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WO1990012041A1 - Polymerisation par precipitation de copolymeres d'un lactame de vinyl et d'un acide carboxylique polymerisable dans un solvant d'hydrocarbure aliphatique - Google Patents

Polymerisation par precipitation de copolymeres d'un lactame de vinyl et d'un acide carboxylique polymerisable dans un solvant d'hydrocarbure aliphatique Download PDF

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Publication number
WO1990012041A1
WO1990012041A1 PCT/US1990/001561 US9001561W WO9012041A1 WO 1990012041 A1 WO1990012041 A1 WO 1990012041A1 US 9001561 W US9001561 W US 9001561W WO 9012041 A1 WO9012041 A1 WO 9012041A1
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WIPO (PCT)
Prior art keywords
process according
acid
vinyl
carboxylic acid
vinyl lactam
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Application number
PCT/US1990/001561
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English (en)
Inventor
Jenn S. Shih
Terry E. Smith
Robert B. Login
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Gaf Chemicals Corporation
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Filing date
Publication date
Application filed by Gaf Chemicals Corporation filed Critical Gaf Chemicals Corporation
Publication of WO1990012041A1 publication Critical patent/WO1990012041A1/fr

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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
    • 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
    • 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
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • 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

Definitions

  • This invention relates to precipitation polymerization of copolymers of a vinyl lacta and a polymerizable carboxylic acid, and, more particularly, to such copolymers having a wide compositional range, prepared in high yield, as a white powder, which can be filtered and dried easily, and which have advantageous physical properties.
  • Copolymers of vinyl lactams e.g. vinyl pyrrolidone (VP) or vinyl caprolactam (VCL)
  • polymerizable carboxylic acids e.g. acrylic acid (AA) or methacrylic acid (MAA)
  • AA acrylic acid
  • MAA methacrylic acid
  • Solution polymerization and precipitation polymerization are two available methods for making these copolymers; see in U.S. Patent Nos. 3,044,873; 3,862,915; and 4,283,384; and articles by Takeski, in J. Makro ol. Chem. 148, 205 (1971); and by Uelzmann, in J. Polymer Sci. 33, 377 (1958).
  • the solution polymerization process is used when both reactant monomers and the copolymer product are soluble in a reaction solvent.
  • this method suffers from the following disadvantages:
  • 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 colored; (4) 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, acetone and methyl ethyl ketone are known precipitation polymerization solvents. Unfortunately, these solvents have one or more of the following disadvantages:
  • Useful copolymer compositions may not be insoluble in a selected reaction solvent, which restricts the process to a narrow copolymer compositional range; (2) the copolymer may precipitate only as a gelatinous mass which is difficult to filter; (3) low yields of polymer may be obtained; and (4) the solvent may be toxic.
  • Another object of this invention is to provide an improved method of making copolymers of a vinyl lactam and a polymerizable carboxylic acid.
  • Another object of the present invention is to provide an effective reaction solvent in a precipitation polymerization process which will provide copolymers having advantageous physical properties, including low hygroscopicity, high glass transition temperatures, a high average molecular weights, polyelectrolyte behavior.
  • Yet another object herein is to provide a precipitation polymerization process in which the copolymers will precipitate in high yield as a fine white powder which is insoluble in the reaction solvent over the entire compositional range of the copolymer.
  • a feature of the invention is the provision of a precipitation polymerization process for making copolymers of a vinyl lactam and a polymerizable carboxylic acid in which an aliphatic hydrocarbon is used as the reaction solvent.
  • Another feature of the invention is the provision of copolymers of a vinyl lactam and a polymerizable carboxylic acid made by a precipitation polymerization process in which the reaction solvent is selected from heptane and cyclohexane.
  • Still another feature of the invention is the provision of copolymers of a vinyl lactam and a polymerizable carboxylic acid over the complete compositional range of monomers, which copolymers are characterized by having a high average molecular weight, low hygroscopicity, a high glass transition temperature, being a white powder, exhibiting polyelectrolyte behavior, and which are soluble in an aqueous basic solution of pH 8 and insoluble in an aqueous acid solution of pH 3.
  • the polymerization is carried out in 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 an aliphatic hydrocarbon solvent, preferably, a C 3 -C 10 saturated, branched or unbranched, cyclic or acyclic, and preferably heptane or cyclohexane.
  • a vinyl lactam e.g. vinyl pyrrolidone or vinyl caprolactam
  • a polymerizable carboxylic acid e.g. acrylic acid or methacrylic acid
  • a polymerization initiator e.g. a free radical initiator
  • 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.
  • copolymers herein have a unique set of physical and chemical properties which are advantageous for commercial use.
  • copolymers of a vinyl lactam and a polymerizable carboxylic acid are made by a precipitation polymerization process in an aliphatic hydrocarbon solvent in the presence of a polymerization initiator.
  • Suitable vinyl la ⁇ tams 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. from 1-99 weight percent vinyl lactam and 99:1 weight percent of acrylic acid. Accordingly, 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.
  • the reaction solvent of the invention suitably is a C 3 -C 10 saturated hydrocarbon which is branched or unbranched, cyclic or acyclic.
  • the solvent is a C 5 -Cg aliphatic hydrocarbon or mixtures thereof.
  • 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.
  • 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 polymerization. Generally, up to about 40% solids, 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 initiator, and most suitably, a peroxy ester, e.g. t-butylperoxy pivalate, although other free radical initiators such as acylperoxides, alkyl peroxides and azo-nitriles, known in the art or described in the aforementioned references, may be used as well.
  • a polymerization initiator preferably a free radical initiator, and most suitably, a peroxy ester, e.g. t-butylperoxy pivalate, although other free radical initiators such as acylperoxides, alkyl peroxides and azo-nitriles, known in the art or described in the aforementioned references, may be used as well.
  • the amount of such initiator may vary widely; generally about 0.2-5.0% is used, based on the weight of total monomers charged.
  • 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 monomers and initiator used herein are commercially available materials, as described below.
  • 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 aliphatic hydrocarbon solvent, 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.
  • a selected amount of the polymerizable carboxylic acid e.g. acrylic acid
  • the reaction mixture is held for an additional period of time for polymerization to occur.
  • 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 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 and the acrylic acid monomer are introduced over a period of time into the precharged reactor.
  • Other process variations will be apparent to those skilled in the art.
  • copolymers 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, as described below.
  • the weight average molecular weight for a 75:25 wt. ratio VP:AA copolymer for example, having a Fikentscher K-value of about 70, was about 180,000, as determined by light scattering.
  • the hygroscopicity of the copolymers is lower than the weighted average of the homopolymers. This effect is maximized for copolymers, for example, having a VP:AA mole ratio of about 1:1, where the hydroscopicity may be actually lower than the value of either homopolymer.
  • Hygroscopicity is measured by the equilibrium moisture pickup of the copolymer powders at 50% relative humidity.
  • This property shows the effect of strong hydrogen bonding in the copolymer which causes a strong positive deviation from typical behavior, which is most prominent at a vinyl lactam:acrylic or methacrylic acid mole ratio of about 1:1.
  • the copolymer exhibits very unusual solubility characteristics: it is insoluble in aqueous acid solution of pH 3 but soluble in basic solution of pH 8.
  • Table I illustrates the solubility characteristics of copolymers of different compositions in several aqueous and organic solvents.
  • NMP N-methylpyrrolidone
  • the viscosity in water is pH dependent in the pH range of about 4-12.
  • the maximum viscosity occurs at a pH of about 8-9.
  • Dilute aqueous solutions exhibit polyelectrolyte behavior.
  • a 1-liter, 4-necked reaction kettle was equipped with a mechanical stirrer, thermometer, dropping funnel and a nitrogen purge tube.
  • the reactor was precharged with 75 g. of vinyl pyrrolidone in 500 g. of heptane.
  • the solution then was heated to 65°C. during 20 minutes and held there for 30 min. , while stirring under nitrogen gas.
  • 260 microliter (0.3 g.) of t-butylperoxy pivalate initiator was added.
  • 25 g. of acrylic acid was admitted during a period of 1 hour and the mixture was held for an hour.
  • an additional 140 microliter (0.2 g.) of initiator was admitted into the reaction mixture and the solution was maintained at 65°C. with stirring for another 2 hours.
  • the product had a K-value of about 70 (1% copolymer in 0.1 N NaOH and 0.2N LiN0 3 aqueous solution).
  • the weight average molecular weight of the copolymer was about 180,000, as measured by light scattering in dimethylformamide solvent.
  • Example 1 The procedure of Example 1 was followed using 99, 95, 50, 25 and 1 g. of vinyl pyrrolidone and 1, 5, 50, 75 and 99 g. of acrylic acid, to produce the corresponding 99:1, 95:5, 50:50, 25:75 and 1:99 wt. ratio VP:AA copolymers.
  • Example 2 The procedure of Example 1 was followed to compare the effect of using different reaction solvents at various copolymer compositions. The results are shown in Table 2 below.
  • copolymer products of the invention find particular utility in such applications as thickeners, adhesives, in paper manufacture and coatings thereon, in ion-exchange resins and membranes, in controlled release polymers, in textile sizings, as dispersants, in oil recovery chemicals, in surface cleaning, as anti-scaling agents in boilers, and in personal care products.

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  • 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

L'invention concerne un procédé de polymérisation par précipitation et des produits copolymères ainsi produits. On procède à la polymérisation dans un mélange de réaction d'un lactame de vinyle, par exemple une pyrrolidone de vinyle ou un caprolactame de vinyle, et d'un acide carboxylique polymérisable, par exemple de l'acide acrylique ou de l'acide méthacrylique, en présence d'une amorce de polymérisation, dans un solvant d'hydrocarbure aliphatique notamment un hydrocarbure saturé contenant 3 à 10 atomes de carbone, lequel est ramifié ou non, cyclique ou acyclique et de préférence est un heptane ou un cyclohexane.
PCT/US1990/001561 1989-04-07 1990-03-26 Polymerisation par precipitation de copolymeres d'un lactame de vinyl et d'un acide carboxylique polymerisable dans un solvant d'hydrocarbure aliphatique WO1990012041A1 (fr)

Applications Claiming Priority (2)

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US33442089A 1989-04-07 1989-04-07
US334,420 1989-04-07

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WO1990012041A1 true WO1990012041A1 (fr) 1990-10-18

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EP (1) EP0467959A4 (fr)
JP (1) JPH04504870A (fr)
CA (1) CA2014022A1 (fr)
WO (1) WO1990012041A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5191043A (en) * 1992-03-16 1993-03-02 Isp Investments Inc. 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
EP0532536A1 (fr) * 1990-06-04 1993-03-24 Isp Investments Inc. Polymerisation par precipitation de copolymeres d'un lactame vinylique et d'un acide carboxylique polymerisable par acheminement sous la surface
US5252611A (en) * 1992-07-20 1993-10-12 Isp Investments Inc. Controlled release tablets including strongly swellable, moderately crosslinked polyvinylpyrrolidone
WO1994001079A1 (fr) * 1992-07-14 1994-01-20 Basf Aktiengesellschaft Produits pour le traitement des cheveux renfermant des copolymerisats servant d'agents filmogenes
WO2005032701A3 (fr) * 2003-09-19 2005-07-21 Basf Ag Utilisation de copolymeres contenant du n-vinyllactame pour produire des membranes fonctionnalisees
WO2010113176A3 (fr) * 2009-03-31 2010-11-18 Reliance Life Sciences Pvt. Ltd. Nouveaux copolymères pour système d'administration à libération contrôlée

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011511117A (ja) * 2008-02-01 2011-04-07 ビーエーエスエフ ソシエタス・ヨーロピア 直鎖状沈殿ポリマー

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036788A (en) * 1975-02-11 1977-07-19 Plastomedical Sciences, Inc. Anionic hydrogels based on heterocyclic N-vinyl monomers
US4190718A (en) * 1975-05-27 1980-02-26 Gaf Corporation Process for increasing molecular weight of vinylpyrrolidone polymer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284414A (en) * 1963-05-23 1966-11-08 Dow Chemical Co Process for preparing water-soluble copolymers of acrylic acids and n-vinyl heterocyclic monomers in a halogenated hydrocarbon
US4600759A (en) * 1984-12-10 1986-07-15 Gaf Corporation Process for making copolymers of vinylpyrrolidone and maleic anhydride

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036788A (en) * 1975-02-11 1977-07-19 Plastomedical Sciences, Inc. Anionic hydrogels based on heterocyclic N-vinyl monomers
US4190718A (en) * 1975-05-27 1980-02-26 Gaf Corporation Process for increasing molecular weight of vinylpyrrolidone polymer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Journal of polymer Science, Vol. 33 pp. 377-379, 1958 "Copolyers of Acrylic Acid and N-vinyl pyrrolidone-2". *
See also references of EP0467959A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0532536A1 (fr) * 1990-06-04 1993-03-24 Isp Investments Inc. Polymerisation par precipitation de copolymeres d'un lactame vinylique et d'un acide carboxylique polymerisable par acheminement sous la surface
EP0532536A4 (en) * 1990-06-04 1993-04-21 Isp Investments Inc. Precipitation polymerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid using sub-surface feeding
US5191043A (en) * 1992-03-16 1993-03-02 Isp Investments Inc. 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
WO1994001079A1 (fr) * 1992-07-14 1994-01-20 Basf Aktiengesellschaft Produits pour le traitement des cheveux renfermant des copolymerisats servant d'agents filmogenes
US5252611A (en) * 1992-07-20 1993-10-12 Isp Investments Inc. Controlled release tablets including strongly swellable, moderately crosslinked polyvinylpyrrolidone
WO2005032701A3 (fr) * 2003-09-19 2005-07-21 Basf Ag Utilisation de copolymeres contenant du n-vinyllactame pour produire des membranes fonctionnalisees
WO2010113176A3 (fr) * 2009-03-31 2010-11-18 Reliance Life Sciences Pvt. Ltd. Nouveaux copolymères pour système d'administration à libération contrôlée

Also Published As

Publication number Publication date
EP0467959A1 (fr) 1992-01-29
JPH04504870A (ja) 1992-08-27
EP0467959A4 (en) 1992-09-23
CA2014022A1 (fr) 1990-10-07

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