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WO1993019098A1 - Polymerisation par precipitation de copolymeres d'un lactame de vinyle et d'un acide carboxylique polymerisable et solubilisation de ceux-ci - Google Patents

Polymerisation par precipitation de copolymeres d'un lactame de vinyle et d'un acide carboxylique polymerisable et solubilisation de ceux-ci Download PDF

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Publication number
WO1993019098A1
WO1993019098A1 PCT/US1993/001363 US9301363W WO9319098A1 WO 1993019098 A1 WO1993019098 A1 WO 1993019098A1 US 9301363 W US9301363 W US 9301363W WO 9319098 A1 WO9319098 A1 WO 9319098A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymers
mixture
carboxylic acid
vinyl lactam
copolymer
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
PCT/US1993/001363
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English (en)
Inventor
Jenn S. Shih
Terry E. Smith
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.)
ISP Investments LLC
Original Assignee
ISP Investments LLC
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
Priority claimed from US07/851,707 external-priority patent/US5191043A/en
Priority claimed from US07/862,147 external-priority patent/US5219906A/en
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Publication of WO1993019098A1 publication Critical patent/WO1993019098A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing compounds
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • 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
    • C08F226/10—N-Vinyl-pyrrolidone
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2339/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

Definitions

  • Copolymers of vinyl lactams e.g. vinyl
  • carboxylic acids e.g. acrylic acid or methacrylic acid
  • acrylic acid or methacrylic acid have found application in the photographic industry, as coatings, as biological membranes, in drug release systems, as preservatives, in oil recovery processes, in
  • a solution polymerization process is used for making the copolymers when both reactant monomers and the copolymer product are soluble in a reaction solvent.
  • Desirable compositions of the copolymer may not be soluble in a selected solvent; (2) the yields of such copolymer may be low; (3) the copolymer may be
  • the solvent may be a high boiling liquid which is difficult to separate from the copolymer; and (5) the solvent may be a protic liquid, e.g. water or mixtures thereof, which causes considerable hydrolysis of the vinyl lactam under acidic reaction conditions.
  • the precipitation polymerization method is useful when the monomers are soluble in the reaction solvent and the copolymers are insoluble in the solvent.
  • Benzene, tetrahydrofuran, heptane, acetone and methyl ethyl ketone are known precipitation polymerization solvents.
  • the copolymer may precipitate only as a gelatinous mass which is difficult to filter; (3) low yields of polymer may be obtained; (4) the solvent may be toxic; and (5) low molecular weight copolymers may be difficult to make by available processes.
  • the polymerization is carried out on a reaction mixture of a vinyl lactam, e.g. vinyl pyrrolidone or vinyl caprolactam, and a polymerizable carboxylic acid, e.g. acrylic acid or methacrylic acid, in the presence of a polymerization initiator, e.g. a free radical initiator, in a cosolvent mixture of an aliphatic hydrocarbon solvent, preferably, a C 3 -C 10 saturated, branched or unbranched, cyclic or acyclic, and, preferably is heptane or
  • isopropanol and, preferably, about 30% or less, most preferably 5-15%, by weight of the latter.
  • the process herein provides copolymers having a weight ratio of vinyl lactam to polymerizable carboxylic acid of 1:99 to 99:1, and as a white powder, which powder precipitates readily from the aliphatic hydrocarbon solvent and is easily filtered and dried.
  • the copolymers obtained have a low weight average molecular weight, Mw suitably less than about 20,000, as compared to the medium to high molecular weight copolymers made using the aliphatic hydrocarbon solvent alone.
  • Suitable vinyl lactams for use herein include vinyl pyrrolidone, vinyl caprolactam and alkylated vinyl derivatives thereof.
  • Suitable polymerizable carboxylic acids include e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crotonic acid. Acrylic acid itself, or methacrylic acid, is a preferred coreactant monomer in the polymerization. These monomers may be employed in weight ratios over the entire compositional range of the copolymers, i.e.
  • weight ratios of VP:AA in the copolymer of 99:1, 75:25, 50:50, 25:75 and 1:99, for example, may be conveniently prepared in this invention in substantially quantitative yields.
  • copolymerizable monomers may be included as additional coreactants, in an amount of 0-30% by weight of the copolymer.
  • Suitable optional comonomers include acrylic acid esters, vinyl esters, acrylamide,
  • N-alkylacrylamides and the like.
  • the reaction solvent of the invention includes a C 3 -C 10 saturated hydrocarbon which is branched or
  • the solvent includes a C 5 -C 8 aliphatic hydrocarbon or mixtures
  • a preferred aliphatic hydrocarbon solvent over other known precipitation polymerization solvents is selected from heptane and cyclohexane.
  • Heptane the most preferred solvent, provides high yields of a precipitate of the desired copolymer composition as a fine white powder which is easy to filter and dry. This advantageous result is surprising since vinyl pyrrolidone itself readily homopolymerizes in heptane to produce gummy products.
  • Suitable secondary alcohols for use as a cosolvent herein have the formula R 1 R 2 CHOH, where R 1 and R 2
  • R 1 and R 2 are independently lower alkyl, preferably C 1 -C 6 , and, most preferably R 1 and R 2 are metnyl, i.e. isopropanol.
  • the amount of solvent used in the process of the invention should be sufficient to dissolve an appreciable amount of the reactants and to maintain the copolymer precipitate in a stirrable state at the end of the
  • reaction mixture preferably 15-20% solids, is maintained in the reaction mixture.
  • the precipitation polymerization process of the invention is carried out in the presence of a
  • polymerization initiator preferably a free radical
  • a peroxy ester e.g.
  • initiators such as acylperoxides, alkyl peroxides and azo-nitriles, known in the art or described in the
  • the amount of such initiator may vary widely;
  • the initiator may be precharged or added during the polymerization run.
  • the reaction temperature may vary widely; generally the reactants are maintained at about 50°-150°C, preferably 60°-70°C., during the polymerization. Pressure usually is kept at atmospheric pressure, although higher and lower pressures may be used as well.
  • the reaction mixture should be stirred vigorously under an inert atmosphere, e.g. nitrogen, during the polymerization.
  • a stirring rate of about 400-600 rpm in a 1-liter lab reactor is quite adequate to effect the desired polymerization and to keep the precipitate in a stirrable state during the polymerization.
  • the precipitation polymerization process of the invention may be carried out by first precharging a suitable reactor with a predetermined amount of a vinyl lactam in the solvent mixture of aliphatic hydrocarbon solvent and secondary alcohol, and heating the solution to a desired reaction temperature while stirring vigorously under an inert gas atmosphere. The initiator is then charged into the reactor. Then a selected amount of the polymerizable carboxylic acid, e.g. acrylic acid,
  • the reaction mixture is admitted into the reactor over a period of time, generally about an hour or more. Then the reaction mixture is held for an additional period of time for polymerization to occur. Finally, the mixture is cooled to room temperature. Filtering, washing with solvent, and drying provides the copolymer in yields approaching quantitative, and, substantially, in a
  • composition predetermined by the weight ratio of monomers introduced into the reactor.
  • the aliphatic hydrocarbon solvent and secondary alcohol can be precharged into the reactor, purged with nitrogen, heated to reaction temperature, the initiator added, and then separate streams of the vinyl lactam monomer, the acrylic acid monomer and optional comonomer are introduced over a period of time into the precharged reactor.
  • the polymers of the invention are generally characterized by their having high average molecular weights, low hygroscopicity, high glass transition temperatures, and exhibiting polyelectrolyte behavior in water.
  • N-vinylpyrrolidone and acrylic acid (in amounts given in Tables 1, 2 & 3) were fed into the reactor over a period of 4 hours. After completion of feeding of N-vinyl
  • Water insoluble vinyl pyrrolidone/acrylic acid (VP/AA) copolymers such as made herein, are important coating and textile sizing agents which are compatible with monovalent inorganic salts, plasticizers and many soluble gums and resins and which possess excellent moisture resistance. These copolymers are also useful in adhesive formulations and display good anti-deposition properties for reduced soiling of textiles. Additionally, hard, transparent films of these copolymers. can be cast for use in cramps or as water proof coatings on paper, metal, textile and plastic surfaces.
  • a solubilizing composition for normally water insoluble copolymers of vinyl pyrrolidone and acrylic acid which comprises a mixture of water and an oxygen-containing solubilizing agent in a critical weight ratio of between about 5:1 and about 1:3, preferably between about 2:1 and about 1:1.5.
  • solubilizing agents which are contemplated for this invention are oxygen-containing compounds having an oxygen to carbon ratio of from about 1:1 to about 0.1:1,
  • Suitable solvents include methanol, ethanol, isopropanol, acetone, ethylene glycol, methyl cellosolve and tetrahydrofuran and mixtures thereof. Of this group, the organic solvents or their mixtures which boil below 125°C. are more desireable and ethanol and isopropanol are most preferred.
  • the weight ratio of solvent to polymer can vary between about 20:1 and about 1:1, however a ratio between about 10:1 and about 4:1 is most desirable.
  • Solutions of the present copolymers are formed by agitating the polymeric product in the water/solvent mixture for a period of from about 0.5 to about 8 hours at a temperature of from about 20° to about 50°C., preferably under ambient conditions until a desired amount of polymer is dissolved.
  • stable polymer solutions containing up to 40 wt. % of dissolved polymer can be obtained.
  • the prepared solutions can be coated on a surface and cured at low temperature by techniques, without damage to the substrate. Further, the resulting anionic VP/AA polymeric coatings, which retain hydrogen bonding

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

Abstract

L'invention concerne un procédé de polymérisation par précipitation destiné à produire des copolymères d'un lactame de vinyle et d'un acide carboxylique polymérisable dans un mélange en cosolvant d'un solvant d'hydrocarbure aliphatique, de préférence, l'heptane ou le cyclohexane, et d'un alcool secondaire, de préférence l'isopropanol. Les copolymères ainsi obtenus et autres copolymères normalement insolubles dans l'eau, peuvent être solubilisés dans un mélange d'eau et d'un composé aliphatique contenant de l'oxygène.
PCT/US1993/001363 1992-03-16 1993-02-16 Polymerisation par precipitation de copolymeres d'un lactame de vinyle et d'un acide carboxylique polymerisable et solubilisation de ceux-ci Ceased WO1993019098A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US851,707 1977-11-15
US07/851,707 US5191043A (en) 1992-03-16 1992-03-16 Precipitation polmerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid having a molecular weight of less than 20,000 in a cosolvent mixture of an aliphatic hydrocarbon solvent and isopropanol
US07/862,147 US5219906A (en) 1992-04-02 1992-04-02 Low boiling solubilizer for vinyl pyrrolidone/acrylic acid copolymers
US862,147 1992-04-02

Publications (1)

Publication Number Publication Date
WO1993019098A1 true WO1993019098A1 (fr) 1993-09-30

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PCT/US1993/001363 Ceased WO1993019098A1 (fr) 1992-03-16 1993-02-16 Polymerisation par precipitation de copolymeres d'un lactame de vinyle et d'un acide carboxylique polymerisable et solubilisation de ceux-ci

Country Status (2)

Country Link
AU (1) AU3668693A (fr)
WO (1) WO1993019098A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2456807A1 (de) * 1974-11-30 1976-06-10 Basf Ag Verfahren zur herstellung von polymerisaten des vinylpyrrolidons
US4058655A (en) * 1975-03-29 1977-11-15 Basf Aktiengesellschaft Manufacture of low molecular weight poly-N-vinylpyrrolidone-2
US4177345A (en) * 1974-07-10 1979-12-04 Schweiger Richard Georg Process for preparing a sulfate ester of a polyhydroxy polymer
US4520180A (en) * 1982-09-20 1985-05-28 Gaf Corporation Polymerization of vinylpyrrolidone to various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate
US4956115A (en) * 1989-05-23 1990-09-11 Hoechst Celanese Corporation Water borne solvent strippers
US5011895A (en) * 1990-06-04 1991-04-30 Gaf Chemicals Corporation Precipitation polymerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid using sub-surface feeding

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4177345A (en) * 1974-07-10 1979-12-04 Schweiger Richard Georg Process for preparing a sulfate ester of a polyhydroxy polymer
DE2456807A1 (de) * 1974-11-30 1976-06-10 Basf Ag Verfahren zur herstellung von polymerisaten des vinylpyrrolidons
US4058655A (en) * 1975-03-29 1977-11-15 Basf Aktiengesellschaft Manufacture of low molecular weight poly-N-vinylpyrrolidone-2
US4520180A (en) * 1982-09-20 1985-05-28 Gaf Corporation Polymerization of vinylpyrrolidone to various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate
US4956115A (en) * 1989-05-23 1990-09-11 Hoechst Celanese Corporation Water borne solvent strippers
US5011895A (en) * 1990-06-04 1991-04-30 Gaf Chemicals Corporation Precipitation polymerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid using sub-surface feeding

Also Published As

Publication number Publication date
AU3668693A (en) 1993-10-21

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