EP1285007A2 - Moyens de purification - Google Patents

Moyens de purification

Info

Publication number
EP1285007A2
EP1285007A2 EP01950455A EP01950455A EP1285007A2 EP 1285007 A2 EP1285007 A2 EP 1285007A2 EP 01950455 A EP01950455 A EP 01950455A EP 01950455 A EP01950455 A EP 01950455A EP 1285007 A2 EP1285007 A2 EP 1285007A2
Authority
EP
European Patent Office
Prior art keywords
butyl
tert
propyl
methanol
group
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.)
Ceased
Application number
EP01950455A
Other languages
German (de)
English (en)
Inventor
Michael Thomas Sheehan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TriQuest LP
Original Assignee
TriQuest LP
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TriQuest LP filed Critical TriQuest LP
Publication of EP1285007A2 publication Critical patent/EP1285007A2/fr
Ceased legal-status Critical Current

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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/04—Fractionation
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
    • 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
    • C08F12/00—Homopolymers and 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
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • 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
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F214/00—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 halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
    • C08F6/28—Purification

Definitions

  • Copolymers and terpolymers when isolated from reaction solution are a mixture of compounds of varying composition and molecular weight. Typically they contain small quantities of starting material and by-products which are undesirable in the final polymer.
  • the polymer mixture is precipitated from the solvent or solvent mixture by adding the mixture to a non-solvent, as for example water, hexane, heptane, octane, petroleum ether, or a mixture thereof.
  • the polymer is then dried in air or a nitrogen atmosphere.
  • the subject of this invention pertains to a method of purifying the polymer.
  • Zempini et al. in U. S. 5,789,522 and U. S. 5,939.511, extracts impurities from a phenolic resin by dissolving the resin in a photoresist solvent and extracting the water-soluble impurities therefrom.
  • the present invention provides a novel process for improving the glass transition temperatures of polymer intermediates that have been polymerized by precipitation from methanol.
  • the polymers that are susceptible to treatment with the method of this invention are polymers of 4-alkoxystyrene.
  • the 4-alkoxystyrene polymers are then hydrolyzed or transesterified to 4-hydroxystyrene-containing polymers useful in paints, resins, thickening agents, and in photoresist compositions.
  • the process is an improvement over the prior art and is quite efficient.
  • the invention provides a method of removing unreacted monomers, low molecular weight polymers, and the like from the crude polymer mixture. Many analytical methods can be utilized to quantify the improvement in the purity of polymers. Average molecular weight, nuclear magnetic resonance, chromatography, and glass transition temperature are all effective in certain instances with certain molecules and characteristic side chains.
  • the crude polymer after polymerization is separated from the alcohol by filtration, centrifugation, decantation, or the like.
  • the polymer is reslurried in methanol and the solid is separated from the methanol. This procedure is repeated as long as necessary to remove by-products and low molecular weight materials that are more soluble in the methanol than the desired polymer.
  • This invention provides a process for the improvement in the composition of polymers of the monomer I,
  • R 1 and R 2 may be the same or different and independently selected from the group consisting of: hydrogen; fluorine, chlorine or bromine; alkyl or fluoroalkyl group having the formula C n H x F y where n is an integer from 1 to 4, x and y are integers from 0 to 2n+l, and the sum of x and y is 2
  • the alcoholic solvent for the polymerization is an alcohol having 1 to 4 carbon atoms ⁇ and is selected from the group consisting of methanol, ethanol, propanol, isopropanol, t-butanol, and combinations thereof.
  • the amount of solvent used is not critical and can be any amount which accomplishes the desired end result.
  • the free radical initiator for the polymerization may be any initiator that achieves the desired end result.
  • the initiator may be selected from the group consisting of 2,2'-azobis(2,4-dimethylpentanenitrile), 2,2'-azobis(2- methyipropanenitrile), 2,2'-azobis(2-methylbutanenitrile), 1,1'- azobis(cyclohexanecarbonitrile), t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-amyl peroxypivalate, diisononanoyl peroxide, decanoyl peroxide, succinic acid peroxide, di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, t-butylperoxyneodecanoate, - 2,5-dimethyl
  • the initiator is typically selected from the group consisting of 2,2'-azobis(2,4- dimethylpentanenitrile), 2,2'-azobis(2-methylpropanenitrile), 2,2'-azobis(2- methylbutanenitrile), l,l'-azobis(cyclohexanecarbonitrile), t-butyl peroxy-2- ethylhexanoate, t-butyl peroxypivalate, t-amyl peroxypivalate, and combinations thereof.
  • the polymerization conditions are not critical and can be any temperature and pressure that will produce the desired end result.
  • the temperatures are from about 30°C to about 100°C, preferably from about 40°C to about 100°C, and most preferably from about 45°C to about 90°C.
  • the pressure may be atmospheric, sub- atmospheric or super-atmospheric.
  • the polymerization time is not critical, but generally will take place over a period of at least one minute in order to produce a polymer of corresponding composition.
  • step (1) in a transesterification, the crude polymer from step (a) is subjected to said transesterification conditions in an alcoholic solvent in the presence of catalytic amounts of a base catalyst.
  • the base catalyst is such that it will not substantially react with said alkyl acrylate monomer ⁇ , or with said co-polymerizable monomers.
  • the base catalyst is either an alkalic metal hydroxide or an alkalic metal alkoxide.
  • the base catalyst is selected from the group consisting of lithium hydroxide, lithium methoxide, lithium ethoxide, lithium isopropoxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, cesium hydroxide, cesium methoxide, cesium ethoxide, cesium isopropoxide, and combinations thereof. If a hydrolysis is utilized to effect removal of the phenol blocking group, the acid should be a member of the strong acids, as for example hydrochloric acid, hydrobromic acid, sulfuric acid, or the like.
  • the crude polymer is slurried in methanol.
  • the slurry is then stirred vigorously or is heated to boiling for several minutes and then chilled or allowed to stand until cool.
  • the purified polymer is removed by centrifugation, filtration, decantation, or by similar means, and the process is repeated until no further purification is identified, as for example, until a small sample of the decanted methanol upon evaporation to dryness shows no residue.
  • Example The following example illustrates the use of the method of this invention on the purification of a copolymer of 4-acetoxystyrene/tert.-butyl acrylate.
  • 3282.8 g. 4- acetoxystyrene, and 254 g. tert.-butyl acrylate is polymerized in 3140 g. methanol using 204.3 g. tert.-butyl peroxypivalate as a catalyst.
  • a sample of the polymer is isolated for analytical purposes. After polymerization was complete, 1390 g. of methanol was removed at 58°C. and replaced with 1392 g. of fresh methanol. The slurry was heated to reflux and cooled to 48°C. Another 1595 g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polymères de 4-alcoxystyrène, qui sont purifiés par de multiples mises en suspension du polymère dans du méthanol.
EP01950455A 2000-06-27 2001-06-25 Moyens de purification Ceased EP1285007A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US60414000A 2000-06-27 2000-06-27
US604140 2000-06-27
PCT/US2001/020227 WO2002000736A2 (fr) 2000-06-27 2001-06-25 Moyens de purification

Publications (1)

Publication Number Publication Date
EP1285007A2 true EP1285007A2 (fr) 2003-02-26

Family

ID=24418332

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01950455A Ceased EP1285007A2 (fr) 2000-06-27 2001-06-25 Moyens de purification

Country Status (6)

Country Link
EP (1) EP1285007A2 (fr)
JP (1) JP4129177B2 (fr)
KR (1) KR100574132B1 (fr)
AU (1) AU2001271444A1 (fr)
TW (1) TW538060B (fr)
WO (1) WO2002000736A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6787611B2 (en) * 2000-06-27 2004-09-07 Chemfirst Electronic Materials L.P. Purification means
JP4929552B2 (ja) * 2000-10-30 2012-05-09 住友化学株式会社 固体樹脂の製造方法
US6864324B2 (en) * 2002-04-19 2005-03-08 Chem First Electronic Materials L.P. Anhydrous, liquid phase process for preparing hydroxyl containing polymers of enhanced purity
US7534837B2 (en) * 2005-09-26 2009-05-19 E.I. Du Pont De Nemours And Company Random copolymers of ethylene and 4-vinylphenyl esters and method for preparing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4898916A (en) * 1987-03-05 1990-02-06 Hoechst Celanese Corporation Process for the preparation of poly(vinylphenol) from poly(acetoxystyrene) by acid catalyzed transesterification
US5239015A (en) * 1990-06-29 1993-08-24 Hoechst Celanese Corporation Process for making low optical density polymers and copolymers for photoresists and optical applications
WO1994015972A1 (fr) * 1993-01-11 1994-07-21 Idemitsu Kosan Co., Ltd. Procede pour purifier un polymere de styrene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0200736A2 *

Also Published As

Publication number Publication date
JP2004501988A (ja) 2004-01-22
JP4129177B2 (ja) 2008-08-06
AU2001271444A1 (en) 2002-01-08
WO2002000736A3 (fr) 2002-05-23
TW538060B (en) 2003-06-21
WO2002000736A2 (fr) 2002-01-03
KR20020037349A (ko) 2002-05-18
KR100574132B1 (ko) 2006-04-25

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