Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-06-10
2003-03-11
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S259000, C526S264000, C526S272000, C526S318300, C526S318400, C526S318600, C526S328500, C526S332000, C526S335000, C526S347000
Reexamination Certificate
active
06531563
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a polymer based on a conjugated diene and dienophilic component, to its production and to its use.
2. Discussion of Related Art
Such polymers are known. Thus, Japanese patent JA 93/1121 describes a copolymer produced from a maleic anhydride, a conjugated diene and an aliphatic monoolefin. Butadiene was used as the conjugated diene and isobutene as the aliphatic monoolefin. The polymerization was carried out in the presence of a peroxide at temperatures of around 150° C. The molecular weight Mw is in the range from 500 to 50,000.
SUMMARY OF THE INVENTION
In Bull. Chem. Soc. Japan 40 (1967), pages 1272 to 1273, Iwamoto and Yuguchi describe alternating copolymers of 2,4-hexadiene and maleic anhydride. The polymerization is initiated by heating and/or by radical-forming initiators. It may be carried out both in bulk and in solution. The yields are of the order of 2 to 97%.
Japanese patent JA 93/295041 also describes a copolymer of a conjugated diene and maleic anhydride. Conjugated dienes are butadiene or isoprene. The catalyst used is an acetyl acetonate with metals of Group VII or Group VIII. The polymer is used for coating, for surface treatment, for sealing and as an adhesive.
These known polymers have the following disadvantages:
DETAILED DESCRIPTION OF THE INVENTION
On the one hand, both monomers are based on petrochemicals and thus lead to a more negative ecological assessment by comparison with the use of monomers based on renewable raw materials. On the other hand, the range of raw materials for petrochemical conjugated dienes is limited to butadiene and simple derivatives or homologs thereof. The use of these short-chain dienes represents not only a process-related disadvantage on account of the volatility and ready inflammability of these monomers. From the chemical perspective, too, these compounds only allow minor variations in the chemical properties of the polymers. For example, no reactions with functionalized dienes are possible or indeed described.
Reaction products of maleic anhydride with fatty acids containing conjugated double bonds are also known. However, the reactions involved here are additions based on the Diels-Alder Reaction. This reaction is described, for example, by Behr and Handwerk in Sci. Technol. 94 (1992), pages 206 to 208.
The problem addressed by the present invention was to provide new high-performance polymers based on renewable raw materials by an economic method.
The solution provided by the invention is defined in the claims and lies essentially in a polymer obtainable from:
A) at least one fatty acid with a conjugated C—C double bond or derivatives thereof,
B) at least one alkene or alkine component containing electron acceptor substituents and optionally
C) at least one copolymerizable alkene component with no electron acceptor substituents.
Component A
The “fatty acid containing a conjugated C—C double bond” (component A) is an aliphatic unsaturated carboxylic acid containing 6 to 32 and, more particularly, 16 to 24 carbon atoms which has two or more conjugated C—C double bonds. This so-called conjuene fatty acid may be used in functionalized form as an ester or amide for the polymerization reaction.
One preferred embodiment of the invention is characterized by the use of esters or partial esters of the conjuene fatty acids with monohydric or polyhydric alcohols. “Alcohols” are understood to be hydroxyl derivatives of aliphatic or alicyclic, saturated or unsaturated, linear or branched hydrocarbons. Both monohydric and dihydric alcohols or higher alcohols may be used. Specific examples from the low molecular weight range include methanol, ethanol, propanol, butanol, pentanol, decanol, octadecanol, 2-ethylhexanol, 2-octanol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, hexamethylenediol, octamethylenediol, neopentyl glycol, 1,4-bis-hydroxymethyl cyclohexane, Guerbet alcohol, 2-methylpropane-1,3-diol, hexane-1,2,6-triol, glycerol, trimethylol propane, trimethylol ethane, penta-erythritol, sorbitol, formitol, methyl glycoside, butylene glycol, reduced dimer and trimer fatty acids and higher polyethylene, polypropylene and polybutylene glycols. Alcohols derived from colophony resins, such as abietyl alcohol, may also be used for the esterification. OH-containing tertiary amines may also be used.
Other suitable derivatives of the conjuene fatty acids are amides which may be obtained by reaction with ammonia, primary and secondary amines or polyamines, for example with monoethanolamine, stearylamine, diethanolamine, ethylenediamine and hexamethylenediamine.
The “fatty acid containing a conjugated C—C double bond” may be obtained in various ways.
The conjugated double bond may also have been originally present (naturally occurring conjuene fatty acids).
The conjugated double bond may be formed by selective hydrogenation of fatty acids containing conjugated triple bonds (conjuene fatty acids by selective hydrogenation).
The conjugated double bond may also be formed by isomerization of so-called isolene fatty acids either thermally or by the action of catalysts (conjuene fatty acids by isomerization). For example, the isolated double bonds in linoleic, linolenic, arachidonic and clupanodonic acid are converted into conjugated double bonds by the action of catalysts. Specific isomerization catalysts are nickel on supports, transition metals
oble metals, tert.butyl hypochloride, iodine/iodide, sulfur dioxide, selenium/selenium-containing catalysts, metal complexes, alkali metals, treated clays, sulfur-containing catalysts, alkali metal alcoholates and alkali metal hydroxides.
In addition, the conjugated double bond may be formed by dehydration of hydroxyfatty acids either from hydroxy compounds already containing a correspondingly positioned double bond or from dihydroxyfatty acids. The dehydration of hydroxyfatty compounds to conjugated fatty compounds is largely achieved by the addition of acidic catalysts.
Numerous catalysts are described in the literature, for example for the dehydration of castor oil, including for example hetero polyacids (U.S. Pat. No. 2,261,633, 1939), Na
2
S
2
O
7
(Paint Manuf. 19, 118, 1949), sulfuric acid (U.S. Pat. No. 2,392,119, 1946), phosphorous acid (GB 671,368, 1952), boric acid (U.S. Pat. No. 2,278,425, 1939) and phthalic anhydride (U.S. Pat. No. 224,678), which lead to dehydrated castor oils. The conjugated fatty acids may be obtained from these oils by hydrolysis. However, acetylated hydroxyfatty compounds may be converted into the conjugated fatty acids by thermal ester pyrolysis. Thus, DE-C3-20 18 712, for example, describes the pyrolysis of diacetoxystearic acid methyl ester at 420 to 580° C. which is said to give conjuene yields of 80%.
Finally, the conjugated double bonds may be produced by partial or total syntheses.
The polymerization may have to be preceded by stereoisomerization into the E,Z-, Z,E- or Z,Z-configuration.
The following are specific examples of fatty acids containing conjugated double bonds:
naturally occurring conjuene fatty acids, such as sorbic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 10,12-octadecadienoic acid, 9-hydroxy-10,10-octadecadienoic acid, 13-hydroxy-9,11-octadecadienoic acid, 9,14-dihydroxy-10,12-octadecadienoic acid, 9,12,14-octadecatrienoic acid, 8,10,12-octadecatrienoic acid, elaeostearic acid (trichosanoic acid: punicic acid; catalpa acid), licanic acid, camolenic acid, parinaric acid;
conjuene fatty acids by selective hydrogenation, such as isanoic acid, isanolic acid, ximenynic acid, matricaria acid, lachnophyllic acid, mycomycinic acid;
conjuene fatty acids by isomerization of isolene fatty acids, for example Edenor UKD 60/10(Henkel KGaA);
conjuene fatty acids by dehydration of hydroxyfatty acids, such as ricinene fatty acid from ricinoleic acid.
Preferred components A are ricinene fatty acid, ricinene fatty acid methyl ester, UKD fatty acids, UKD fatty acid methyl ester, dehydrated castor oil, conjugated safflower oil
Boege Kai
Klauck Wolfgang
Klein Johann
Harper Stephen D.
Henkel Kommanditgesellschaft auf Aktien
Pezzuto Helen L.
Seifert Arthur G.
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