Oligo- and poly-carbonates terminated with silicon containing groups as surface modifiers
The instant invention relates to oligo- and poly-carbonates terminated with silicon containing groups which are useful as reducers of surface energy for organic materials such as polycarbonates, polyesters or polyketones or their mixtures, blends or alloys. Polymers with such reduced surface energy possess self-cleaning, anti-soiling, anti-graffiti, oil resistance, solvent resistance, chemical resistance, self-lubricating, scratch resistance, low moisture absorption, dirt pickup resistance, slip properties and a hydrophobic surface; and display anti-adhesion properties against proteins and against microorganisms such as for example, bacteria, fungi and algae.
1. A composition comprising
(a) a synthetic polymer which is susceptible to oxidative, thermal or light-induced degradation and
(b) at least one compound of the formula I
wherein
R 0 is a direct bond,
R 1 and R 2 are each independently of the other a silicon containing group,
R 3 and R 4 are each independently of the other hydrogen, a fluorine containing group, a silicon containing group, C 1 -C 12 alkyl, phenyl or
R 3 and R 4 , together with the carbon atom to which they are bonded, form a C 5 -C 8 cycloalkylidene ring that is unsubstituted or substituted by from 1 to 3 C 1 -C 4 alkyl groups;
R 5 , R 6 , R 7 and R 8 are each independently of the other hydrogen, C 1 -C 12 alkyl or C 3 -C 12 alkenyl,
X 1 and X 2 are each independently of the other C 1 -C 12 alkylene or C 4 -C 25 alkylene interrupted with oxygen;
Y 1 and Y 2 are each independently of the other a direct bond, oxygen,
R 9 and R 10 are each independently of the other a direct bond or C 1 -C 4 alkylene,
R 11 , R 12 and R 13 are each independently of the other hydrogen, C 1 -C 12 alkyl or C 3 -C 12 alkenyl,
R 14 is hydrogen, C 1 -C 12 alkyl or a silicon containing group,
m is 0 to 10,000, and
n is 0 to 10,000 and
where the silicon containing group is of formula II
wherein
R 17 , R 18 , R 19 and R 20 are each independently of the other C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted with hydroxy or amino; C 4 -C 12 hydroxyalkyl interrupted with oxygen; or
R 21 is C 1 -C 12 alkyl or
R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently of the other C 1 -C 12 alkyl or C 1 -C 12 alkyl substituted with hydroxy or amino;
p is 0 to 200 and
q is 0 to 200.
2. A composition according to claim 1 , wherein the compounds of formula I
R 0 is
R 1 and R 2 are each independently of the other a silicon containing group,
R 3 and R 4 are each independently of the other hydrogen, trifluoromethyl, a silicon containing group,
C 1 -C 12 alkyl, phenyl or
R 3 and R 4 , together with the carbon atom to which they are bonded, form a C 5 -C 8 cycloalkylidene ring that is unsubstituted or substituted by from 1 to 3 C 1 -C 4 alkyl groups;
R 5 , R 6 , R 7 and R 8 are hydrogen,
X 1 and X 2 are each independently of the other C 1 -C 12 alkylene or C 4 -C 25 alkylene interrupted with oxygen;
Y 1 and Y 2 are each independently of the other a direct bond, oxygen,
R 9 and R 10 are each independently of the other a direct bond or methylene,
R 11 , R 12 and R 13 are each independently of the other hydrogen, C 1 -C 4 alkyl or C 3 -C 4 alkenyl,
R 14 is hydrogen or C 1 -C 12 alkyl,
m is 0 to 10,000 and
n is 0 to 10,000.
3. A composition according to claim 1 , wherein the compounds of formula I
R 17 , R 18 , R 19 and R 20 are each independently of the other methyl or
R 21 is methyl or
R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are methyl and
p and q are each independently of the other 0 to 100.
4. A composition according to claim 1 , wherein the compounds of formula I
R 0 is
R 3 is hydrogen, CF 3 , C 1 -C 12 alkyl, phenyl or
R 4 is hydrogen, CF 3 , C 1 -C 12 alkyl or phenyl; or R 3 and R 4 , together with the carbon atom to which they are bonded, form a C 5 -C 8 cycloalkylidene ring that is unsubstituted or substituted by from 1 to 3 C 1 -C 4 alkyl groups;
R 5 , R 6 , R 7 and R 8 are hydrogen,
X 1 and X 2 are each independently of the other C 1 -C 12 alkylene or C 4 -C 25 alkylene interrupted with oxygen;
Y 1 and Y 2 are each independently of the other a direct bond, oxygen,
R 9 and R 10 are each independently of the other a direct bond or methylene,
R 14 is hydrogen or C 1 -C 12 alkyl,
m is 0 to 10,000 and
n is 0 to 10,000.
5. A composition according to claim 1 , wherein the compounds of formula I
R 3 and R 4 are each independently of the other hydrogen or C 1 -C 4 alkyl; or R 3 and R 4 , together with the carbon atom to which they are bonded, form a cyclohexylidene ring.
6. A composition according to claim 1 , wherein the compounds of formula I
X 1 and X 2 are each independently of the other C 2 -C 8 alkylene or C 4 -C 25 alkylene interrupted with oxygen.
7. A composition according to claim 1 , wherein the compounds of formula I
m is 0 to 100 and n is 0 to 100.
8. A composition according to claim 1 , wherein the compounds of formula I
R 0 is
R 3 and R 4 are each independently of the other C 1 -C 4 alkyl; or R 3 and R 4 , together with the carbon atom to which they are bonded, form a cyclohexylidene ring;
R 5 , R 6 , R 7 and R 8 are hydrogen,
X 1 and X 2 are each independently of the other C 2 -C 4 alkylene or C 4 -C 25 alkylene interrupted with oxygen;
Y 1 and Y 2 are each independently of the other a direct bond, oxygen,
R 9 and R 10 are each independently of the other a direct bond or methylene,
m is 0 to 100 and
n is 0 to 100.
9. A composition according to claim 1 further comprising
(β) one or more additives selected from the group consisting of phenolic antioxidants, light-stabilizers, processing stabilizers, nucleating agent, biocides, antistatic agents, flame retardants and fillers.
10. A composition according to claim 9 , wherein the weight ratio of the components (b):(β) is from 100:0.01 to 0.01:100.
11. A composition according to claim 1 wherein component (a) is a polycarbonate, polyester, polyacrylate or polymethacrylate or their mixtures, blends or alloys.
12. A composition according to claim 1 wherein component (b) is present in an amount of from 0.1 to 20%, based on the weight of component (a).
13. A composition according to claim 1 , comprising in addition, besides components (a) and (b), further additives.
14. A composition according to claim 13 , comprising as further additives phenolic antioxidants, light-stabilizers and/or processing stabilizers.
15. A process for reducing the surface energy of synthetic polymers which process comprises incorporating therein or applying thereto a compound of the formula I
wherein
R 0 is a direct bond
—O—, —S—, —SO—, —SO 2 — or
R 1 and R 2 are each independently of the other a silicon containing group,
R 3 and R 4 are each independently of the other hydrogen a fluorine containing group a silicon containing group, C 1 -C 12 alkyl, phenyl or
R 3 and R 4 together with the carbon atom to which the are bonded form a C 5 -C 8 cycloalkylidene ring that is unsubstituted or substituted by from 1 to 3 C 1 -C 4 alkyl groups;
R 5 R 6 R 7 and R 8 are each independently of the other hydrogen, C 1 -C 12 alkyl or C 3 -C 12 alkenyl,
X 1 and X are each independently of the other C 1 -C 12 alkylene or C 4 -C 25 alkylene interrupted with oxygen;
Y 1 and Y 2 are each independently of the other a direct bond, oxygen,
R 9 and R 10 are each independently of the other a direct bond or C 1 -C 4 alkylene,
R 11 , R 12 and R 13 are each independently of the other hydrogen, C 1 -C 12 alkyl or C 3 -C 12 alkenyl,
R 14 is hydrogen, C 1 -C 12 alkyl or a silicon containing group,
m is 0 to 10,000, and
n is 0 to 10,000 and
where the silicon containing group is of formula II
wherein
R 17 , R 18 , R 19 and R 20 are each independently of the other C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted with
hydroxy or amino; C 4 -C 12 hydroxyalkyl interrupted with oxygen; or
R 21 is C 1 -C 12 alkyl or
R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently of the other C 1 -C 12 alkyl or C 1 -C 12 alkyl substituted with hydroxy or amino;
p is 0 to 200 and
q is 0 to 200.