Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2003-11-24
2004-12-21
Zalukaeva, Tatayana (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S277000, C526S250000, C526S303100, C526S307100, C526S307200
Reexamination Certificate
active
06833419
ABSTRACT:
The present invention relates to fluorine-modified comb polymers based on acryloyldimethyltaurine.
In recent years water-soluble polymers have acquired a continually increasing importance in industry and science. In volume terms, polyelectrolytes are occupying a very large proportion of the overall annual production. They find application, for example, in paper processing, in the laundry detergents industry, in textile processing, in petroleum extraction or as important base materials for cosmetics. In the cosmetics sector a supporting role is played by polyelectrolytes. Besides water-soluble surface-active substances there is a high demand in this sector for systems which thicken oil and water. Thickeners of this kind, particularly the “superabsorbents” prepared on the basis of polyacrylic acid, have progressed since their development in the 1970s to become a pillar of the hygiene sector. In their crosslinked versions, partly or fully neutralized polyacrylic acids and their water-soluble copolymers are employed in numerous cosmetic formulations as bodying agents. The diversity of possible structures and the diverse possible applications associated therewith are manifested not least in a host of patents filed worldwide since the mid-1970s. In the 1990s, innovative thickeners based on 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and their salts were introduced into the market (EP 816 403 and WO 98/00094). In both homopolymer and copolymer form (®Aristoflex AVC, Clariant GmbH) such thickeners are superior in many respects to the corresponding polycarboxylates (Carbopols). For example, thickener systems based on AMPS display outstanding properties in pH ranges below pH 6, i.e., in a pH range in which it is no longer possible to operate with conventional polycarboxylate thickeners. Moreover, the microgel structure of such thickeners leads to a particularly pleasant skin sensation. The ease of processing and the favorable toxicological profile of the principal monomer imbue these thickeners with a high application potential.
Over recent years representatives of a new thickener design have entered the market. In these thickeners two different properties have been combined in one polymer, thereby opening up new fields of application. Thickening emulsifiers or dispersants are but two examples of this new class of substance. Brand names that may be mentioned include the Pemulens® TR-1 and TR-2 from BF Goodrich or the Aculyn® products from Rohm & Haas. All existing versions are based on hydrophobically modified versions of the conventional polyacrylates.
Comparable polymers which develop hydrophobic interactions and hence physical crosslinking through fluorine-containing groups were hitherto unknown. Some fluorotelomers which possess one or a maximum of two fluorine-containing groups per polymer chain are available.
Through free-radical copolymerization of acryloyldimethyltaurine (AMPS) and/or its salts with suitable vinylically monofunctional or polyfunctional fluorine derivatives, in the presence where appropriate of comonomers and polymeric additives, it was possible to synthesize both crosslinked and noncrosslinked structures having highly advantageous performance properties.
The invention provides water-soluble or water-swellable copolymers preparable by free-radical copolymerization of:
A) acryloyldimethyltaurine and/or acryloyldimethyltaurates,
B) if desired, one or more other olefinically unsaturated, optionally crosslinking, comonomers containing at least one oxygen, nitrogen, sulfur or phosphorus atom and possessing a molecular weight of less than 500 g/mol, and
C) one or more at least monofunctional, fluorine-containing components capable of free-radical polymerization, the copolymerization
D) taking place in the presence or absence of at least one polymeric additive having number-average molecular weights of from 200 g/mol to 10
9
g/mol.
The copolymers of the invention preferably possess a molecular weight of from 10
3
g/mol to 10
9
g/mol, more preferably from 10
4
to 10
7
g/mol, very preferably from 5*10
4
to 5*10
6
g/mol.
The acryloyldimethyltaurates can be the organic or inorganic salts of acryloyl-dimethyltaurine. Preference is given to the Li
+
, Na
+
, K
+
, Mg
++
, Ca
++
, All
+++
and/or NH
4
+
salts. Likewise preferred are the monoalkylammonium, dialkylammonium, trialkylammonium and/or tetraalkylammonium salts, in which the alkyl substituents of the amines may independently of one another be (C
1
-C
22
)-alkyl radicals or (C
2
-C
10
)-hydroxyalkyl radicals. Preference is also given to mono- to triethoxylated ammonium compounds with a different degree of ethoxylation. It should be noted that the invention also embraces mixtures of two or more of the abovementioned representatives.
The degree of neutralization of the acryloyldimethyltaurine can be between 0 and 100%, particular preference being given to a degree of neutralization of more than 80%.
Based on the total mass of the copolymers, the amount of acryloyldimethyltaurine and/or acryloyldimethyltaurates is at least 0.1% by weight, preferably from 20 to 99.5% by weight, more preferably from 50 to 98% by weight.
As comonomers B) it is possible to use all olefinically unsaturated monomers whose reaction parameters allow copolymerization with acryloyldimethyltaurine and/or acryloyldimethyltaurates in the respective reaction media. Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols having a carbon number of from 1 to 22. Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and senecic acid. Preferred counterions are Li
+
, Na
+
, K
+
, Mg
++
, Ca
++
, Al
+++
, NH
4
+
, monoalkylammonium, dialkylammonium, trialkylammonium and/or tetraalkylammonium radicals, in which the alkyl substituents of the amines independently of one another are (C
1
-C
22
)-alkyl radicals or (C
2
-C
10
)-hydroxyalkyl radicals. It is additionally possible to employ mono- to triethoxylated ammonium compounds with a different degree of ethoxylation. The degree of neutralization of the carboxylic acids can be between 0 and 100%. Further preferred comonomers are open-chain N-vinyl amides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N,N-diisopropylacrylamide; alkoxylated acrylamides and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethylmethacrylamide; hydroxyethylmethacrylamide, hydroxypropylmethacrylamide, and mono[2-(methacryloyloxy)ethyl] succinate; N,N-dimethylamino methacrylate; diethylaminomethyl methacrylate; acrylamido- and methacrylamidoglycolic acid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl methacrylate; styrene; acrylonitrile; vinyl chloride; stearyl acrylate; lauryl methacrylate; vinylidene chloride; and/or tetrafluoroethylene. Likewise suitable comonomers B) are inorganic acids and their salts and esters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid, and methallylsulfonic acid.
The weight fraction of the comonomers B), based on the total mass of the copolymers, can be from 0 to 99.8% by weight and is preferably from 0.5 to 80% by weight, more preferably from 2 to 50% by weight.
Suitable polymerizable fluorine-containing components C) include all compounds which are olefinically at least monounsaturated and which are capable of free-radical copolymerization with acryloyldimethyltaurine and/or acryloyldimethyl-taurates—and optionally further comonomers—under the reaction conditio
Kayser Christoph
L{hacek over (o)}ffler Matthias
Morschhäuser Roman
Clariant GmbH
Silverman Richard P.
Zalukaeva Tatayana
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