WO2000068286A1 - Styrol-haltige popcorn-polymerisate, verfahren zu deren herstellung und verwendung - Google Patents
Styrol-haltige popcorn-polymerisate, verfahren zu deren herstellung und verwendung Download PDFInfo
- Publication number
- WO2000068286A1 WO2000068286A1 PCT/EP2000/003809 EP0003809W WO0068286A1 WO 2000068286 A1 WO2000068286 A1 WO 2000068286A1 EP 0003809 W EP0003809 W EP 0003809W WO 0068286 A1 WO0068286 A1 WO 0068286A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- styrene
- popcorn polymers
- popcorn
- vinylpyrrolidone
- Prior art date
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- Popcorn polymers containing styrene process for their preparation and use
- the invention relates to insoluble, styrene-containing popcorn polymers, processes for their preparation and the use of the popcorn polymers as adsorbents, ion exchangers, carrier materials and filter aids.
- popcorn polymer stands for foamy, crusty polymer grains with a cauliflower-like structure. Because of their usually strong crosslinking, popcorn polymers are generally insoluble and hardly swellable.
- DE 2 255 263 discloses a process for the preparation of insoluble, crosslinked and only slightly absorbable polymers of N-vinylpyrrolidone, in which N-vinylpyrrolidone in aqueous solution in the presence of a cyclic acid amide which contains at least two ethylenically unsaturated groups as crosslinking agents polymerized.
- the polymerization reaction is started by heating the reaction solution to at least 80 ° C. and ending at the boiling point of the water.
- No. 3,277,066 relates to a process for the production of insoluble polymers of N-vinyl lactams by heating N-vinyl lactams in water in the presence of alkali and alkaline earth metal oxides and hydroxides as catalysts.
- Popcorn polymers have the properties that when they come into contact with the monomers from which they consist or with other monomers, they can convert them into popcorn polymers. They act as a seed for the polymerization, so to speak. However, the activity is lost when they come into contact with air.
- EP-A-0 177 812 discloses a process for the preparation of insoluble, only slightly swellable, powdery polymers based on monoethylenically unsaturated carboxamides, carboxylic acids and carboxylic esters, in which an active popcorn polymer is used to start the polymerization, which by heating a mixture of 99.6 to 98.8% by weight of N-vinylpyrrolidone and 0.4 to 1.2% by weight of a compound having at least 2 ethylenically unsaturated double bonds as crosslinking agent to a temperature of 100 to 150 ° C. is available in the absence of oxygen and polymerization initiators.
- popcorn polymers are used, for example, to absorb tannins from beverages and as ion exchangers.
- Popcorn polymers containing carboxyl groups can also be obtained by saponification of polymers containing acrylic ester and acrylamide units.
- US 2,341,175 describes the popcorn polymerization of styrene with polyunsaturated organic esters (e.g. allyl acrylate).
- the spontaneous bulk polymerization of styrene and comonomer is carried out at temperatures of 80 ° C and reaction times of 6-7 days.
- the reaction product is worked up with benzene, separated off, dried and ground. Powdery, porous, insoluble and non-filling styrene copolymers are obtained.
- EP-A-0 088 964 describes a process for the production of popcorn polymers from basic vinyl heterocycles and up to 30% by weight of various comonomers.
- a mixture of N-vinylpyrrolidone and divinylethylene urea is used as the starting template.
- the water-soluble, basic vinyl heterocycle e.g. N-vinylimidazole
- Styrene is also mentioned as a possible comonomer.
- a further object of the present invention was to provide new substances which can be used as adsorbents, ion exchangers, carrier materials and filter aids.
- Mono-unsaturated styrene derivatives mean, inter alia, sulfone-containing styrenes, such as, for example, styrene-3-sulfonic acid or sodium styrene-3-sulfonate, and styrene containing amino groups.
- Styrenes containing amino groups are, for example, styrenes which have the following substituents in the 3-position: -CH 2 N + (CH 3 ) 3 C1 " , -CH 2 N + (CH 3 ) 2 CH 2 CH 2 0HC1 ", -CH 2 N (CH 3 ) 2 , -CHNHCH, -CHNH 2 .
- the above styrene derivatives are known, inter alia, as monomers for the preparation of ion exchange resins.
- the monomers a) are used in amounts of 50 to 99% by weight, preferably 70 to 99% by weight, particularly preferably in amounts of 75 to 97% by weight, based on the total amount of the popcorn polymer used.
- Hydrophilic components b) are generally N-vinyl lactams or N-vinyl amines.
- the following polymerizable comonomers are preferred:
- N-vinyl lactams and N-vinyl amines especially N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl imidazole, N-vinyl 2-methylimidazole, N-vinyl 4-methyl imidazole and N-vinyl formamide.
- Preferred hydrophilic components are N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam, particularly preferably N-vinylpyrrolidone.
- the monomers b) are used in amounts of 0.1 to 40% by weight, preferably 0.5 to 30% by weight, particularly preferably in amounts of 1 to 25% by weight, based on the total amount of the popcorn polymer used.
- Monomers c) are generally compounds which contain at least 2 ethylenically unsaturated non-conjugated double bonds in the molecule and thus act as difunctional crosslinkers in the polymerization.
- Preferred representatives of the monomers c) are, for example, alkylenebisacrylamides such as methylenebisacrylamide and N, N'-acryloylethylenediamine, N, N'-divinylethylene urea, N, N'-divinylpropylene urea, ethylidene-bis-3- (N-vinylpyrrolidone), N, N'-divinyldiimidazolyl (2, 2 ') butane and l, l'-bis- (3,3'-vinylbenzimidazolith-2-one) 1,4-butane.
- crosslinking agents are, for example, alkylene glycol di (meth) - acrylates, such as Et ylenglykoldiacrylat, ethylene glycol dimethacrylate, Tetraethylenglykolacrylat, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, Diethylenglykolmethacrylat, aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and vinyl acrylate, allyl acrylate, allyl methacrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures of crosslinkers.
- alkylene glycol di (meth) - acrylates such as Et ylenglykoldiacrylat, ethylene glycol dimethacrylate, Tetraethylenglykolacrylat, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, Diethylenglykolmethacryl
- crosslinkers are N, N '-divinylethylene urea and divinylbenzene.
- the crosslinking agents are used in amounts of 0.1 to 10, preferably 0.1 to 8% by weight, particularly preferably in amounts of 0.2 to 5% by weight, based on the total amount of the popcorn polymer.
- Popcorn polymers containing are preferred
- N-vinyl lactam or N-vinylamine selected from the group consisting of
- N-vinyl pyrrolidone N-vinyl piperidone, N-vinyl caprolactam, N-vinyl imidazole and methylated N-vinyl imidazole or N-vinyl formamide;
- the popcorn polymers according to the invention can additionally contain up to 20% by weight of further free-radically polymerizable monomers d), in which case the% by weight of the monomers a) to d) add up to 100%.
- free-radically polymerizable monomers d) include Acrylic acid and methacrylic acid and their esters and amides, for example methyl, ethyl, isopropyl, n-butyl and tert-butyl esters or amides, and also vinyl acetate, acrylonitrile or vinyl methyl ether.
- the invention also relates to a process for the production of insoluble, only slightly swellable popcorn polymers, characterized in that
- N-vinyllactam or N-vinylamine selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole and methylated N-vinylimidazole or N -Vinylformamide and
- the popcorn polymerization is carried out by known processes, for example as precipitation polymerization or by bulk polymerization.
- a procedure is preferred in which, as described in EP-A-0 177 812, the popcorn polymerization is started by mixing a mixture of 99.6 to 98.8% by weight of N-vinylpyrrolidone and 0, 4 to 1.2% by weight of a compound having at least two ethylenically unsaturated double bonds as crosslinking agent is heated to a temperature of 100 to 150 ° C. in the absence of oxygen and polymerization initiators.
- This polymerization is initiated in particular by the presence of small amounts of sodium hydroxide solution or potassium hydroxide solution.
- a polymerizable popcorn polymer is formed within a short time and, when the remaining monomer mixture, ie in particular the styrene monomer and the remaining amount of monomers c), is added, the popcorn polymerization of these monomers starts without an induction period.
- the polymerizable popcorn polymer into a template which contains monomer and crosslinking agent, or into which monomer and crosslinking agent are then metered in.
- the popcorn polymerization can also be carried out without a solvent.
- the monomer mixture of a), b) and c) is rendered inert by introducing nitrogen and then heated to a temperature in the range from 20 to 200 ° C., preferably 100 to 5 200 ° C., particularly preferably 150 to 180 ° C. It is advantageous to continue to conduct a weak nitrogen flow through the monomers even during the polymerization.
- the exclusion of oxygen is also achieved by polymerizing the batch at a pressure below that
- the mixture polymerizes within 1 to 20 hours.
- the first polymer particles the amount of which slowly increases, form after 2.5 hours. until after about 10 hours of polymerization the reaction mixture consists of a powder.
- the popcorn polymer is obtained therefrom in 0 yields of over 90% in the form of a powder with an average particle size of about 10 ⁇ m to 5 mm, preferably 10 ⁇ m to 500 ⁇ m.
- Precipitation polymerization in water is preferred for the preparation of the popcorn polymers.
- concentration of the monomers is expediently chosen so that the reaction mixture can be stirred well over the entire duration of the reaction. If the concentration of the monomers in water is too high, e.g. at 95%, the polymer grains often become sticky, so that stirring is more difficult than in the absence of water.
- monomer concentrations, based on the aqueous mixture of about 5 to 30, preferably 10 to 20,% by weight are chosen. If more powerful stirrers are available, the monomer concentration 5 of the aqueous solution can also be increased to 50% by weight, if appropriate also above this.
- the popcorn polymerization is preferably carried out at pH values above 6 in order to avoid possible saponification of the monomers b) and / or c).
- the pH can be adjusted by adding small amounts of bases 5 such as sodium hydroxide or ammonia or the customary buffer salts such as soda, sodium hydrogen carbonate or sodium phosphate.
- bases 5 such as sodium hydroxide or ammonia or the customary buffer salts such as soda, sodium hydrogen carbonate or sodium phosphate.
- the exclusion of oxygen can best be achieved by heating the mixture to be polymerized to boiling and, if appropriate, additionally working in an inert gas atmosphere, for example by passing nitrogen through the reaction mixture.
- the polymerization temperature can be varied within a wide range, for example from about 20 to 200, preferably 50 to 150 ° C.
- a reducing agent such as sodium sulfite, sodium pyrosulfite, sodium dithionite, ascorbic acid or mixtures of the reducing agents to completely remove dissolved oxygen.
- the water-soluble comonomer, part of the crosslinking agent, water and optionally a buffer and a reducing agent are heated in a gentle stream of nitrogen until the first polymer particles show up. Then a mixture of styrene, in particular crosslinking agent and optionally water, which has been rendered inert by blowing in nitrogen, is added as a diluent within 0.2 to 10 hours.
- the styrene and the crosslinking agent can also be dissolved in a water-miscible solvent. This can e.g. lower alcohols such as methanol, ethanol, isopropanol, n-propanol or t-butanol. This procedure has the advantage that the popcorn polymerization takes only a relatively short time.
- the popcorn polymers can be isolated and purified from the aqueous solution.
- the popcorn polymers are usually obtained in a yield of about 90 to> 99% of the theoretical yield. They can be isolated from the aqueous suspension by filtration or centrifugation with subsequent washing out with water and drying in conventional dryers such as a circulating air or vacuum drying cabinet, paddle dryer or current dryer. The popcorn polymers are practically insoluble in water and all solvents and only swell slightly in them.
- the insoluble, only slightly swellable polymers obtainable in this way can be used as adsorbents, ion exchangers, carrier materials and filter aids.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Grain Derivatives (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT00931078T ATE263197T1 (de) | 1999-05-07 | 2000-04-27 | Styrolhaltige popcorn-polymerisate, verfahren zu deren herstellung und ihre verwendung |
DE50005907T DE50005907D1 (de) | 1999-05-07 | 2000-04-27 | Styrolhaltige popcorn-polymerisate, verfahren zu deren herstellung und ihre verwendung |
US09/959,402 US6525156B1 (en) | 1999-05-07 | 2000-04-27 | Styrene-containing popcorn polymers, method for producing same and utilisation |
JP2000616256A JP2002544301A (ja) | 1999-05-07 | 2000-04-27 | スチレン含有ポップコーンポリマー、その製造および使用 |
DK00931078T DK1177226T3 (da) | 1999-05-07 | 2000-04-27 | Styrenholdige popcorn-polymerisater, fremgangsmåde til disses fremstilling og deres anvendelse |
EP00931078A EP1177226B1 (de) | 1999-05-07 | 2000-04-27 | Styrolhaltige popcorn-polymerisate, verfahren zu deren herstellung und ihre verwendung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19920944.8 | 1999-05-07 | ||
DE19920944A DE19920944A1 (de) | 1999-05-07 | 1999-05-07 | Styrol-haltige Popcorn-Polymerisate, Verfahren zu deren Herstellung und Verwendung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000068286A1 true WO2000068286A1 (de) | 2000-11-16 |
Family
ID=7907226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/003809 WO2000068286A1 (de) | 1999-05-07 | 2000-04-27 | Styrol-haltige popcorn-polymerisate, verfahren zu deren herstellung und verwendung |
Country Status (10)
Country | Link |
---|---|
US (1) | US6525156B1 (de) |
EP (1) | EP1177226B1 (de) |
JP (1) | JP2002544301A (de) |
CN (1) | CN1149236C (de) |
AT (1) | ATE263197T1 (de) |
DE (2) | DE19920944A1 (de) |
DK (1) | DK1177226T3 (de) |
ES (1) | ES2218158T3 (de) |
PT (1) | PT1177226E (de) |
WO (1) | WO2000068286A1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1318159A2 (de) * | 2001-12-07 | 2003-06-11 | Basf Aktiengesellschaft | Verwendung unlöslicher hochvernetzter Popcorn-Polymerisate als Filterhilfs-und/oder Stabilisierungsmittel |
US6677417B2 (en) * | 2000-03-10 | 2004-01-13 | Basf Aktiengesellschaft | Method for adjusting the particle size of popcorn polymers during popcorn polymerization |
WO2006097470A1 (de) * | 2005-03-16 | 2006-09-21 | Basf Aktiengesellschaft | Verfahren zur herstellung von blends aus polystyrol und einem vernetzten polyvinylpyrrolidon mit verringertem styrol-restmonomergehalt |
CN1312186C (zh) * | 2001-02-21 | 2007-04-25 | 巴斯福股份公司 | 用作助滤剂的粒状聚合物 |
US8420737B2 (en) | 2006-09-12 | 2013-04-16 | Basf Se | Method for the production of co-extrudates composed of polystyrene and of a crosslinked polyvinylpyrrolidone with reduced residual styrene monomer content |
CN101612553B (zh) * | 2008-06-26 | 2013-11-06 | 罗门哈斯公司 | 自由基后交联吸附剂及其制备方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10065427A1 (de) * | 2000-12-27 | 2002-07-04 | Basf Ag | Verwendung teilchenförmiger Polymerisate als Filterhilfsmittel für wässrige Flüssigkeiten |
US6876129B2 (en) * | 2001-09-26 | 2005-04-05 | Mitsuba Corporation | Rotary actuator and method of controlling an actuator |
CN104004131B (zh) * | 2014-02-25 | 2017-04-12 | 江苏海普功能材料有限公司 | 含吡咯烷酮基高比表面积两性吸附树脂及其制备方法 |
CN105218730B (zh) * | 2015-09-14 | 2017-08-25 | 清华大学深圳研究生院 | 吸附树脂及其制备方法和用途 |
CN113527578B (zh) * | 2020-04-22 | 2022-11-01 | 北京化工大学 | 一种胺基官能化聚苯乙烯树脂及其制备方法与应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3818868A1 (de) * | 1988-06-03 | 1989-12-14 | Basf Ag | Verfahren zur herstellung stark truebender, sedimantationsstabiler dispersionen |
Family Cites Families (8)
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US2341175A (en) | 1940-03-15 | 1944-02-08 | Dow Chemical Co | Insoluble polymers derived from styrene |
US3306886A (en) | 1963-10-23 | 1967-02-28 | Gen Aniline & Film Corp | Polymerization of n-vinyl lactams using plural stage heating in the presence of catalyst compositions of hydrides or borohydrides of alkali metals and water |
DE2255263C3 (de) | 1972-11-11 | 1975-06-05 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von unlöslichen, vernetzten, nur wenig quellbaren Polymerisaten des N-Vinylpyrrolidon-(2) |
DE3209224A1 (de) * | 1982-03-13 | 1983-09-15 | Basf Ag | Verfahren zur herstellung von unloeslichen, nur wenig quellbaren polymerisaten von basischen vinylheterocyclen und deren verwendung |
DE3434138A1 (de) | 1984-09-18 | 1986-03-27 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von unloeslichen, nur wenig quellbaren pulverfoermigen polymerisaten |
DE4237439A1 (de) * | 1992-11-06 | 1994-05-11 | Basf Ag | Unlösliche, nur wenig quellbare Polymerisate mit Aminogruppen, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4328669A1 (de) * | 1993-08-26 | 1995-03-02 | Basf Ag | Verfahren zur Entfernung von Aluminiumionen aus Getränken |
DE19640365A1 (de) * | 1996-09-30 | 1998-04-02 | Basf Ag | Polymer-Wasserstoffperoxid-Komplexe |
-
1999
- 1999-05-07 DE DE19920944A patent/DE19920944A1/de not_active Withdrawn
-
2000
- 2000-04-27 JP JP2000616256A patent/JP2002544301A/ja not_active Withdrawn
- 2000-04-27 US US09/959,402 patent/US6525156B1/en not_active Expired - Fee Related
- 2000-04-27 DE DE50005907T patent/DE50005907D1/de not_active Expired - Fee Related
- 2000-04-27 WO PCT/EP2000/003809 patent/WO2000068286A1/de active IP Right Grant
- 2000-04-27 DK DK00931078T patent/DK1177226T3/da active
- 2000-04-27 PT PT00931078T patent/PT1177226E/pt unknown
- 2000-04-27 ES ES00931078T patent/ES2218158T3/es not_active Expired - Lifetime
- 2000-04-27 EP EP00931078A patent/EP1177226B1/de not_active Expired - Lifetime
- 2000-04-27 AT AT00931078T patent/ATE263197T1/de not_active IP Right Cessation
- 2000-04-27 CN CNB008073007A patent/CN1149236C/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3818868A1 (de) * | 1988-06-03 | 1989-12-14 | Basf Ag | Verfahren zur herstellung stark truebender, sedimantationsstabiler dispersionen |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6677417B2 (en) * | 2000-03-10 | 2004-01-13 | Basf Aktiengesellschaft | Method for adjusting the particle size of popcorn polymers during popcorn polymerization |
CN1312186C (zh) * | 2001-02-21 | 2007-04-25 | 巴斯福股份公司 | 用作助滤剂的粒状聚合物 |
EP1318159A2 (de) * | 2001-12-07 | 2003-06-11 | Basf Aktiengesellschaft | Verwendung unlöslicher hochvernetzter Popcorn-Polymerisate als Filterhilfs-und/oder Stabilisierungsmittel |
EP1318159A3 (de) * | 2001-12-07 | 2003-12-03 | Basf Aktiengesellschaft | Verwendung unlöslicher hochvernetzter Popcorn-Polymerisate als Filterhilfs-und/oder Stabilisierungsmittel |
WO2006097470A1 (de) * | 2005-03-16 | 2006-09-21 | Basf Aktiengesellschaft | Verfahren zur herstellung von blends aus polystyrol und einem vernetzten polyvinylpyrrolidon mit verringertem styrol-restmonomergehalt |
US7868093B2 (en) | 2005-03-16 | 2011-01-11 | Basf Se | Method for producing blends consisting of polystyrene and of a cross-linked polyvinyl pyrrolidone having a reduced styrene residual monomer content |
US8420737B2 (en) | 2006-09-12 | 2013-04-16 | Basf Se | Method for the production of co-extrudates composed of polystyrene and of a crosslinked polyvinylpyrrolidone with reduced residual styrene monomer content |
CN101612553B (zh) * | 2008-06-26 | 2013-11-06 | 罗门哈斯公司 | 自由基后交联吸附剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2002544301A (ja) | 2002-12-24 |
CN1149236C (zh) | 2004-05-12 |
PT1177226E (pt) | 2004-06-30 |
US6525156B1 (en) | 2003-02-25 |
DK1177226T3 (da) | 2004-08-09 |
DE19920944A1 (de) | 2000-11-09 |
EP1177226B1 (de) | 2004-03-31 |
ATE263197T1 (de) | 2004-04-15 |
CN1350559A (zh) | 2002-05-22 |
EP1177226A1 (de) | 2002-02-06 |
ES2218158T3 (es) | 2004-11-16 |
DE50005907D1 (de) | 2004-05-06 |
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