WO2000014132A1 - Verfahren zur herstellung von copolymerisaten durch radikalische polymerisation - Google Patents
Verfahren zur herstellung von copolymerisaten durch radikalische polymerisation Download PDFInfo
- Publication number
- WO2000014132A1 WO2000014132A1 PCT/EP1999/006224 EP9906224W WO0014132A1 WO 2000014132 A1 WO2000014132 A1 WO 2000014132A1 EP 9906224 W EP9906224 W EP 9906224W WO 0014132 A1 WO0014132 A1 WO 0014132A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- copolymers
- water
- formula
- acid
- Prior art date
Links
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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 heterocyclic ring containing nitrogen
-
- 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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- 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
Definitions
- the invention relates to a process for the preparation of copolymers by radical polymerization of
- a method for inhibiting hydra formation is known from WO 96/41785, ie methods which prevent the formation of gas hydrates in media which contain gas molecules and water.
- copolymers consisting of N-methyl-N-vinylacetamide and an N-vinyllactam are used as gas hydrate inhibitors.
- the copolymers are produced by radical polymerization in benzene or in alcohols.
- these organic solvents are problematic in the preparation and handling of the resulting copolymer solution. In certain cases, they have to be removed before use as gas hydrate inhibitors, which requires energy and time.
- vinylpyrrolidone can be prepared by radical polymerization in organic solvents or in H0, the polymers prepared in H0 being oxidatively sensitive.
- the object of the present invention was to avoid the above-mentioned disadvantages in handling.
- This object has been achieved in that the polymerization is carried out in an aqueous medium.
- the monomers of the formula I are preferably used in amounts of 20 to 80% by weight, the monomers of the formula II preferably in amounts of 80 to 20% by weight.
- IR 2 and R 3 preferably denotes methyl and R 1 in both monomers I and II denotes hydrogen.
- the preferred monomer of formula I is N-methyl-N-vinyl acetamide, the preferred monomer of formula II is vinyl caprolactam.
- a completely or to a limited extent water-soluble comonomer can be used as further copolymerizable comonomers c).
- Preferred comonomers c) are, for example, carboxylic acids and their esters, anhydrides, amides, nitriles, vinyl esters or vinyl ethers. Particular mention are: acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methacrylic klaremethylester, acrylate methacrylate hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, Hydroxyethylmeth-, hydroxypropyl methacrylate, Hydroxyisobutylacrylat, Hydroxyisobutylmethacrylat, maleic acid monomethyl ester, maleic acid dimethyl ester, Maleinklaremonoethylenester, Maleinklaredi- ethyl ester, maleic acid monoethyl ester , Maleic acid diethylene ester, maleimide, ethylhexyl acrylate, 2-ethylhexyl methacrylate,
- Vinyl esters to be mentioned are vinyl acetate, vinyl propionate and vinyl esters of a synthetic fatty acid with 10 C atoms ("Versatic 10 acid”) or with 9 C atoms ("Versatic 9 acid”), both of which are commercially available (for example from Shell ).
- Vinyl C 1 -C 4 alkyl ethers, in particular vinyl isobutyl ether, may be mentioned as vinyl ethers.
- Suitable as monomers are acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methylsulfonic acid, styrenesulfonic acid, acrylic acid (3-sulfopropyl) ester, methacrylic acid (3-sulfopropyl) ester and acrylamidomethylpropanesulfonic acid, and monomers containing phosphonic acid groups, such as vinyl phosphate, allylphosphonic acid and acrylamide phosphate panate.
- mixtures of the monomers mentioned for example mixtures of acrylic esters and vinyl acetate, mixtures of different acrylic esters, mixtures of acrylic esters and acrylamide or mixtures of acrylamide and hydroxyethyl acrylate.
- the aqueous medium can consist exclusively of H 2 0 or a mixture of H 2 0 and alcohol, in particular CH 3 OH or C 2 H 5 OH.
- the initiation takes place with water-soluble initiators in
- Hydrogen peroxide with a simultaneous introduction of traces of Cu (II) salts into the reaction mixture of monomer and water are particularly preferred as the water-soluble initiator.
- the pH during the polymerization is between 4 and 9, particularly preferably between 6 and 8.
- the pH during (total) polymerization is controlled by adding aqueous acids and alkalis.
- aqueous acids and alkalis are added to the polymerization.
- an alkali is sufficient, particularly preferably an aqueous ammonia solution, e.g. 10%, is used.
- the K values of the polymers produced according to the invention are 10 to 100, preferably 15 to 45.
- the molecular weights of the polymers (M w ) are 2000 to 800000, preferably 5000 to 100000.
- the copolymers according to the invention can be used as gas hydrate inhibitors, as described in WO 96/41785.
- the polymers of the liquid systems for example. added to the petroleum or natural gas mixtures in the usual amounts, which the person skilled in the art adapts to the respective circumstances.
- the polymers used according to the invention can be used together with other agents for the purpose of gas hydrate inhibition.
- These other agents can be other polymers such as hydroxyalkyl celluloses, polyvinylpyrrolidone or polyvinylcaprolactam, preferably in an amount of 1 to 3.5% by weight, based on the weight of the entire liquid system, but also alcohols, such as methanol, ethanol or Ethylene glycol or water-soluble salts, preferably in an amount of 10 to 30 wt .-%, based on the weight of the entire liquid system.
- Feed 2 0.50 g copper (II) chloride (0.01%)
- Feed 4 0.50 g of copper (II) chloride (0.1%)
- Feed 5 5.00 g of hydrogen peroxide (30%)
- the template is flushed with nitrogen and heated to an internal temperature of approx. 80 ° C. At an internal temperature of approx. 78 ° C, feed 1 is added, then feed 2.
- VIMA N-methyl-N-vinyl acetamide
- VCap vinyl caprolactam
- the “freezing temperature” was measured by the "ball stop method” analogous to the test method described in Example 1 of WO95 / 32356.
- This method relates to the freezing points of water / THF mixtures to be tested by adding various polymers (detection of hydrate formation), which are frozen to a 0.5% strength in a water / THF (81/19% by weight) mixture.
- a 0.5% solution of the polymer to be examined in water / THF (81/19) is prepared.
- the test tube is filled 2/3 full, provided with a stainless steel bead, closed and fastened in the test tube holder.
- the measurement is started at a bath temperature of 4 ° C and a rotation speed of 20 rpm and the temperature is lowered by 0.5 ° C every hour until the sample is frozen or the steel ball in the test tube no longer moves or the temperature of 0 ° C is reached .
- a blank test runs parallel to each measurement.
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
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99944508A EP1117712A1 (de) | 1998-09-03 | 1999-08-25 | Verfahren zur herstellung von copolymerisaten durch radikalische polymerisation |
HU0103892A HUP0103892A2 (hu) | 1998-09-03 | 1999-08-25 | Eljárás kopolimerizátumok előállítására gyökös polimerizációval |
AU57404/99A AU5740499A (en) | 1998-09-03 | 1999-08-25 | Method for producing copolymers by radical polymerisation |
JP2000568887A JP2003524670A (ja) | 1998-09-03 | 1999-08-25 | ラジカル重合によるコポリマーの製造 |
CA002342323A CA2342323A1 (en) | 1998-09-03 | 1999-08-25 | Method for producing copolymers by radical polymerisation |
KR1020017002734A KR20010073092A (ko) | 1998-09-03 | 1999-08-25 | 라디칼 중합 반응에 의한 공중합체의 제조 방법 |
NO20011097A NO20011097L (no) | 1998-09-03 | 2001-03-02 | Fremgangsmåte for fremstilling av kopolymerer ved radikalpolymerisasjon |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19840268.6 | 1998-09-03 | ||
DE19840268A DE19840268A1 (de) | 1998-09-03 | 1998-09-03 | Verfahren zur Herstellung von Copolymerisaten durch radikalische Polymerisation |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000014132A1 true WO2000014132A1 (de) | 2000-03-16 |
Family
ID=7879740
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/006224 WO2000014132A1 (de) | 1998-09-03 | 1999-08-25 | Verfahren zur herstellung von copolymerisaten durch radikalische polymerisation |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1117712A1 (de) |
JP (1) | JP2003524670A (de) |
KR (1) | KR20010073092A (de) |
AU (1) | AU5740499A (de) |
CA (1) | CA2342323A1 (de) |
DE (1) | DE19840268A1 (de) |
HU (1) | HUP0103892A2 (de) |
NO (1) | NO20011097L (de) |
WO (1) | WO2000014132A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005516942A (ja) * | 2001-12-11 | 2005-06-09 | ビーエーエスエフ アクチェンゲゼルシャフト | N−ビニルラクタム単位を有するコポリマーを少なくとも1種含む化粧用組成物 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006234825B2 (en) * | 2005-04-07 | 2011-08-18 | Exxonmobil Upstream Research Company | Recovery of kinetic hydrate inhibitor |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0115836A2 (de) * | 1983-01-28 | 1984-08-15 | Phillips Petroleum Company | Polymere verwendbar in der Rückgewinnung und Verarbeitung von Bodenschätzen |
GB2301825A (en) * | 1996-03-28 | 1996-12-18 | Exxon Production Research Co | A polymer for inhibiting hydrate formation |
GB2301824A (en) * | 1995-10-04 | 1996-12-18 | Exxon Production Research Co | Clathrate hydrate-inhibiting polymers |
WO1998054234A1 (en) * | 1997-05-28 | 1998-12-03 | Nalco Chemical Company | Preparation of water soluble polymer dispersions from vinylamide monomers |
-
1998
- 1998-09-03 DE DE19840268A patent/DE19840268A1/de not_active Withdrawn
-
1999
- 1999-08-25 WO PCT/EP1999/006224 patent/WO2000014132A1/de not_active Application Discontinuation
- 1999-08-25 EP EP99944508A patent/EP1117712A1/de not_active Withdrawn
- 1999-08-25 AU AU57404/99A patent/AU5740499A/en not_active Abandoned
- 1999-08-25 HU HU0103892A patent/HUP0103892A2/hu unknown
- 1999-08-25 JP JP2000568887A patent/JP2003524670A/ja not_active Withdrawn
- 1999-08-25 KR KR1020017002734A patent/KR20010073092A/ko not_active Application Discontinuation
- 1999-08-25 CA CA002342323A patent/CA2342323A1/en not_active Abandoned
-
2001
- 2001-03-02 NO NO20011097A patent/NO20011097L/no not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0115836A2 (de) * | 1983-01-28 | 1984-08-15 | Phillips Petroleum Company | Polymere verwendbar in der Rückgewinnung und Verarbeitung von Bodenschätzen |
GB2301824A (en) * | 1995-10-04 | 1996-12-18 | Exxon Production Research Co | Clathrate hydrate-inhibiting polymers |
GB2301825A (en) * | 1996-03-28 | 1996-12-18 | Exxon Production Research Co | A polymer for inhibiting hydrate formation |
WO1998054234A1 (en) * | 1997-05-28 | 1998-12-03 | Nalco Chemical Company | Preparation of water soluble polymer dispersions from vinylamide monomers |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005516942A (ja) * | 2001-12-11 | 2005-06-09 | ビーエーエスエフ アクチェンゲゼルシャフト | N−ビニルラクタム単位を有するコポリマーを少なくとも1種含む化粧用組成物 |
US7459148B2 (en) | 2001-12-11 | 2008-12-02 | Basf Aktiengesellschaft | Cosmetic agent containing at least one copolymer having N-vinyllactam units |
Also Published As
Publication number | Publication date |
---|---|
DE19840268A1 (de) | 2000-03-09 |
JP2003524670A (ja) | 2003-08-19 |
NO20011097L (no) | 2001-03-05 |
AU5740499A (en) | 2000-03-27 |
HUP0103892A2 (hu) | 2002-01-28 |
NO20011097D0 (no) | 2001-03-02 |
EP1117712A1 (de) | 2001-07-25 |
CA2342323A1 (en) | 2000-03-16 |
KR20010073092A (ko) | 2001-07-31 |
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