Silicone-containing graft copolymers of blockwise structure
View Patent ↗The invention describes novel silicone-containing graft copolymers and processes for their preparation. In particular, it relates to silicone-containing graft copolymers P, which are obtained by grafting olefinic monomers M onto polyether-containing radicals of polyoxyalkylene-polysiloxane block copolymers S with (AB) n structure.
1. Graft copolymers P based on polyoxyalkylene-polysiloxane block polymers S of the general formula (V)
where the radical
A is a polyoxyalkylene block of the average formula (VI),
[(C 2 H 4-d R′ d O) n (C x H 2x O) r (C 2 H 4-d R″ d O) t ] (VI)
where
d is from 1 to 3,
n is ≧0,
x is from 2 to 10,
r is ≧0,
t is ≧0,
n+r+t is ≧1,
and
R′ is a monovalent aromatic, optionally substituted hydrocarbon radical,
R″ is a hydrogen radical or a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R 1 is a hydrogen atom, a monovalent organic linear or branched alkyl radical of chain length C 1 -C 40 or a carboxyl radical or an optionally branched alkyl or aryl ester,
(VIII)
where the R 1 , A, B radicals and m, p and q are each as defined above and C is a linear or branched alkylene radical having from 2 to 20 carbon atoms
wherein the graft copolymers P are prepared by free radical graft polymerization of ethylenically unsaturated monomers M in the presence of polyoxyalkylene-polysiloxane block polymers of the formula (VIII);
wherein the monomers M are selected from the group of acrylic acid, methacrylic acid, vinyl ethers, vinyl alcohols, vinyl esters, styrene, methyl styrene, tert-butylstyrene, and mixtures and derivatives thereof; and
wherein the graft copolymers P further include derivatives of acrylic acid and methacrylic acid of the general formula (I),
X—C(O)CR 7 ═CHR 6 (I)
where
X is selected from the group of the OH, OL, OR 8 , NH 2 , NHR 8 , N(R 8 ) 2 radicals,
R 7 and R 6 are each independently selected from the group consisting of —H, C 1 -C 8 linear or branched alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl,
R 8 are C 1 -C 40 linear, C 3 -C 40 branched-chain, aromatic or C 3 -C 40 carbocyclic alkyl radicals, C 6 -C 12 polyfunctional alcohols having from 2 to 10 hydroxyl groups, such as ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol, alcohol ethers such as methoxyethanol and ethoxyethanol, or polyethylene glycols,
L is a cation selected from the group consisting of Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ , NH 4 + , alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium and analogous phosphorus ammonium derivatives.
2. Graft copolymers P according to formula (I) as claimed in claim 1 , wherein the free radical graft polymerization of ethylenically unsaturated monomers M is carried out in the presence of dihydroxy-functional polyethers of the general formula (X)
[HO(C 2 H 4-d R′ d O) n (C x H 2x O) r (C 2 H 4-d R″ d O) t H] (X)
where R′, R″, d, n, x, t and r have the meanings stated in claim 1 in the description of the polyoxyalkylene block A.
3. Graft copolymers P as claimed in claim 1 , wherein the amount of ethylenically unsaturated monomers M in relation to the polyether siloxanes S with a blockwise structure is between 2 and 500% by weight.
4. Graft polymers P as claimed in claim 1 , wherein, in the formula (VI) d=1, R′=phenyl and 1≧n<15.
5. Graft copolymers P as claimed in claim 1 , obtainable by using initiators which form oxygen-centered free radicals.
6. A method of softening textile fabrics, nonwovens and/or fibers formed from synthetic and/or natural raw materials which comprises adding a grafted polyoxyalkylene polysiloxane copolymer P of claim 1 to a textile fabric, nonwoven and/or fiber formed from synthetic and/or natural raw material.
7. The method of claim 6 wherein the textile fabric is a cotton fabric and the grafted polyoxyalkylene polysiloxane copolymer P is present in concentrations of from 0.01 to 20% by weight, based on the solvent or dispersant.
8. Graft copolymers P as claimed in claim 3 , wherein the amount of ethylenically unsaturated monomers M in relation to the polyether siloxanes S with a blockwise structure is between 2 and 200% by weight.
9. Graft copolymers P as claimed in claim 8 , wherein the amount of ethylenically unsaturated monomers M in relation to the polyether siloxanes S with a blockwise structure is between 2 and 100% by weight.