CA2014022A1

CA2014022A1 - Precipitation polymerization of copolymers of a vinyl lactam and a polymerizable carboxylic acid in an aliphatic hydrocarbon solvent

Info

Publication number: CA2014022A1
Application number: CA 2014022
Authority: CA
Inventors: Jenn S. Shih; Terry E. Smith; Robert B. Login
Original assignee: Individual
Current assignee: GAF Chemicals Corp; GAF Corp
Priority date: 1989-04-07
Filing date: 1990-04-06
Publication date: 1990-10-07
Also published as: EP0467959A4; EP0467959A1; WO1990012041A1; JPH04504870A

Abstract

PRECIPITATION POLYMERIZATION OF COPOLYMERS OF
A VINYL LACTAM AND A POLYMERIZABLE CARBOXYLIC ACID
IN AN ALIPHATIC HYDROCARBON SOLVENT

ABSTRACT OF THE DISCLOSURE

What is described herein is a precipitation polymerization process and copolymer products produced thereby. Polymerization is carried out in 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, in an aliphatic hydrocarbon solvent, particularly, a C3-C10 saturated hydrocarbon, which is branched or unbranched, cyclic or acylic and preferably, is heptane or cyclohexane.

Description

20~ 4022 ~ :

PRECIPITATION POLYMERIZATION OF CQPOLYMERS OF
VINYL LACTAM AND A POLYMERIZABLE CARBOXYLIC ACID
IN AN ALIPHATIC HYDROC~RBON SOLVENT

BACKGROUND OF THE INVENTION

l. Field of the Invention This invention relates to precipitation polymerization of copolymers of a vinyl lactam 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.

2. Description of the Prior Art Copolymers of vinyl lactams,- e.g. vinyl pyrrolidone (VP) or vinyl caprolactam (VCL), and polymerizable carboxylic acids, e.g. acrylic acid (AA) or methacrylic acid (MAA), have found application in the photographic industry, as coatings, as biological membranes, in drug release systems, as preservatives, in oil recovery processes, in immunochemicals, and in cosmetic materials.
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. Makromol.
Chem. 148, 205 (1971); and by Uelzmann, in J. Polymer Sci.
33, 377 (1958).

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The solution polymerization process is used when both reactant monomers and the copolymer product are soluble in a reaction solvent. However, this method suffers from the following disadvantages:
(1) Desirable compositions of the copolvmer 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:
(1) 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.
For these and other reasons, present solution polymerization and precipitation polymerization processes for making copolymers of a vinyl lactam and an acrylic acid have not been very successful on a commercial scale.
Accordingly, it is an object of this invention to provide an improved method of making copolymers of a vinyl lactam and a polymerizable carboxylic acid.

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201~02'~

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 i9 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 copoly~ers 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.

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SUMMARY OF THE INYENTION

What is described herein is a precipitation polymerization process and copolymer products produced thereby. 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 C3-C10 saturated, branched or unbranched, cyclic or acyclic, and preferably heptane or cyclohexane.
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 herein have a uni~ue set of physical and chemical properties which are advantageous for commercial use.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the invention, 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 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 201~2f~

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~-C10 saturated hydrocarbon which is branched or unbranched, cyclic or acyclic. Preferably the solvent is a C5-C8 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.

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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 50-150C., preferably 60-70C., 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.

Monomers Source Form Vinyl pyrrolidone GAF Liquid or Vinyl caprolactam Aldrich Solid Acrylic acidRohm and Haas Liquid or Methacrylic acidAldrich Liquid Initiator t-Butylperoxy Pennwalt Corp. Liquid; 75% solution pivalate (Lupersol 11) in mineral spirits 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 201~2 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, 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.
Alternatively, 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 acryl,c 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.
The 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.

a. Molecular Weight 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.

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b. HygroscoPicitY

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.

c. Glass Transition Temperature, Tg 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.

d. Solubility The copolymer exhibits very unusual solubility characteristic-: it is insoluble in aqueous acid solution of pH 3 but soluble in basic solution of pH 8.
Table I below illustrates the solubility characteristics of copolymers of different compositions in several aqueous and organic solvents.

201~22 TABLE I

P(VP/AA~ SOLUBILITY

WATER S
0.lN NaOH S S S S S S
ETHANOL PS
DMF S S S S S S
NMP S S S S S S
ACETONE
CHLOROFORM PS
TOLUENE
HEPTANE

SYMBOLS

P = Polymer VP = Vinyl Pyrrolidone AA = Acrylic Acid DMF = Dimethylformamide NMP = N-methylpyrrolidone W/W = Weight to weight M/M = Mole to mole S = Soluble I = Insoluble PS = Partly soluble ~ ~ r ~ ~ ~ ~

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e. Viscosity 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.

The invention will be illustrated hereinafter by the following working examples.

1. PREPARATION OF COPOLYMERS OF VINYL PYRROLIDONE AND
ACRYLIC ACID

A l-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 65C. during 20 minutes and held there for 30 min., while stirring under nitrogen gas. Then 260 microliter (0.3 g.) of t-butylperoxy pivalate initiator was added. Then 25 g. of acrylic acid was admitted during a period of 1 hour and the mixture was held for an hour. Then an additional 140 microliter (0.2 g.) of initiator was admitted into the reaction mixture and the solution was maintained at 65C.
with stirring for another 2 hours. Then another 100 microliter of initiator was added and the mixture held for 2 hours.

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The reaction product then was cooled to room temperature during a period of about an hour. A fine white powder precipitate of copolymer product was obtained which was filtered, washed twice with heptane and dried overnight at 100C. and then overnight again in a vacuum oven at 100 C .
A 75:25 VP:AA copolymer (wt. ratio) was obtained in 97% yield.

PROPERTIES OF COPOLYMER PRODUCT

K-VALUE AND AVERAGE MOLECULAR WEIGHT

The product had a K-value of about 70 (1%
copol~mer in 0.1 N NaOH and 0.2N LiNo3 aqueous solution).
The weight average molecular weight of the copolymer was about 180,000, as measured by light scattering in dimethylformamide solvent.

The procedure of Example 1 was followed using g9, 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.

20~ 4~22 The procedure of Examples 1-6 was followed using cyclohexane and hexane in place of heptane, with similar results.

. . _ The procedure of Examples 1-8 was repeated using vinyl caprolactam in place of vinyl pyrrolidonè to produce the corresponding vinyl caprolactam/acrylic acid copolymer in 95-100% yield.

The procedure of Examples 1-8 was repeated using methacrylic acid in place of acrylic acid to produce the corresponding vinyl pyrrolidone/methacrylic acid copolymer in 95-100% yield.

The procedure of Example 1 was followed to compare the efect of usinq different reaction solvents at various copolymer compositions. The results are shown in Table 2 below.

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H O O 1~ .C ~D ~1 0 3 N _I ~1 _ _ O O t~ X
~ .~ O ~

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h O
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,~ ,~ h~ ~ N J~ h a~ ' u~ ~ ~ ~0 ~ ~ U~
P. E~ ~ m O
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The results in comparative Examples 11-14 above show that heptane is the solvent of choice in the precipitation polymerization of copolymers of vinyl pyrrolidone and acrylic acid. Successful products were obtained in heptane over the entire compositional range of monomers, whereas failure in one or more respects was evident with either tetrahydrofuran, acetone or benzene as the solvent.
The 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.
While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, ~-it is intended to be bound only by the following claims, in which:

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Claims

1. A precipitation polymerization process for making copolymers of a vinyl lactam and a polymerizable carboxylic acid which comprises copolymerizing a vinyl lactam and a polymerizable carboxylic acid in an aliphatic hydrocarbon solvent in the presence of a polymerization initiator.

2. A method according to claim 1 wherein said solvent is a C3-C10, saturated hydrocarbon which is branched or unbranched, cyclic or acyclic.

3. A method according to claim 2 wherein said solvent is a C5-C8 compound.

4. A method according to claim 1 in which said aliphatic hydrocarbon is heptane or cyclohexane.

5. A process according to claim 2 wherein said solvent is heptane.

6. A process according to claim 1 in which said vinyl lactam is vinyl pyrrolidone or vinyl caprolactam.

7. A process according to claim 1 in which the polymerizable carboxylic acid monomer is acrylic acid, methacrylic acid, itaconic acid, maleic acid or crotonic acid.

8. A process according to claim 1 in which the polymerization initiator is a free radical initiator.

9. A process according to claim 5 wherein said initiator is a peroxy ester.

10. A process according to claim 6 wherein said vinyl lactam is vinyl pyrrolidone.

11. A process according to claim 7 wherein said monomer is acrylic acid or methacrylic acid.

12. A process according to claim 11 wherein the weight ratio of vinyl lactam to an acrylic acid in the reaction mixture ranges from 1:99 to 99:1.

13. A process according to claim 1 which includes the steps of precipitating the copolymer as a powder from solution, filtering and drying.

14. A process according to claim 1 wherein the polymerization is carried out at about 50°-150°C., under an inert gas, with agitation.

15. A process according to claim 13 wherein the copolymer is precipitated from the solvent as a white powder.

16. A process according to claim 1 wherein the solvent is present in an amount sufficient to keep the reactants in solution during the polymerization and to keep the copolymer precipitate in a stirrable state.

17. A process according to claim 1 wherein up to about 40% solids are present in the reaction mixture.

18. A process according to claim 17 wherein about 15 to 20% solids are present during the polymerization.

19. A process according to claim 1 wherein the copolymer product is characterized by having low hygroscopicity, a high glass transition temperature, a high average molecular weight, and a substantial absence of by-products.

20. A process according to claim 1 wherein the precipitation polymerization reaction is carried out by precharging a solution of the vinyl lactam in the aliphatic hydrocarbon solvent, then adding the initiator, and then feeding the carboxylic acid thereto.

21. A process according to claim 20 wherein the carboxylic acid is added over a predetermined period of time while stirring the reaction mixture.

22. A process according to claim 12 wherein the reaction mixture contains predominately vinyl pyrrolidone or vinyl caprolactam.

23. A process according to claim 1 wherein the aliphatic hydrocarbon solvent is precharged into a reactor, purged with an inert gas, heated to reaction temperature, the initiator added, and then separate streams of the vinyl lactam monomer and the carboxylic acid monomer are introduced into the reactor over a period of time.

24. Copolymers of a vinyl lactam and a polymerizable carboxylic acid having a compositional weight ratio of vinyl lactam to carboxylic acid of 1:99 to 99:1, a high average molecular weight, which are white powders insoluble in heptane over said range, low hygroscopicity, high glass transition temperatures, exhibiting polyelectrolyte behavior in water, solubility in an aqueous basic solution of pH 8, and insolubility in an aqueous acid solution of pH 3.

25. Copolymers according to claim 24 wherein said vinyl lactam is selected from vinyl pyrrolidone and vinyl caprolactam, and said carboxylic acid monomer is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crotonic acid.

26. Copolymers according to claim 25 wherein said vinyl lactam predominates in said copolymer.

27. Copolymers according to claim 24 wherein said polymerizable carboxylic acid is acrylic acid or methacrylic acid.