하여 고분자 제조 후 폴리알킬렌옥사이드 및 이를 포함한 블록 공중합체의 정제 과정에서 많은 작업 시간이 소요될 뿐만 아닐, 정제 과정자체가 매우 어렵다고 하는 단점이 있다.In such a conventional polymerization method, a polar solvent must be used, and the polar solvent used is highly toxic and causes various safety problems. In addition, due to the use of a polar solvent, not only takes a lot of time in the purification process of the polyalkylene oxide and the block copolymer including the same after the preparation of the polymer, there is a disadvantage that the purification process itself is very difficult.
한편, 알킬리튬을 개시제로 사용하는 비닐계 및 디엔계 단량체의 음이온 중합 방법이 공지되어 있다[Advanced in Polymer Science, 제56권 1페이지 참조]. 그러나, 이 중합 방법을 사용할 경우, 비극성 용매는 물론, 극성 용매인 THF를 사용하더라도 개시제로서 알킬리튬을 사용하여 에폭사이드 고분자 및 이를 포함하는 블록 공중합체를 제조하는 것은 사실상 불가능하다고 알려져 있다[Ring-Opening Polymerization, ACS Symposium series, No. 286, 37페이지 참조].On the other hand, a method of anionic polymerization of vinyl-based and diene-based monomers using alkyllithium as an initiator is known [Advanced in Polymer Science, Vol. 56, page 1]. However, when using this polymerization method, it is known that it is practically impossible to prepare an epoxide polymer and a block copolymer containing the same using alkyllithium as an initiator even if THF, a polar solvent as well as a polar solvent, is used. Opening Polymerization, ACS Symposium series, No. See pages 286, 37].
콜로이드 안정화제로서 친수성 고분자와 소수성 고분자와의 블록 형태인 공중합체가 널리 사용되고 있다. 예를 들면, 친수성 고분자인 폴리알킬렌옥사이드와 소수성 고분자인 비닐계 또는 디엔계 고분자와의 블록 공중합체는 안정화제로서 특히 유용하다고 알려져 있다.As a colloidal stabilizer, a copolymer having a block form of a hydrophilic polymer and a hydrophobic polymer is widely used. For example, a block copolymer of a hydrophilic polymer polyalkylene oxide and a hydrophobic polymer vinyl or diene polymer is known to be particularly useful as a stabilizer.
그러나, 종래에는 비닐계 또는 디엔계 단량체와 에폭사이드계 단량체와의 블록 공중합체는 다수의 반응 및 정제 단계를 거쳐 제조하여 왔다. 즉, 알킬리튬을 개시제로 하여 스티렌이나 디엔계 단량체를 리빙 중합한 후, 에틸렌옥사이드로 정지 반응시키고, 산과 반응시켜서 쇄말단에 히드록시(-OH) 기를 갖는 알콜을 생성시킨 다음, 이와 같이 제조된 고분자를 메탄올과 같은 저가 알콜에 침전시켜 다시 건조시킨 후, 수산화 나트륨 또는 수산화 칼륨 등과 반응시키고, 이어서 THF 등과 같은 극성 용매 중에서 다시 에틸렌옥사이드 단량체를 부가시켜 이들 블록 공중합체를 제조한다[Advanced in Polymer Science, 제56권 1 내지 90페이지 참조].However, conventionally, block copolymers of vinyl or diene monomers and epoxide monomers have been prepared through a number of reaction and purification steps. That is, after living polymerization of a styrene or diene monomer with alkyllithium as an initiator, and then quenched with ethylene oxide, and reacted with an acid to produce an alcohol having a hydroxy (-OH) group at the end of the chain. These block copolymers are prepared by precipitating the polymer in a low-cost alcohol such as methanol, drying it, reacting with sodium hydroxide or potassium hydroxide, and then adding ethylene oxide monomer again in a polar solvent such as THF. [Advanced in Polymer Science , Vol. 56, pp. 1 to 90].
더욱이, 개시제서 알킬리튬을 비극성 용매와 함께 사용할 경우, 단일 반응기 내에서 비닐계 고분자와 에폭사이드계 고분자와의 블록 공중합체를 단량체 부가법으로 제조할 수 없다고 알려져 있다[Die Makromolecular Chemie, Macromolecular Symposium, 제42/43권, 463 내지 473페이지 참조].Moreover, it is known that when copolymerizing alkyllithium with a non-polar solvent, a block copolymer of vinyl polymer and epoxide polymer cannot be prepared by monomer addition method in a single reactor [Die Makromolecular Chemie, Macromolecular Symposium, 42, 43, pages 463-473].
따라서, 본 발명의 목적은 독성 및 정제의 문제를 초래하지 않는 비극성 용매를 사용하는 것이 가능한 폴리알킬렌옥사이드를 포함하는 다양한 블록 공중합체의 음이온 중합 방법을 제공하는 것이다.It is therefore an object of the present invention to provide a process for the anionic polymerization of various block copolymers comprising polyalkylene oxides which makes it possible to use nonpolar solvents which do not cause toxicity and purification problems.
본 발명의 다른 목적은 종래의 제조 과정에서는 여러 가지 부반응 때문에 불가능하였던 분자량을 쉬게 조절할 수 있는 폴리알킬렌옥사이드의 음이온 중합 방법을 제공하는 것이다.Another object of the present invention is to provide a method for the anionic polymerization of polyalkylene oxide which can easily adjust the molecular weight which was not possible due to various side reactions in the conventional manufacturing process.
또 다른 본 발명의 목적은 비닐계 단량체 또는 디엔계 단량체로부터 생성되는 리빙 고분자의 분자량 및 미세 구조를 용이하게 조절할 수 있는 블록 공중합체의 제조 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a block copolymer that can easily control the molecular weight and microstructure of living polymers produced from vinyl monomers or diene monomers.
본 발명의 또 다른 목적은 비극성 용매 중에서 단일의 반응기 내에서 비닐계 또는 디엔계 리빙 고분자를 알킬렌옥사이드와 용이하게 블럭 공중합할 수 있는 방법을 제공하는 것이다.It is another object of the present invention to provide a method for easily block copolymerizing vinyl-based or diene-based living polymers with alkylene oxide in a single reactor in a non-polar solvent.
본 발명의 한 가지 특징에 의하면, 제조 후의 정제가 간편하고, 분자량을 쉽게 조절할 수 있는 폴리알킬렌옥사이드의 제조 방법이 제공된다. 이러한 방법은 적당한 몰비의 알칼리금속 알콕사이드/알킬리튬 혼합물로 된 개시제의 존재 하에, 벤젠, 톨루엔, 시클로헥산, 헥산, 테트라히드로푸란 및 테트라히드로피렌으로 이루어진 군으로부터 선택된 용매를 사용하여 에폭사이드계 단량체를 음이온 중합시키는 것으로 이루어진다.According to one feature of the present invention, there is provided a method for producing a polyalkylene oxide, in which purification after production is simple and molecular weight can be easily adjusted. This process involves the use of a solvent selected from the group consisting of benzene, toluene, cyclohexane, hexane, tetrahydrofuran and tetrahydropyrene in the presence of an initiator of an appropriate molar ratio of alkali metal alkoxide / alkyllithium mixture to It consists of anionic polymerization.
본 발명에서 폴리알킬렌옥사이드 중합체 제조에 사용되는 단량체로는 하기식(1)로 나타내는 에폭사이드 계통의 단량체를 들 수 있다.Examples of the monomer used in the production of the polyalkylene oxide polymer in the present invention include epoxide-based monomers represented by the following formula (1).
상기 식에서 R1,R2,R3및 R4는 각각 독립적으로 수소원자, 저급 알킬 또는 페닐기이다. 특히, 에틸렌옥사이드와 프로필렌옥사이드가 바람직하다.Wherein R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a lower alkyl or a phenyl group. In particular, ethylene oxide and propylene oxide are preferable.
개시제로는 알키리튬, 즉 n-부틸리튬, sec-부틸리튬, tert-부틸리튬 등을 하기식 (II)로 나타내는 알칼리금속 알콕사이드 계통의 물질과 적당한 비율로 혼합한 개시제가 사용된다.As an initiator, the initiator which mixed an alkali metal alkoxide type | system | group substance with an alkali metal, ie, n-butyllithium, sec-butyllithium, tert- butyllithium, etc. by following formula (II) at an appropriate ratio is used.
상기 식에서, R5는 메틸, 프로필, 이소프로필, n-부틸, sec-부틸, tert-부틸 또는 아밀기이며, Mt는 리튬, 나트륨 또는 칼륨이다.Wherein R 5 is methyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl group and Mt is lithium, sodium or potassium.
알킬리튬과 알콕사이드의 바람직한 혼합 몰비는 10~0.5이다.The preferable mixing molar ratio of alkyl lithium and alkoxide is 10-0.5.
또한, 용매로는 벤젠, 톨루엔, 시클로헥산, 헥산 등과 같은 비극성 탄화 수소 용매는 물론, THF, THP(테트라히드로피렌) 등의 극성 용매를 사용할 수 있다.As the solvent, non-polar hydrocarbon solvents such as benzene, toluene, cyclohexane, hexane and the like, as well as polar solvents such as THF and THP (tetrahydropyrene) can be used.
또한, 본 발명의 두 번째 특징에 의하면, 알킬리튬 개시제의 존재 하에 리방중합에 의하여 제조된 비닐계 또는 디엔계 고분자를, 알킬리튬에 대하여 적당한 비율의 알칼리금속 알콕사이드 존재 하에, 알킬렌옥사이드와 단일의 반응기내에서 블록 공중합시키는 것으로 이루어진 공중합체를 고순도로 제조하는 방법이 제공된다.According to a second aspect of the present invention, a vinyl-based or diene-based polymer prepared by lipopolymerization in the presence of an alkyllithium initiator may be separated from an alkylene oxide in the presence of an alkali metal alkoxide in an appropriate ratio with respect to alkyllithium. A method of producing a copolymer of high purity, which comprises block copolymerization in a reactor, is provided.
즉, 본 발명의 블록 공중합체의 제조 방법은 (가) 비극성 용매 중에서, 알킬리튬을 개시제로 사용하여 비닐계 단량체 또는 디엔계 단량체를 리빙 중합하는 단계 및 (나) 알칼리금속 알콕사이드와 알킬리튬과의 몰비가 10~0.5로 되는 양의 알칼리금속 알콕사이드를 (가)단계에서 제조된 리빙 고분자와 혼합한 다음, 에폭사이드계 단량체를 연속 첨가하여 블록 공중합시키는 단계로 이루어진다.That is, the method for producing a block copolymer of the present invention comprises the steps of: (a) living polymerization of a vinyl monomer or a diene monomer using an alkyl lithium as an initiator in a nonpolar solvent and (b) an alkali metal alkoxide and an alkyl lithium. An alkali metal alkoxide having an molar ratio of 10 to 0.5 is mixed with the living polymer prepared in step (a), followed by continuous addition of an epoxide monomer to block copolymerization.
본 발명의 블록 공중합 방법에서 사용되는 에폭사이드 단량체로는 하기 식 (I)로 나타내는 에폭사이드 계통의 단량체들을 들 수 있다.Examples of the epoxide monomer used in the block copolymerization method of the present invention include epoxide monomers represented by the following formula (I).
상기 식에서 R1,R2,R3및 R4는 각각 독립적으로 수소 원자, 저급 알킬 또는 페닐기이다. 특히, 에틸렌옥사이드와 프로필렌옥사이드가 바람직하다.Wherein R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a lower alkyl or a phenyl group. In particular, ethylene oxide and propylene oxide are preferable.
본 발명의 블록 공중합 방법에서 사용되는 공단량체로서는 하기 식(III)로 표시되는 모든 비닐계 단량체 하기 식(IV)로 나타내는 디엔계 단량체들을 들 수 있다.As the comonomer used in the block copolymerization method of the present invention, all vinyl monomers represented by the following formula (III) include diene monomers represented by the following formula (IV).
상기 식에서 R'1및 R'2는 각각 독립적으로 수소 원자, 페닐기 에스테르기, 아크릴레이트기 또는 치환된 페닐기를 나타내고, R'3,R'4,R'6,R'7및 R'8은 수소원자 또는 메틸기를 나타내며, R'5는 수소원자, 메틸기 또는 클로로기를 나타낸다.Wherein R ' 1 and R' 2 each independently represent a hydrogen atom, a phenyl group ester group, an acrylate group or a substituted phenyl group, and R ' 3 , R' 4 , R ' 6 , R' 7 and R ' 8 are A hydrogen atom or a methyl group, R ' 5 represents a hydrogen atom, a methyl group or a chloro group.
상기 비닐계 또는 디엔계 단량체의 중합을 위하여 사용되는 중합법은 리빙중합법인데, 단량체가 중합반응기 내에서 모두 소모된 후 같은 단량체를 주입시키면 다시 분자량이 증가하면서 반응이 계속되어 추가된 단량체가 완전히 반응으로 소모되는 것을 특징으로 한다.The polymerization method used for the polymerization of the vinyl- or diene-based monomer is a living polymerization method. After the monomers are all consumed in the polymerization reactor, when the same monomer is injected, the molecular weight increases again and the reaction is continued. Characterized in that consumed by the reaction.
본 발명의 방법에서는, 먼저 비닐계 또는 디엔계 단량체를 알킬리튬을 개시제로 비극성 용매 중에서 리빙 중합한다. 용매로는 벤젠, 톨루언, 시클로헥산, 헥산 등과 같은 비극성 용매를 사용할 수 있다. 이와같이 생성된 리빙 고분자는 말단에 리튬기가 있는 구조를 가지고 있다. 예를 들면, 폴리스티릴 리튬, 폴리쿠타디에닐 리튬 등이 생성되나, 이 리빙 고분자를 알킬리튬에 대하여 적당한 비율의 알킬리금속알콕사이드와 혼합한 후, 에폭사이드 단량체를 동일 반응깅 첨가하여 블록 공중합시킨다. 특히 알칼리금속의 알콕사이드로는 알칼리금속의 메톡사이드, 프로필옥사이드, n-부톡사이드, sec-부톡사이드, tert-부톡사이드, 아밀옥사이드가 바람직하다 알킬리튬에 대한 알칼리금속 알콕사이드의 몰비는 10~0.5으로 하며, 공중합 온도는 5~70℃의 범위로 한다.In the method of the present invention, first, a vinyl or diene monomer is subjected to living polymerization in a nonpolar solvent with alkyllithium as an initiator. As the solvent, non-polar solvents such as benzene, toluene, cyclohexane, hexane and the like can be used. The living polymer thus produced has a structure with a lithium group at the end. For example, polystyryl lithium, polycutadienyl lithium, and the like are produced, but the living polymer is mixed with alkyllithium alkoxide in an appropriate ratio with respect to alkyllithium, followed by block copolymerization by addition of an epoxide monomer. . Particularly preferred alkoxides of alkali metals are alkali metal methoxide, propyl oxide, n-butoxide, sec-butoxide, tert-butoxide and amyl oxide. The molar ratio of alkali metal alkoxide to alkyllithium is 10 to 0.5. The copolymerization temperature is in the range of 5 to 70 ° C.
종래의 리빙 음이온 중합은 문헌[Rubber chemistry and Technology, 제43권, 22 내지 73페이지]에 기재되어 있으며, 일반적인 블록 공중합체의 합성법은 미합중국 특허 제3,294,768호에 개시되어 있다. 그러나, 본 발명과 같이, 단일 반응기 내에서 비극성용매 중에서, 비닐계 또는 디엔계 단량체와 에폭사이드계의 단량체왕의 블록 공중합체를 합성하는 것은 전혀 알려진 바 없는 새로운 합성 방법이다.Conventional living anion polymerizations are described in Rubber chemistry and Technology, Vol. 43, pages 22-73, and the synthesis of general block copolymers is disclosed in US Pat. No. 3,294,768. However, as in the present invention, synthesizing a block copolymer of a vinyl-based or diene-based monomer and an epoxide-based monomer king in a non-polar solvent in a single reactor is a novel synthesis method that is not known at all.
이하에서, 실시예를 들어 본 발명을 보다 상세히 설명하지만, 본 발명의 범위가 이들 실시예에 의하면 한정되는 것은 아니다.Hereinafter, although an Example is given and this invention is demonstrated in detail, the scope of the present invention is not limited by these Examples.
실시예 1Example 1
벤젠 45ml에 에틸렌옥사이드 40ml를 분별 증류(순도 : 99.9%)하여 단량체앰풀을 만들어 반응기에 부착하고 n-부탈 리튬(1.6mol/시클로헥산) 4.3ml와 칼륨 tert-부톡사이드를 알킬리튬의 몰수에 약 2배로 하여 각각 아르곤 가스하에 반응기에 주입시켰다. 다시 반응기를 진공 펌프를 이용하여 진공화시켰다. 이때 진공도는 10-6mmHg이었으며, 반응기의 외부 온도를 드라이 아이스/이소프로필 알콜 온도 조절조를 이용하여 약 -78℃로 유지시킨 후 반응기 내로 앰풀속에 담겨져 있던 에틸렌옥사이드를 주입한 후, 1시간에 걸쳐서 서서히 승온시켜서 통상의 테프론 코팅된 마그네틱 교반기를 이용하여 교반시키면서 상온 하에서 3일간 반응시켰다.45 ml of benzene and 40 ml of ethylene oxide were fractionally distilled (purity: 99.9%) to form a monomer ampoule, and attached to the reactor. 4.3 ml of n-buttal lithium (1.6 mol / cyclohexane) and potassium tert-butoxide were added to the number of moles of alkyllithium. Doubled and injected into the reactor under argon gas, respectively. The reactor was again evacuated using a vacuum pump. At this time, the degree of vacuum was 10 -6 mmHg, the outside temperature of the reactor was maintained at about -78 ℃ using a dry ice / isopropyl alcohol temperature control tank, and the ethylene oxide contained in the ampoule was injected into the reactor 1 hour, The temperature was gradually raised over the reaction and allowed to react for 3 days at room temperature while stirring using a conventional Teflon-coated magnetic stirrer.
본 실시예로부터 얻어지는 순수 폴리에틸렌옥사이드의 중합도는 110이며, 분자량은 5,000이고, 분자량 분포는 겔투와 크로마토그래피(GPC) 기계에 표본 샘플로 폴리스티렌을 사용하여 측정하여 약 2.0정도이다. 또한, 본 실시예로부터 얻어지는 고분자는 일반적으로 알콜, 몰, THF에 용해되며, 헥산, 펜탄에 침전 · 분리시켜 별도의 정제 단계 없이 여러 용도로 이용할 수 있다.The degree of polymerization of the pure polyethylene oxide obtained from this example was 110, the molecular weight was 5,000, and the molecular weight distribution was about 2.0 measured using polystyrene as a sample sample on a gel-to-chromatography (GPC) machine. In addition, the polymer obtained in this embodiment is generally dissolved in alcohol, mole, THF, and precipitated and separated in hexane and pentane and can be used for various purposes without a separate purification step.
실시예 2Example 2
실시예 1에 기재된 칼륨 알콕사이드 대신에 나트륨 알콕사이드를 테트라히드로푸란 중에 알킬리튬의 몰 수와 동일하게 측정하여 용해시켜서 앰플을 만들고 이를 반응기에 부착한 후, 다시 실시예 1의 에틸렌옥사이드 동일량을 앰풀로 만들어 반응기에 부착한 후 실시예1과 동일한 조건으로 알킬리튬과 나트륨 알콕사이드를 반응기에 주입한 후, 에틸렌옥사이드 단량체를 주입하고 승온시켜서 3일간 반응시켰다. 이와같이 하여 제조된 고분자의 분자량은 1,000이며, 실시예 1과 동일한 방법으로 침전·분리 사용한다.Instead of the potassium alkoxide described in Example 1, sodium alkoxide was measured and dissolved in tetrahydrofuran in the same amount as the molar number of alkyllithium to make an ampoule, which was attached to the reactor, and then the same amount of ethylene oxide as in Example 1 was again converted into ampoules. After making and attaching to the reactor, alkyllithium and sodium alkoxide were injected into the reactor under the same conditions as in Example 1, and then ethylene oxide monomer was injected and heated to react for 3 days. The molecular weight of the polymer thus prepared is 1,000, and precipitation and separation are carried out in the same manner as in Example 1.
실시예 3Example 3
실시예 1에 기재된 것과 개시제의 양을 동일하게 하고, 단량체의 양을 2배로 하여 실시예 1과 동일한 반응 조건하에서 중합을 실시하였다. 제조된 고분자의 분자량은 10,000이었으며, 분자량 분포는 2.0이었다.The polymerization was carried out under the same reaction conditions as in Example 1 with the same amounts of the initiators as those described in Example 1 and twice the amount of the monomers. The prepared polymer had a molecular weight of 10,000 and a molecular weight distribution of 2.0.
실시예 4Example 4
실시예 1에서 중합된 일정량의 중합 용액을 분리해 낸 후, 다시 실시예 1에서와 동일한 방법으로 에틸렌옥사이드 단량체를 첨가시키는 연속 단량체 부가 방법으로 리빙 중합성을 시험하였다. 단량체 20ml와 실시예 1의 용액중 절반을 취하였다. 이때 중합 용액중의 쇄 말단의 농도는 초기 농도의 절반으로 계산되며, 실시예 1과동일한 방법으로 중합하였다. 제조된 고분자의 분자량은 10,000이며, 분자량 분포는 1.0이었다.After separating a certain amount of the polymerization solution polymerized in Example 1, living polymerizability was tested by a continuous monomer addition method in which an ethylene oxide monomer was added in the same manner as in Example 1. 20 ml of monomer and half of the solution of Example 1 were taken. At this time, the concentration of the chain terminal in the polymerization solution was calculated as half of the initial concentration, and was polymerized in the same manner as in Example 1. The molecular weight of the produced polymer was 10,000, the molecular weight distribution was 1.0.
실시예 5Example 5
정제된 스티렌(순도 : 99.9%, 수분함량 : 0.001% 이하)을 사용하여 진공 또는 불활성 기체 하에서 용매로는 벤젠을 사용하여 리빙 폴리스티렌을 합성하였다. 이와 같이 합성된 리빙 폴리스티렌(폴리습릴리튬)을 실시예 1의 저분자 알킬리튬 대신에 개시제로 사용하여 실시예 3과 동일한 방법으로 에틸렌옥사이드 단량체를 반응기에 주입한 후 통상의 단량체 부가법에 의한 블록 공중합체 합성 방법과 동일한 방식으로 공중합하였다.Living polystyrene was synthesized using purified styrene (purity: 99.9%, moisture content: 0.001% or less) under vacuum or inert gas using benzene as a solvent. Thus prepared living polystyrene (polyhydrylithium) was used as an initiator instead of the low molecular weight alkyllithium of Example 1, and the ethylene oxide monomer was injected into the reactor in the same manner as in Example 3, and then the block air was prepared by a conventional monomer addition method. Copolymerization was carried out in the same manner as the synthesis method.
제조된 폴리스티렌의 분자량이 10,000이 되도록 적당량의 중합 용액을 취하였다. 리빙 중합이므로 쇄말단의 활성도가 살아 있어 칼륨 tert-부톡사이드와의 몰비가 1이 되도록 하여 다시 반응기에 투입하고, 에틸렌옥사이드 단량체를 분자량이 10,000이 되게 투입하였다. 실시에 1과 동일한 방법으로 중합하였다. 제조된 블록 공중합체의 전체 분자량은 20,000이었으며, 분자량 분포는 1.5이었고, 헥산 또는 페탄 중에 침전시켜 고분자를 분리하였다.An appropriate amount of polymerization solution was taken so that the molecular weight of the produced polystyrene was 10,000. Because of the living polymerization, the activity at the end of the chain was alive, so that the molar ratio with potassium tert-butoxide was 1, and the reactor was added again, and the ethylene oxide monomer was added at a molecular weight of 10,000. The polymerization was carried out in the same manner as in Example 1. The total molecular weight of the prepared block copolymer was 20,000, the molecular weight distribution was 1.5, and precipitated in hexane or petane to separate the polymer.
실시예 6Example 6
실시예 5에서와 같이 리빙 폴리부타디엔(폴리부타디에닐 리튬)을 합성한 후 다시 실시예 1의 n-부틸리튬 대신 폴리부타디에닐 리튬(1.6mol)을 칼륨 tert-부록사이드와 혼합하고 에틸렌옥사이드 단량체를 반응기에 중입한 후 승온시켜 50℃에서 교반하면서 3일간 공중합시켰다. 제조된 블록 공중합체의 전체 분자량은 20,000이었으며, 분자량 분포는 1.9이었고, 페탄 중에 침전시켜 고분자를 분리하였다.After synthesizing living polybutadiene (polybutadienyl lithium) as in Example 5, again mixed polybutadienyl lithium (1.6 mol) with potassium tert-boxide instead of n-butyllithium of Example 1 and ethylene oxide The monomer was added to the reactor, and then heated to copolymerize for 3 days with stirring at 50 ° C. The total molecular weight of the prepared block copolymer was 20,000, the molecular weight distribution was 1.9, and the polymer was isolated by precipitating in petane.
실시예 7Example 7
실시예 5에서와 같이 분자량 10,000인 리빙 폴리스티렌(폴리스티릴 리튬) 6.88×10-3mol과 칼륨 tert-부톡사이드 0.014mol을 혼합한 후 페닐 에폭사이드(100mol)을 주입하여 공중합시켰다. 제조된 블록 공중합체의 전체 분자량은 20,000이었으며, 분자량 분포는 2.2이었고, 헥산 중에 침전시켜 고분자를 분리하였다.As in Example 5, 6.88 × 10 −3 mol of living polystyrene (polystyryl lithium) having a molecular weight of 10,000 and 0.014 mol of potassium tert-butoxide were mixed and then copolymerized by injecting phenyl epoxide (100 mol). The total molecular weight of the prepared block copolymer was 20,000, the molecular weight distribution was 2.2, and precipitated in hexane to separate the polymer.
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| US8420771B2 (en) | 2008-02-26 | 2013-04-16 | Jung-Ahn Kim | PH-sensitive polyethylene oxide co-polymer and synthetic method thereof |
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