KR20010073092A - Method for Producing Copolymers by Radical Polymerisation - Google Patents
Method for Producing Copolymers by Radical Polymerisation Download PDFInfo
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- C08F226/02—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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Abstract
본 발명은 a) 하기 화학식 I의 단량체 5 내지 95 중량%, b) 하기 화학식 II의 단량체 95 내지 5 중량%, 및 c) 다른 완전 또는 부분 수용성 단량체 0 내지 40 중량%를 라디칼 중합시키는 것을 포함하는, 공중합체의 제조 방법에 관한 것이다.The present invention comprises a) radically polymerizing 5 to 95% by weight of monomers of Formula I, b) 95 to 5% by weight of monomers of Formula II, and c) 0 to 40% by weight of other fully or partially water soluble monomers. And a method for producing a copolymer.
<화학식 I><Formula I>
<화학식 II><Formula II>
상기 각 식에서, R1및 R2는 H 또는 C1-C3-알킬을 나타내고, R3은 H 또는 C1-C6-알킬을 나타내며, n은 1 내지 3이다. 본 발명의 방법은 상기 중합 반응을 수성 매질 중에서 수행하는 것을 특징으로 한다.In each of the above formulas, R 1 and R 2 represent H or C 1 -C 3 -alkyl, R 3 represents H or C 1 -C 6 -alkyl, and n is 1 to 3. The process of the invention is characterized in that the polymerization reaction is carried out in an aqueous medium.
Description
국제 특허 공개 제WO 96/41785호에서는 수화물 형성을 억제하는 방법, 즉, 기체 분자와 물을 함유하는 매질 중에서 기체 수화물의 형성을 억제하는 방법을 개시하였다.WO 96/41785 discloses a method for inhibiting hydrate formation, ie, a method for inhibiting gas hydrate formation in a medium containing gas molecules and water.
이러한 공지 방법에서 사용되는 기체 수화물 억제제는 N-메틸-N-비닐아세트아미드와 N-비닐락탐으로 이루어진 공중합체이다. 이 공중합체는 벤젠 또는 알코올 중에서 유리 라디칼 중합시켜 제조한다. 그러나, 이들 유기 용매는 생성된 공중합체 용액의 제조와 취급에 있어서 문제가 있다. 이들은 몇몇 경우에 기체 수화물 억제제로서 사용하기 전에 제거해야 하며, 여기에는 에너지와 시간이 요구된다.The gas hydrate inhibitor used in this known method is a copolymer consisting of N-methyl-N-vinylacetamide and N-vinyllactam. This copolymer is prepared by free radical polymerization in benzene or alcohol. However, these organic solvents have problems in the preparation and handling of the resulting copolymer solution. They must in some cases be removed before use as a gas hydrate inhibitor, which requires energy and time.
문헌[Polymer Journal, 17, No.1 (1985), 143-152]에서는 유기 용매 또는 H2O 중에서 유리 라디칼 중합시켜 비닐피롤리돈을 제조할 수 있으며, H2O 중에서 제조된 중합체는 산화 반응에 민감하다는 것을 개시하였다.In Polymer Journal, 17, No. 1 (1985), 143-152, vinylpyrrolidone can be prepared by free radical polymerization in an organic solvent or in H 2 O, wherein the polymer prepared in H 2 O It is disclosed that it is sensitive to.
본 발명은The present invention
a) 하기 화학식 I의 단량체 5 내지 95 중량%,a) 5 to 95% by weight of the monomer of formula (I)
b) 하기 화학식 II의 단량체 95 내지 5 중량%, 및b) 95 to 5% by weight of monomer of formula II, and
c) 완전 수용성이거나 제한된 수용해도를 갖는 추가의 단량체 0 내지 40 중량%를 수성 매질 중에서 유리 라디칼 중합시키는 것을 포함하는 공중합체의 제조 방법, 이러한 방법으로 제조한 공중합체 및 기체 수화물 억제제로서의 이들의 용도에 관한 것이다.c) a process for the preparation of a copolymer comprising free radical polymerization of 0 to 40% by weight of an additional monomer having completely water soluble or limited water solubility in an aqueous medium, copolymers prepared in this way and their use as gas hydrate inhibitors It is about.
상기 각 식에서, R1및 R2는 H 또는 C1-C3-알킬이고, R3은 H 또는 C1-C6-알킬이며, n은 1 내지 3이다.In each of the above formula, R 1 and R 2 are H or C 1 -C 3 -alkyl, R 3 is H or C 1 -C 6 -alkyl, and n is 1 to 3.
본 발명의 목적은 취급하는 동안 상기 언급한 단점들을 피하는 것이다.It is an object of the present invention to avoid the above mentioned disadvantages during handling.
본 발명자들은 상기 목적이 중합 반응을 수성 매질 중에서 수행함으로써 성취된다는 것을 발견하기에 이르렀다.The inventors have found that this object is achieved by carrying out the polymerization reaction in an aqueous medium.
화학식 I의 단량체는 바람직하게는 20 내지 80 중량%의 양으로 사용하고, 화학식 II의 단량체는 바람직하게는 80 내지 20 중량%의 양으로 사용한다. 화학식 I에서, R2및 R3은 바람직하게는 각각 메틸이고, 단량체 I 및 II 모두에서 R1은 수소이다. 화학식 I의 바람직한 단량체는 N-메틸-N-비닐아세트아미드이고, 화학식 II의 바람직한 단량체는 비닐카프로락탐이다.The monomer of formula (I) is preferably used in an amount of 20 to 80% by weight, and the monomer of formula (II) is preferably used in an amount of 80 to 20% by weight. In formula (I), R 2 and R 3 are each preferably methyl, and in both monomers I and II, R 1 is hydrogen. Preferred monomers of formula (I) are N-methyl-N-vinylacetamide and preferred monomers of formula (II) are vinylcaprolactam.
완전 수용성이거나 제한된 수용해도를 갖는 공단량체를 추가의 공중합성 공단량체 c)로서 사용할 수 있다.Comonomers that are either completely water soluble or have limited water solubility can be used as further copolymerizable comonomer c).
바람직하게는 사용되는 공단량체 c)로는 예를 들어 카르복실산과 그의 에스테르, 무수물, 아미드, 니트릴, 비닐 에스테르 또는 비닐 에테르가 있다. 구체적인 예로는 아크릴산, 메타크릴산, 메틸 아크릴레이트, 에틸 아크릴레이트, 메틸 메타크릴레이트, 에틸 메타크릴레이트, 히드록시에틸 아크릴레이트, 히드록시프로필 아크릴레이트, 히드록시부틸 아크릴레이트, 히드록시에틸 메타크릴레이트, 히드록시프로필 메타크릴레이트, 히드록시이소부틸 아크릴레이트, 히드록시이소부틸 메타크릴레이트, 모노메틸 말레에이트, 디메틸 말레에이트, 모노에틸렌 말레에이트, 디에틸 말레에이트, 모노에틸 말레에이트, 디에틸렌 말레에이트, 말레이미드, 에틸헥실 아크릴레이트, 2-에틸헥실 메타크릴레이트, 아크릴아미드, 메타크릴아미드, N-디메틸아크릴아미드, N-3급-부틸아크릴아미드: N-이소프로필메타크릴아미드, 메타크릴로일피롤리딘, 아크릴로니트릴, 메타크릴로니트릴, 디메틸아미노에틸 아크릴레이트, 디메틸아미노에틸 메타크릴레이트, 디에틸아미노에틸 아크릴레이트, 디에틸아미노에틸 메타크릴레이트, 및 마지막에 언급한 단량체들과 카르복실산 또는 광산과의 염 및 4급화 생성물이 있다. 비닐 에스테르의 예로는 비닐 아세테이트, 비닐 프로피오네이트, 및 탄소 원자 10 (versatic-10 acid) 또는 탄소 원자 9 (versatic-9 acid)의 합성 지방산의 비닐 에스테르가 있다 (둘 모두 예를 들어 쉘(Shell)로부터 입수가능함). 비닐 에테르의 예로는 비닐 C1-C4-알킬 에테르, 특히 비닐 이소부틸 에테르가 있다. 또한, 아크릴아미도글리콜산, 비닐술폰산, 알릴술폰산, 메트알릴술폰산, 스티렌술폰산, 3-술포프로필 아크릴레이트, 3-술포프로필 메타크릴레이트 및 아크릴아미도메틸프로판술폰산, 및 포스폰산기 함유 단량체, 예를 들어, 비닐 포스페이트, 알릴 포스페이트 및 아크릴아미도메틸프로판포스폰산이 단량체로서 적합하다. 물론 상기 단량체들의 혼합물, 예를 들어, 아크릴레이트와 비닐 아세테이트의 혼합물, 상이한 아크릴레이트들의 혼합물, 아크릴레이트와 아크릴아미드의 혼합물, 또는 아크릴아미드와 히드록시에틸 아크릴레이트의 혼합물을 사용하는 것도 또한 가능하다.Preferably comonomer c) used is, for example, carboxylic acids and their esters, anhydrides, amides, nitriles, vinyl esters or vinyl ethers. Specific examples include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate Latex, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, monomethyl maleate, dimethyl maleate, monoethylene maleate, diethyl maleate, monoethyl maleate, diethylene Maleate, maleimide, ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide: N-isopropylmethacrylamide, meta Cryloylpyrrolidine, acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate Agent, a dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the last-mentioned monomer and a carboxylic acid or a salt with a mining and quaternized product. Examples of vinyl esters are vinyl acetate, vinyl propionate, and vinyl esters of synthetic fatty acids having 10 carbon atoms (versatic-10 acid) or 9 carbon atoms (versatic-9 acid) (both shells, for example, Available from). Examples of vinyl ethers are vinyl C 1 -C 4 -alkyl ethers, in particular vinyl isobutyl ether. Furthermore, acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, metallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and acrylamidomethylpropanesulfonic acid, and phosphonic acid group-containing monomers, For example, vinyl phosphate, allyl phosphate and acrylamidomethylpropanephosphonic acid are suitable as monomers. It is of course also possible to use mixtures of the above monomers, for example mixtures of acrylates and vinyl acetate, mixtures of different acrylates, mixtures of acrylates and acrylamides, or mixtures of acrylamides and hydroxyethyl acrylates. .
아크릴아미드 및 아크릴레이트가 특히 바람직하다.Acrylamide and acrylate are particularly preferred.
수성 매질은 독점적으로 H2O로 이루어질 수 있거나, H2O와 알코올, 특히 CH3OH 또는 C2H5OH와의 혼합물일 수 있다.The aqueous medium can consist exclusively of H 2 O or can be a mixture of H 2 O with an alcohol, in particular CH 3 OH or C 2 H 5 OH.
개시 반응은 수용성 개시제를 단량체를 기준으로 0.1 내지 5 중량%, 특히 바람직하게는 0.2 내지 2 중량%의 양으로 사용하여 수행한다.The initiation reaction is carried out using the water-soluble initiator in an amount of 0.1 to 5% by weight, particularly preferably 0.2 to 2% by weight, based on the monomers.
수용성 개시제로서 단량체와 물을 포함한 반응 혼합물에 미량의 Cu(II)염을 동시에 투입하면서 과산화수소가 특히 바람직하다.Hydrogen peroxide is particularly preferred while simultaneously introducing a small amount of Cu (II) salt into the reaction mixture containing the monomer and water as the water-soluble initiator.
중합 반응 동안 pH는 4 내지 9, 특히 바람직하게는 6 내지 8이다. (전체) 중합 반응 동안 pH는 수성 산과 알칼리를 첨가하여 조절한다. 일반적으로, 알칼리를 첨가하는 것이 충분하며, 예를 들어 10% 농도의 암모니아 수용액이 특히 바람직하게 사용된다.The pH during the polymerization reaction is 4 to 9, particularly preferably 6 to 8. During the (overall) polymerization reaction the pH is adjusted by addition of aqueous acid and alkali. In general, it is sufficient to add an alkali, for example an aqueous ammonia solution of 10% concentration is particularly preferably used.
본 발명에 따라 제조한 중합체의 K값 (문헌[Fikentscher, Cellulose Chemie, 13 (1932), 58-64 및 71-74; 1% 농도 수용액, 20℃, K=k·103]에 따라 측정함)은 10 내지 100, 바람직하게는 15 내지 45이다. 중합체의 분자량 (Mw)은 2000 내지 800,000, 바람직하게는 5000 내지 100,000이다.K value of polymers prepared according to the invention (Fikentscher, Cellulose Chemie, 13 (1932), 58-64 and 71-74; measured in 1% aqueous solution, 20 ° C., K = k · 10 3 ) ) Is 10 to 100, preferably 15 to 45. The molecular weight (Mw) of the polymer is 2000 to 800,000, preferably 5000 to 100,000.
신규 공중합체는 국제 특허 공개 제WO 96/41785호에 기재된 바와 같이 기체 수화물 억제제로서 사용할 수 있다. 이러한 목적을 위해, 중합체들을 액체계, 예를 들어 광유 또는 천연 가스 혼합물에 당업계의 숙련인이 개별 조건에 적합화시킨 일반적인 양으로 첨가할 수 있다.The novel copolymers can be used as gas hydrate inhibitors as described in WO 96/41785. For this purpose, the polymers can be added to liquid systems, for example mineral oils or natural gas mixtures, in general amounts adapted to the individual conditions by one skilled in the art.
본 발명에 따라 사용된 중합체는 기체 수화물 억제의 목적으로 다른 조성물과 함께 사용할 수 있다. 이들 다른 조성물로는 전체 액체계의 중량을 기준으로 바람직하게는 1 내지 3.5 중량%의 양으로 사용한 히드록시알킬셀룰로스, 폴리비닐피롤리돈 또는 폴리비닐카프로락탐과 같은 다른 중합체, 또한 바람직하게는 전체 액체계의 중량을 기준으로 10 내지 30 중량%의 양으로 사용한 메탄올, 에탄올 또는 에틸렌 글리콜과 같은 알코올 또는 수용성 염일 수 있다.The polymers used according to the invention can be used with other compositions for the purpose of gas hydrate inhibition. These other compositions include other polymers, such as hydroxyalkylcellulose, polyvinylpyrrolidone or polyvinylcaprolactam, preferably all of which are preferably used in amounts of 1 to 3.5% by weight based on the weight of the total liquid system. Alcohol or water soluble salts such as methanol, ethanol or ethylene glycol, used in amounts of 10 to 30% by weight based on the weight of the liquid system.
제조예Production Example
처음 취한 혼합물: 탈염수 1125.00 gFirst taken mixture: 1125.00 g demineralized water
비닐카프로락탐 300.00 g300.00 g of vinyl caprolactam
N-비닐메틸아세트아미드 200.00 g200.00 g of N-vinylmethylacetamide
공급물 1: 과산화수소 (30% 농도) 8.30 gFeed 1: hydrogen peroxide (30% concentration) 8.30 g
공급물 2: 염화구리(II) (0.01% 농도) 0.50 gFeed 2: copper (II) chloride (0.01% concentration) 0.50 g
공급물 3: 암모니아수 (5% 농도) xx gFeed 3: aqueous ammonia (5% concentration) xx g
공급물 4: 염화구리(II) (0.1% 농도) 0.50 gFeed 4: copper (II) chloride (0.1% concentration) 0.50 g
공급물 5: 과산화수소 (30% 농도) 5.00 gFeed 5: hydrogen peroxide (30% concentration) 5.00 g
절차step
처음 취한 혼합물을 질소로 플러싱하고 약 80℃의 내부 온도로 가열하였다.The first taken mixture was flushed with nitrogen and heated to an internal temperature of about 80 ° C.
약 78℃의 내부 온도에서 공급물 1을 첨가한 후 공급물 2를 첨가하였다.Feed 2 was added after addition of feed 1 at an internal temperature of about 78 ° C.
공급물 3에 있어서, 전체 중합 시간 동안 pH를 7.0으로 유지시켰다.For feed 3, the pH was maintained at 7.0 for the entire polymerization time.
3.5시간의 중합시간 후, 공급물 4와 공급물 5를 첨가하였다.After 3.5 hours of polymerization, feed 4 and feed 5 were added.
공급물 4와 공급물 5를 첨가한 후, 약 80℃의 내부 온도에서 추가로 4시간 동안 계속 중합시켰다.After addition of Feed 4 and Feed 5, the polymerization was continued for an additional 4 hours at an internal temperature of about 80 ° C.
이어서, 실험실 배치를 실온으로 냉각시켰다.The laboratory batch was then cooled to room temperature.
특성화Specialization
고체 함량: 30 중량%Solids content: 30% by weight
K값: 34 (물 중 1% 농도)K value: 34 (1% concentration in water)
pH값: 6.pH value: 6.
"동결점"은 국제 특허 공개 제WO 95/32356호의 실시예 1에 기재된 시험 방법과 유사한 볼-스탑 (ball-stop)법으로 측정하였다.The "freeze point" was determined by a ball-stop method similar to the test method described in Example 1 of WO 95/32356.
이 방법은 각종 중합체를 첨가함으로써 물/THF 혼합물에 대해 시험한 동결점에 관한 것이며 (수화물 형성의 검출), 물/THF (81/19 중량%) 혼합물 중의 0.5% 농도에서 동결시킨다.This method relates to the freezing point tested on the water / THF mixture by the addition of various polymers (detection of hydrate formation) and frozen at a 0.5% concentration in the water / THF (81/19 wt%) mixture.
각종 중합체/(물/THF) 혼합물의 동결점을 측정하기 위해 다음 장치와 시약이 요구된다:To determine the freezing point of various polymer / (water / THF) mixtures the following equipment and reagents are required:
- 물/THF 혼합물 (81/19 중량%)Water / THF mixture (81/19 wt%)
- 물/에틸렌 글리콜 (5:1) 냉각제 혼합물을 갖는 Julabo F18 써모스타트 조Julabo F18 thermostat bath with water / ethylene glycol (5: 1) coolant mixture
- 멀티픽스 콘스탄트(Multifix Constant) 교반기Multifix Constant Stirrers
- 시험관 (5 ㎖) 홀더-Test tube (5 ml) holder
- 시험관 내에서 잘 혼합시키기 위한 작은 스테인레스강 볼Small stainless steel balls for good mixing in test tubes
물/THF (81/19) 중의 연구하고자 하는 중합체의 0.5% 농도 용액을 제조하였다. 시험관을 2/3 채우고, 작은 스테인레스강 볼을 공급하고, 밀폐하여 시험관 홀더에 고정시켰다. 4℃의 조 온도 및 20 rpm의 속도에서 측정을 시작하였고, 샘플이 동결되거나, 또는 시험관 내의 스테인레스강 볼이 더이상 움직이지 않거나, 또는 0℃의 온도에 도달할 때까지 온도를 0.5℃/시로 하강시켰다. 각 측정과 동시에 블랭크 시험을 실시하였다.A 0.5% concentration solution of the polymer to be studied in water / THF (81/19) was prepared. The test tube was filled with two thirds, a small stainless steel ball was fed, sealed and held in the test tube holder. The measurement was started at a bath temperature of 4 ° C. and a speed of 20 rpm and the temperature was lowered to 0.5 ° C./hour until the sample was frozen or the stainless steel balls in the test tube were no longer moving or reached a temperature of 0 ° C. I was. The blank test was performed simultaneously with each measurement.
Claims (11)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19840268.6 | 1998-09-03 | ||
| DE19840268A DE19840268A1 (en) | 1998-09-03 | 1998-09-03 | Process for the preparation of copolymers by radical polymerization |
| PCT/EP1999/006224 WO2000014132A1 (en) | 1998-09-03 | 1999-08-25 | Method for producing copolymers by radical polymerisation |
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| Publication Number | Publication Date |
|---|---|
| KR20010073092A true KR20010073092A (en) | 2001-07-31 |
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| KR1020017002734A KR20010073092A (en) | 1998-09-03 | 1999-08-25 | Method for Producing Copolymers by Radical Polymerisation |
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| Country | Link |
|---|---|
| EP (1) | EP1117712A1 (en) |
| JP (1) | JP2003524670A (en) |
| KR (1) | KR20010073092A (en) |
| AU (1) | AU5740499A (en) |
| CA (1) | CA2342323A1 (en) |
| DE (1) | DE19840268A1 (en) |
| HU (1) | HUP0103892A2 (en) |
| NO (1) | NO20011097L (en) |
| WO (1) | WO2000014132A1 (en) |
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| DE10160720A1 (en) | 2001-12-11 | 2003-06-18 | Basf Ag | New water-soluble or -dispersible copolymer, useful in cosmetic products e.g. skin cleansers, prepared by polymerization of an N-vinyl lactam and a comonomer, and polymerization of an anionic monomer in the presence of the product |
| EP1874439A4 (en) * | 2005-04-07 | 2012-09-19 | Exxonmobil Upstream Res Co | Recovery of kinetic hydrate inhibitor |
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| US4951921A (en) * | 1983-01-28 | 1990-08-28 | Phillips Petroleum Company | Polymers useful in the recovery and processing of natural resources |
| US5874660A (en) * | 1995-10-04 | 1999-02-23 | Exxon Production Research Company | Method for inhibiting hydrate formation |
| GB2301825A (en) * | 1996-03-28 | 1996-12-18 | Exxon Production Research Co | A polymer for inhibiting hydrate formation |
| US6426383B1 (en) * | 1997-05-28 | 2002-07-30 | Nalco Chemical Company | Preparation of water soluble polymer dispersions from vinylamide monomers |
-
1998
- 1998-09-03 DE DE19840268A patent/DE19840268A1/en not_active Withdrawn
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1999
- 1999-08-25 KR KR1020017002734A patent/KR20010073092A/en not_active Application Discontinuation
- 1999-08-25 WO PCT/EP1999/006224 patent/WO2000014132A1/en not_active Application Discontinuation
- 1999-08-25 CA CA002342323A patent/CA2342323A1/en not_active Abandoned
- 1999-08-25 HU HU0103892A patent/HUP0103892A2/en unknown
- 1999-08-25 JP JP2000568887A patent/JP2003524670A/en not_active Withdrawn
- 1999-08-25 EP EP99944508A patent/EP1117712A1/en not_active Withdrawn
- 1999-08-25 AU AU57404/99A patent/AU5740499A/en not_active Abandoned
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| AU5740499A (en) | 2000-03-27 |
| CA2342323A1 (en) | 2000-03-16 |
| JP2003524670A (en) | 2003-08-19 |
| NO20011097D0 (en) | 2001-03-02 |
| HUP0103892A2 (en) | 2002-01-28 |
| NO20011097L (en) | 2001-03-05 |
| DE19840268A1 (en) | 2000-03-09 |
| WO2000014132A1 (en) | 2000-03-16 |
| EP1117712A1 (en) | 2001-07-25 |
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