TW538060B - Method of purifying polymers containing 4-alkoxystyrene - Google Patents

Abstract

Polymers containing 4-alkoxystyrene are purified by multiple slurrying of the polymer in methanol.

Description

538060 A7 B7) 5. Description of the invention (1 Background of the invention

When singly isolated from the reaction solution, copolymers and terpolymers are mixtures of compounds of different compositions and molecular weights. Generally, it contains small amounts of starting materials and by-products, which are unwanted in the final polymer. The polymer mixture is precipitated from a solvent or a solvent mixture by adding the mixture to a non-solvent such as water, hexane, heptane, octane, petroleum, or a mixture thereof. The mixture was then dried under air or nitrogen pressure. The object of the present invention is a way to purify the polymer. Davidson in U.S. Pat. No. 5,945,251 discloses a method for purifying a poly (vinyl) basic ethylene polymer by adding an amine, a hydrophilic solvent, a hydrophobic solvent, and water to the polymer; separating the aqueous phase; and then removing the hydrophilicity. Solvents and hydrophobic solvents form purified polymers. Zempini et al., In U.S. Patent No. 5,789,522 and U.S. Patent No. 5,939,511, extract impurities from a phenol resin by dissolving the resin in a photoresist solvent and extracting water-soluble impurities therefrom.

SUMMARY OF THE DISCLOSURE The present invention provides a novel method for improving the glass transition temperature of polymer intermediates polymerized by precipitation from methanol. The polymer which is sensitive to the process of the present invention is a polymer of 4_oxyoxystyrene. The 4-oligomeric acetophenone polymer is then hydrolyzed or trans-esterified to a 4- phenylphenylene-containing polymer for use in paints, resins, thickeners, and photoresist compositions. This method is an improvement over conventional techniques and is quite efficient. Specifically, the present invention provides a method for removing unreacted monomers, low molecular weight polymers, and the like from a crude polymer mixture. Many analysis methods can be used. -4- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 538060 A7.

Improvement in purity with 2 li of polymer. In some instances, the average molecular NMR "vibration, chromatographic analysis, and glass transition temperature and characteristic branching are all effective. As before, the crude polymer after polymerization is filtered from the alcohol and separated from the t Separation by decantation. According to the method of the present invention, the polymer is re-sludged in methanol, and the solid is separated from the methanol. As long as it is necessary to remove byproducts that are more soluble in methanol than the desired polymer and low This step can be repeated for molecular weight substances.-Detailed description of the present invention The present invention provides an improved method for polymer composition of monomer j,

Is a homopolymer and / or generally with one or more of the following monomers: an acrylate monomer having Formula 11:

And / or together with one or more ethylenic unsaturated copolymerizable monomers, namely: styrene, 4-methylstyrene, tertiary-butyl acetofluorene, cyclohexyl acrylate, tertiary butyl acrylate Esters, tertiary-butyl methacrylate, maleic anhydride, -5- ^ Paper size Seco ® ® Standard (CNS) A4 specification (Outline x 297 male & 538060 five A7 B7, invention description (3 ) Maleic acid dialkyl esters, fumaric acid dialkyl esters, and vinyl chloride and the like. Where i) R1 and R2 may be the same or different and are independently selected from the following groups: hydrogen; 'fluorine , Chlorine or bromine; an alkyl or fluoroalkyl group having the formula CnHxFy, where n is an integer from 1 to 4, X and y are integers from 0 to 2 η + 1, and the sum of X and y is 2 η + 1; and phenyl or tolyl; ii) R3 may be selected from the group consisting of: hydrogen; and methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tertiary -Butyl; iii) R4 may be methyl, ethyl, n-propyl, iso-propyl, or tertiary-butyl; and iv) R5 may be fluorenyl or ethyl and have 1 to 4 carbon atoms Alkyl, generally the monomer of formula 1C:

Or a monomer of formula I and / or monomer II, and / or one or more of the copolymerizable monomers, in an alcohol-based solvent and in the presence of a free radical initiator, at an appropriate temperature-6-this paper Standards apply to China National Standard (CNS) A4 specifications (210X 297 mm)

Outfit-order

Line 538060 A7 B7 V. Description of the invention (4), manufactured with appropriate polymerization conditions, to produce a corresponding composition of polymer in a sufficient period of time. After purification by the method of the present invention, the purified polymer is hydrolyzed or transesterified to a polymer containing a monomer of formula nj ...

(1) The conditions for transesterification of the polymer in the alcohol-based solvent, in the presence of the test reagents of Yihua, at an appropriate temperature, so that the transesterified by-product esters formed are reacted from the reaction. The mixture is continuously removed to form a homopolymer of J, or a copolymer of I, II and the copolymerizable monomer, or (2) the polymer is subjected to acidic hydrolysis for strong reasons. The polymer is then optionally passed through an ion exchange bed to remove the base or acid catalyst; the alcoholic solvent used for the polymerization is an alcohol having 1 to 4 carbon atoms, and is selected from the group consisting of methanol, ethanol, and propanol , Isopropanol, tertiary butanol, and combinations thereof. The amount of solvent used is not critical and can be any amount that will achieve the desired end result. The free radical initiator used in the polymerization can be any initiator capable of achieving the desired end result. The initiator can be selected from the group consisting of 2,2, _azobis (2,4 • diamidinopentanenitrile), 2,2, -azobis (2-methylpropanenitrile), 2,2, _ Azobis (2-methyl butane), 1,1_azobis (cyclohexyl carbonyl nitrile), peroxyethylhexanoic acid second-butyl ester, peroxypivalic acid third-butyl Ester, peroxypivalic acid tertiary-pentyl ester, diisononyl peroxide, decylfluorenyl peroxide, butyl paper. Applicable to China National Standard (CNS) A4 (210 X 297 mm) 538060 A7 B7 V. Description of the invention (5) Diacid peroxide, di (n-propyl) peroxydicarbonate, di (second-butyl) peroxydicarbonate, peroxydicarbonate Di (2-ethylhexyl) ester, tertiary-butylperoxy neodecanoate, 2,5-dimethyl-2,5- (2-ethylhexylperoxy) hexane, tertiary- Amylperoxy neodecanoate and combinations thereof. The initiator is generally selected from the group consisting of 2,2, -azobis (2,4-dimethylpentanenitrile), 2,2'-azobis (2-methylpropanenitrile), 2,2 , -Azobis (2-fluorenylbutyronitrile), 1,1'-Azobis (cyclohexylfluorenylcarbonylnitrile), Peroxy-2-ethylhexanoic acid third-butyl ester, Peroxy Tert-butyl pivalate, tert-pentyl peroxy pivalate, and combinations thereof. The conditions of the polymerization are unimportant and can be any temperature and pressure that will produce the desired end result. Generally, the temperature is from about 300 t to about 100 t, 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 pressure, sub-atmospheric pressure, or greater than atmospheric pressure. The time of the polymerization is not important, but it is usually carried out over a period of at least one minute to produce a corresponding composition of the polymer. In the transesterification in step (I), the crude polymer from step (a) is subjected to the transesterification conditions in an alcohol-based solvent in the presence of a catalytic amount of a base catalyst. The alkali catalyst is such that it does not substantially react with the alkyl acrylate monomer II, or the monomer copolymerizable with the monomer. The alkali catalyst is an alkali metal hydroxide or an alkali metal alkoxide. The base catalyst is selected from the group consisting of lithium hydroxide, lithium rhenium oxide, lithium ethoxylate, lithium propylene oxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium propylene oxide, potassium thorate, potassium methoxide, and ethyl acetate. Potassium oxide, isopropyl oxide, cesium hydroxide, methooxide, ethoxylate, cesium isooxide and combinations thereof. -8-This paper is suitable for National Standards (CNS) A4 size (210X2 ^ 17

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Line 538060 A7 B7

If hydrolysis is used to effectively remove the phenol-blocking group, the acid must be a member of a strong acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, or the like. According to the method of the present invention, after the alkoxystyrene-containing polymer is completely polymerized 'and before hydrolysis or transesterification, the crude polymer is slurried in methanol. The slurry is then stirred vigorously or heated to boiling for several minutes, and then cooled or allowed to stand until cooled. The purified polymer is removed by centrifugation, filtration, decantation or similar and the method is repeated 'until no further purification is identified, for example: until a small sample of decanted methanol shows no residue when evaporated to dryness Thing. Examples The following examples illustrate the use of the method of the present invention for the purification of a 4-ethoxyethyphenamidine / third acrylate copolymer. 3282.8 grams of 4-ethoxyethoxybenzene and 254 grams of tertiary-butyl acrylate were copolymerized in 3,140 grams of methanol, and 204.3 grams of tert-butyl peroxypivalate were used as a catalyst. Polymer samples were isolated for analytical purposes. After the polymerization was completed, 1390 g of methanol was removed at 5 8 ° C and replaced with 1392 g of fresh methanol. The slurry was heated to reflux and cooled to 48 ° C. An additional 1595 grams of methanol was removed and replaced with 1590 grams of fresh methanol. The slurry was heated to reflux and cooled. Methanol was removed and replaced with 1800 grams of fresh methanol, and the mixture was then transesterified with 39.8 grams of sodium methoxide. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 〆 ·, — ,,? · F Application date: '90. 06; 27: — 090115612 Category—One —___ each of the above 襕Filled by this Bureau) A4 C4 Chinese manual replacement page (December 91) Snow g patent specification 538060 Cloud | Name inventor III. Applicant Chinese and English purification method of polymer containing 4-cathoxyoxyphenylene

METHOD OF PURIFYING POLYMERS CONTAINING 4-ALKOXYSTYRENE

Mike T. Xi and MICHAEL T. SHEEHAN Nationality Domicile and Residence f Name f Nationality United States 6145 Tyrafaya Road, Koberskresti, Texas, USA

American Tricrest Limited TRIQUEST, LP

United States 14785 Preston Road, Dallas, Texas, USA Mike T. Shee and MICHAEL T. SHEEHAN This paper ruler is reduced in use g 1 home turn (CNS) M size ⑽ 挪 Norwegian company) Binding

Claims (1)

538060 11 ^ Take the year to modify No. 090 阿 12 Chinese is called lingling, knowing #_ 和 1 年 December) Shen "special brake, Fan belongs to: == method, called ... group Is a homopolymer and / or a propionate monomer having Formula II, generally with one or more of the following: Hold And / or together with one or more ethylenic unsaturated copolymerizable monomers, namely, ethylene, 4-methylphenethylhydrazone, tertiary-butylstyrene, cyclohexyl propionate, acrylic acid Tri-butyl ester, tertiary butyl methacrylate, maleic anhydride, maleic acid dialkyl, maleic acid dialkyl, and ethyl chloroacetamate and the like, where: i) R 1 and R2 may be the same or different and are independently selected from the following groups: hydrogen; fluorine, chlorine or bromine; alkyl or fluoroalkyl groups of the formula CnHxFy, where n is 1 to 4 National Standard (CNS) A4 specification (210 X 297 mm) 8 8 8 8 AB CD 538060 6. Number of patent applications, X and y are integers from 0 to 2n + 1, and the sum of X and y is 2n + l And phenyl or tolyl; ii) R3 may be selected from the group consisting of: hydrogen; and methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tertiary- Butyl; iii) R4 can be methyl, ethyl, n-propyl, iso-propyl or tertiary-butyl; and iv) R5 can be methyl or ethyl and has 1 to 4 carbon atoms in it Alkyl; contains the polymer Slurried in methanol, heating or stirring the slurry, and the methanol was removed to provide a purified product. -2- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)