Claims
- 1. Polycarboxylic acid salts corresponding to the following general formula
- X--NHCO--Y--COO.sup..crclbar.).sub.n nM.sup..sym.
- in which
- X represents the residue of a hydrophobic, linear or branched vinyl oligomer having an average molecular weight M.sub.n of from 200 to 5000,
- Y is the 1,2-vinylene, 1,2-ethylene, 1,3-propylene, 1,2-phenylene, 1,2-cyclohexene-4-ylene or 1,2-cyclohexylene group,
- n is a number of from 1.4 to 3.0,
- M represents an alkali metal, an ammonium, C.sub.1 -C.sub.4 alkylammonium or C.sub.2 -C.sub.3 hydroxyalkylammonium group.
- 2. Polycarboxylic acid salts according to claim 1 wherein X is the residue of an oligobutadiene or an oligoisoprene.
- 3. Polycarboxylic acid salts according to claim 1 wherein S is the residue of a hydrogenated oligobutadiene or oligoisoprene.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 3643792 |
Dec 1986 |
DEX |
|
Parent Case Info
This invention relates to polycarboxylic acids and salts of polycarboxylic acids corresponding to the following general formula
The present invention also relates to the application of the compounds corresponding to formula I as surfactants and emulsifiers in aqueous systems.
Examples of the vinyl oligomers on which X is based are oligobutadienes and oligoisoprenes and also the corresponding products with partly or completely hydrogenated double bonds, oligomers of ethylene, propene, styrene, vinyl esters containing from 2 to 4 carbon atoms in the carboxylic acid part, (cyclo)aliphatic esters of (meth)acrylic acid containing from 1 to 12 carbon atoms in the alcohol component, triethoxyvinyl silane or trimethyl vinyl silane.
Examples of M are sodium, potassium, ammonium, mono-, di- or trimethylammonium, mono-, di- or tri-(hydroxyethyl)ammonium or mono- or di-(hydroxypropyl)-ammonium.
The present invention also relates to the use of the polymeric emulsifiers for the production of emulsion polymers, more especially graft bases for improved high-impact thermoplasts.
The compounds corresponding to formula I are produced in known manner by reacting amino-terminated vinyl oligomers corresponding to the following formula
X and n are as defined above, with dicarboxylic acid anhydrides corresponding to the following formula ##STR1## in which Y is as defined above, at temperatures of from 20.degree. to 120.degree. C. and preferably at temperatures of from 40.degree. to 70.degree. C. and optionally in the presence of inert solvents in a molar ratio of at least 1:n, after which the reaction products obtained are optionally neutralized with alkali hydroxides, ammonia, C.sub.1 -C.sub.4 alkylamines or C.sub.2 -C.sub.3 hydroxyalkylamines.
The amino-terminated vinyl oligomers corresponding to formula II, which are referred to hereinafter as aminotelechelic vinyl oligomers, are known.
Suitable aminotelechelic oligomers are, for example, the products described in DOS No. 2 151 848, providing they are insoluble in water, and also aminotelechelic oligopropylenes, oligobutadienes, oligoisoprenes and aminotelechelic oligobutadienes and oligoisoprenes of which the double bonds have been complete or partly hydrogenated.
The production of aminotelechelic vinyl oligomers such as these is known and comprises polymerizing vinyl monomers using large quantities of nitrile-containing aliphatic azoinitiators to form nitrile-terminated vinyl oligomers which are converted into the aminotelechelic vinyl oligomers of formula II by catalytic hydrogenation of the terminal nitrile groups to primary amino groups.
U.S. Pat. No. 2,561,068 for example describes inter alia the production of low molecular weight polybutadienes, polyisoprenes and polypropylenes containing approximately two terminal nitrile groups by batch polymerization of the corresponding monomers using large quantities of nitrile-containing aliphatic azo-initiators.
The catalytic hydrogenation of the terminal nitrile groups of products such as these to primary terminal amino-groups is described in U.S. Pat. No. 2,647,146. The wax-like consistency of the diamine prepared in Example 2 of this patent suggests at least partial hydrogenation of the double bonds of the oligobutadiene.
The nitrilotelechelic oligobutadienes of oligoisoprenes are preferably produced continuously in a flooded stirrer-equipped autoclave under pressures below 25 bar. The molecular weight of the oligomers may be regulated through the ratio of azodinitrile initiator to monomer. Suitable azodinitrile initiators are, for example, 2,2'-azobisisobutyonitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 1,1'-azodicyclopentanecarbonitrile, 1,1-azodicyclohexanecarbonitrile, 2,2'-azobiscyclopentylpropionitrile, 1,1'-azodicamphorcarbonitrile, 2,2'-azobis-(.beta.,.gamma.-dimethylvaleronitrile), 2,2'-azobis-2-phenylpropionitrile, 2,2'-azobis-2-benzylpropionitrile and 2,2'-azobis-2-(4-methoxyphenyl)-propionitrile.
Preferred initiators are AIBN, 2,2'-azobismethylbutyronitrile and 2,2'-azobis-(.alpha.,.gamma.-dimethylvaleronitrile).
Where AIBN is used as initiator, the preferred polymerization temperatures are in the range from 90.degree. to 130.degree. C. while the average residence times are from 1 to 6 hours.
Suitable nitrilotelechelic oligobutadienes and oligoisoprenes may of course also be produced by a feed process.
The terminal nitrile groups are hydrogenated in known manner by catalytic hydrogenation of the oligomer dissolved in a solvent, such as toluene for example. Raney cobalt for example is suitable for the selective hydrogenation of the nitrile groups; the formation of secondary and tertiary amino groups may be suppressed by an addition of NH.sub.3.
The H.sub.2 pressure is preferably from 100 to 200 bar while the hydrogenation temperature is in the range from 100.degree. to 200.degree. C. With very long hydrogenation times or where Raney nickel is added to the Raney cobalt, it is also possible to hydrogenate the C--C--double bonds of the oligobutadienes or oligoisoprenes.
The production of aminotelechelic oligostyrenes, aminotelechelic oligoethylenes, aminotelechelic oligoacrylic acid ethyl ester, aminotelechelic oligomethacrylic acid methyl ester and aminotelechelic oligovinyl acetate is described in the Examples of DOS No. 2 151 848. The nitrilotelechelic starting products are produced by the process according to DOS No. 2 030 589. In addition, the production of dinitrilotelechelic oligostyrenes was described in detail by Konter, Bomer, Kohler and Heitz in Makromol, Chem. 182 (1981) 2619-2632. Suitable dicarboxylic acid anhydrides corresponding to formula III are, for example, succinic acid, glutaric acid, maleic acid and phthalic acid anhydride and also tetra- and hexahydrophthalic acid anhydride.
Suitable solvents for the reaction of the aminotelechelic vinyl oligomers of formula II with the dicarboxylic acid anhydrides of formula III are, for example, aliphatic or aromatic hydrocarbons, more especially toluene and xylene, aliphatic or aromatic halogenated hydrocarbons, such as for example methylene chloride, ethylene chloride or chlorobenzene, esters or ketones, such as for example ethyl acetate or acetone.
The aminotelechelic vinyl oligomers are preferably dissolved in the solvent and the dicarboxylic acid anhydrides added to the resulting solutions at the selected reaction temperature. The quantitative ratio between the components is selected so that, for every amine equivalent of the aminotelechelic vinyl oligomers, there is at least one equivalent of the dicarboxylic acid anhydrides; the dicarboxylic acid anhydrides may be used in a slight excess.
The reaction products are then neutralized, optionally after removal of the solvents by distillation, by addition of alkali hydroxides, ammonia, C.sub.1 -C.sub.4 alkylamines or C.sub.2 -C.sub.3 hydroxyalkylamines, preferably in the form of aqueous or alcoholic solutions.
The polymeric emulsifiers are used in quantities of from 0.2 to 20% by weight and preferably in quantities of from 1 to 10% by weight, based on the quantity of monomer.
They are suitable, for example, for the emulsion polymerization of butadiene, isoprene, chloroprene, styrene and styrenes substituted in the aromatic nucleus, .alpha.-methyl styrene, (meth)acrylic acid esters containing from 1 to 20 carbon atoms in the alcohol component, vinyl esters containing from 2 to 10 carbon atoms in the carboxylic acid component, ethylene, vinyl chloride, vinylidene chloride, acrylonitrile and methacrylonitrile and combinations of these monomers suitable for emulsion copolymerization. In addition, small quantities (approx. 0.1 to 10% by weight) of (meth)acrylic acid, (meth)acrylamide, maleic acid, itaconic acid, vinyl sulfonic acid, methallylsulfonic acid, vinyl phosphonic acid or acrylamido-2-methylpropanesulfonic acid (AMPS) may also be incorporated in order additionally to stabilize the emulsions. The polymeric emulsifiers according to the invention are preferably used for the polymerization of butadiene, isoprene and chloroprene and also for the copolymerization of butadiene-styrene, butadiene-acrylonitrile, ethylene-vinyl acetate, ethylene-vinyl chloride, styrene, butyl acrylate and styrene-acrylonitrile.
For the production of polybutadiene latices which are particularly suitable as graft bases for the production of high-impact thermoplasts of the ABS type, it is (particularly) preferred to use those polymeric emulsifiers of which the residue X consists of polybutadiene, polyisoprene or polyisoprene or polybutadiene of which the double bonds are completely or partly hydrogenated.
US Referenced Citations (4)
Foreign Referenced Citations (1)
| Number |
Date |
Country |
| 1495086 |
Aug 1967 |
FRX |
Patent Grant
4959419
