Fluorinated acrylate block copolymers with low dynamic surface tension

Abstract

The present invention relates to a composition, comprising a binder resin, a block copolymer which comprises at least a block A and a block B, wherein the block A comprises monomer units derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl aromatic compound, or any mixture thereof, the block B comprises monomer units derived from a compound selected from a fluorinated (meth)acrylic ester having the following formula (I): H.sub.2CC(R.sub.1)(C(0)OR.sub.F-1), wherein R1 is H or methyl; and R.sub.F-1 is an organic residue containing a perfluorinated C.sub.4-6 alkyl group, a fluorinated alpha-olefin having the following formula (II): H.sub.2CCH(R.sub.F-2) (II) wherein R.sub.F-2 is an organic residue containing a perfluorinated C.sub.4-6 alkyl group, i.e. (CF.sub.2).sub.3-5CF.sub.3 or any mixture thereof.

Claims

1. A composition, comprising: a binder resin; and a block copolymer comprising: a block A and a block B, wherein the block A comprises monomer units derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl aromatic compound, or a mixture thereof, and the block B comprises monomer units derived from a compound selected from a a fluorinated alpha-olefin having the following formula (II):
H.sub.2CCH(R.sub.F-2)(II) wherein R.sub.F-2 is an organic residue containing a perfluorinated C.sub.4-6 alkyl group.

2. The composition according to claim 1, wherein R.sub.F-2 is of formula (III):
(R.sub.2).sub.x(CF.sub.2).sub.3-5CF.sub.3(III) wherein x is 0 or 1, and R.sub.2 is a divalent non-fluorinated C.sub.1-4 alkylene group.

3. The composition according to claim 1, wherein the block B has an average number of monomer units which are derived from the fluorinated alpha-olefin of formula (II) of at least 0.25.

4. The composition according to claim 1, wherein the block A has an average number of monomer units which are derived from a compound selected from (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, or a vinyl aromatic compound, of at least 5.

5. The composition according to claim 1, wherein the block copolymer has a number average molecular weight Mn of from 1000 to 100,000 g/mol, the block copolymer has a polydispersity index PDI of less than 1.90, or the block copolymer has a number average molecular weight Mn of from 1000 to 100,000 g/mol and a polydispersity index PDI of less than 1.90.

6. The composition according to claim 1, wherein the block copolymer comprises the monomer units derived from the fluorinated alpha-olefin of formula (II) in an amount of from 0.1 wt % to 70 wt %, and/or the block copolymer has a fluorine content of from 0.05 wt % to 35 wt %.

7. The composition according to claim 1, wherein the block copolymer is obtained by a nitroxide-mediated controlled polymerization (NMP).

8. The composition according to claim 1, wherein two neighboring blocks of the block copolymer are directly linked to each other.

9. The composition according to claim 1, wherein two neighboring blocks of the block copolymer are linked to each other via a linking group LG, wherein the linking group LG is of formula (VII):
IN.sub.1YIN.sub.2(VII) wherein the IN.sub.1 and IN.sub.2 groups, which can be the same or different from each other, are derived from initiator fragments IN.sub.1 and IN.sub.2 of the controlled free radical polymerization, and Y is a divalent group covalently linked to the IN.sub.1 and IN.sub.2 groups or represents a covalent bond between the IN.sub.1 and IN.sub.2 groups.

10. The composition according to claim 1, wherein an amount of the block copolymer, relative to the total composition, is from 0.05 wt % to 15 wt %.

11. The composition according to claim 1, wherein the block copolymer is a gradient block copolymer.

12. The composition according to claim 1, wherein the block copolymer is obtained by nitroxide-mediated controlled polymerization with a polymerization regulator compound selected from the group consisting of formulas (IV), (V) and (VI) or selected from the group consisting of a polymerization regulator comprising the stable free nitroxyl radicals of formulas (IV), (V) and (VI) in conjunction with a radical source: ##STR00014## wherein R is hydrogen, C.sub.1-18 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an ,-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, R.sub.101 is C.sub.1-12 alkyl, C.sub.5-7cycloalkyl, C.sub.7-8aralkyl, C.sub.2-18alkanoyl, C.sub.3-5alkenoyl or benzoyl, R.sub.102 is C.sub.1-18alkyl, C.sub.5-7cycloalkyl, C.sub.2-8alkenyl, which can be unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula CH.sub.2CH(OH)Z or of the formula COZ or CONHZ wherein Z is hydrogen, methyl or phenyl, G.sub.6 is hydrogen, G.sub.5 is hydrogen or C.sub.1-4alkyl, G.sub.1 and G.sub.3 are methyl, G.sub.2 and G.sub.4 are ethyl or propyl, or G.sub.1 and G.sub.2 are methyl and G3 and G4 are ethyl or propyl; and X is selected from CH.sub.2-phenyl, CH.sub.3CH-phenyl, (CH.sub.3).sub.2C-phenyl, (C.sub.5-6cycloalkyl).sub.2CCN, (CH.sub.3).sub.2CCN, ##STR00015## CH.sub.2CHCH.sub.2, CH.sub.3CHCHCH.sub.2 , (C.sub.1-4alkyl)CR.sub.20C(O)phenyl, (C.sub.1-4)alkyl-CR.sub.20C(O)(C.sub.1-4)alkoxy, (C.sub.1-4)alkyl-CR.sub.20C(O)(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.20C(O)N-di(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.20C(O)NH(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.20C(O)NH.sub.2, wherein R.sub.20 is hydrogen or (C.sub.1-4)alkl.

13. The composition according to claim 1, wherein the composition is at least one of a coating composition, an ink composition, and an adhesive composition.

Description

EXAMPLES

(1) I. Measuring Methods

(2) If not indicated otherwise, parameters defined in the present application are measured by the measuring methods described below:

(3) Number Average Molecular Weight Mn, Polydispersity Index PDI

(4) Mn and PDI are measured by gel permeation chromatography (GPC) with polystyrene standards. The eluent is THF.

(5) Amount of F (in Wt %) and Amount of Fluorine-Containing Monomer Units (in Wt %) in the Block Copolymer

(6) Determined by .sup.1H NMR, 400 MHz.

(7) II. Preparation Examples

Inventive Example 1

Synthesis of a Linear A-B Block-Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA)

(8) Synthesis of A Block

(9) ##STR00003##

(10) In a 5000 mL glass reactor with overhead mechanical stirrer, condenser, metering pumps, computerized temperature control and data acquisition, the following A-blocks are synthesized.

(11) GK3023-360 (10 Units nBA)

(12) 1816.70 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), 150.00 g of the initiator compound NOR 1 (317.48 g/mol) and 271.38 g of ethyl acetate (EtAc, Mw 88.11 g/mol) are mixed together, purged with N.sub.2 and reacted for 3 h at 120 C. Residual monomer and ethyl acetate is distilled off at 105 C. and 20 mbar.

(13) Yield: 33.3%; GPC (THF, PS-Standard, Mn=1706 g/mol, PDI=1.26, liquid)

(14) GK3023-264 (20 Units)

(15) 1211.13 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 60.00 g of the initiator compound NOR 1 (317.48 g/mol) are mixed together, purged with N.sub.2 and reacted for 3.5 h at 115 C. Residual monomer is distilled off at 105 C. and 20 mbar.

(16) Yield: 42.83%; GPC (THF, PS-Standard, Mn=2435 g/mol, PDI=1.36, viscous liquid)

(17) GK3023-335 (35 Units)

(18) 1383.92 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), 40.00 g of the initiator compound NOR 1 (317.48 g/mol) and 206.70 g of ethyl acetate (EtAc, Mw 88.11 g/mol) are mixed together, purged with N.sub.2 and reacted for 3 h at 120 C. Residual monomer and ethyl acetate is distilled off at 105 C. and 20 mbar.

(19) Yield: 38.3%; GPC (THF, PS-Standard, Mn=3649 g/mol, PDI=1.44, viscous liquid)

(20) GK3023-387 (75 Units)

(21) 1211.13 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 60.00 g of NOR 1 (317.48 g/mol) are mixed together, purged with N2 and reacted for 1.5 h at 115 C. A feed of 2422.26 g of nBA is fed to the reactor over 3 hours. At 125 C., the reaction continues for a further 4.5 h. Residual monomer is distilled off at 105 C. and 20 mbar.

(22) Yield: 50.36%; GPC (THF, PS-Standard, Mn=9650 g/mol, PDI=1.21, viscous liquid)

(23) Synthesis of B Block

(24) ##STR00004##

(25) In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, A g of Poly-nBA (see table) and B g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128 C. Residual monomer is distilled off at 105 C. and 20 mbar. The polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of TFOA is negative) and .sup.1H-NMR (in CDCl.sub.3).

(26) TABLE-US-00001 Description A-block wt % F (units of Poly- A B Yield Mn .sup.a wt. % in nBA:units Product nBA (g of A block) (g TFOA) (%) (g/mol) PDI .sup.a TFOA .sup.b polymer .sup.b of TFOA) .sup.b GK3479- GK3023- 10.00 13.94 82.59 2029 1.29 50.90 30.03 10:3.96 039 360 GK3479- GK3023- 15.00 12.54 88.56 2035 1.23 40.40 23.87 10:2.59 040 360 GK3479- GK3023- 20.00 5.58 89.12 1771 1.22 19.07 11.25 10:0.90 041 360 GK3479- GK3023- 27.00 3.00 87.93 2055 1.21 7.51 4.43 10:0.31 076 360 GK3479- GK3023- 27.90 2.10 88.40 2016 1.22 5.91 3.49 10:0.24 077 360 GK3479- GK3023- 20.00 13.94 95.01 3510 1.20 36.93 21.79 20:4.03 044 264 GK3479- GK3023- 20.00 8.36 92.01 3121 1.22 24.97 14.73 20:2.29 046 264 GK3494- GK3023- 30.00 4.18 92.44 3377 1.24 10.30 6.07 20:0.79 071 264 GK3494- GK3023- 30.00 20.91 94.96 4331 1.22 37.22 21.96 20:4.08 014 264 GK3479- GK3023- 45.00 5.00 93.31 2949 1.26 6.26 3.70 20:0.46 080 264 GK3479- GK3023- 46.50 3.50 93.57 3012 1.26 4.97 2.93 20:0.36 081 264 GK3479- GK3023- 30.00 7.84 94.09 4476 1.17 17.36 10.24 35:2.41 043 335 GK3494- GK3023- 30.00 13.07 91.04 5068 1.16 28.26 16.67 35:4.53 028 335 GK3479- GK3023- 30.00 2.61 96.33 5218 1.19 6.29 3.71 35:0.77 070 335 GK3479- GK3023- 27.00 3.00 96.90 4869 1.20 6.21 3.66 35:0.76 079 335 GK3494- GK3023- 50.00 10.59 94.47 8638 1.16 14.89 8.78 75:4.15 026 387 GK3494- GK3023- 50.00 20.91 91.77 9119 1.18 24.86 14.67 75:7.85 027 387 GK3479- GK3023- 50.00 6.27 98.86 8223 1.19 10.22 6.03 75:2.70 042 387 GK3479- GK3023- 50.00 2.09 98.93 8012 1.19 3.65 2.16 75:0.90 047 387 GK3479- GK3023- 45.00 5.00 97.24 9907 1.23 7.81 4.61 75:2.01 078 387 GK3479- GK3023- 40.00 14.65 83.99 7803 1.19 5.19 3.06 75:1.30 48.sup.c 387 GK3479- GK3023- 46.50 3.50 98.11 9476 1.22 5.80 3.42 75:1.46 082 387 .sup.a by GPC with polystyrene standards .sup.b by H.sup.1 NMR .sup.cPolymerization at 115 C. for 2 hours.

Comparative Example 2

Synthesis of a Linear, Low Polydispersity, Random Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA)

(27) GK3479-027

(28) ##STR00005##

(29) In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, C 65.70 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), D 3.70 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) and E 2.50 g of NOR 1 (317.48 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 3-4 hours at 125 C. Residual monomer is distilled off at 95 C. and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and .sup.1H-NMR (in CDCl.sub.3).

(30) TABLE-US-00002 wt % F C D E Yield Mn .sup.a wt. % in Product (g of nBA) (g of TFOA) (g NOR1) (%) (g/mol) PDI .sup.a TFOA .sup.b polymer .sup.b GK3479- 65.70 3.70 2.50 60.14 3724 1.20 8.02 4.73 027 GK3479- 62.00 7.40 2.50 61.80 4031 1.23 14.27 8.42 026 GK3479- 58.00 11.40 2.50 60.71 3814 1.25 19.46 11.48 024 GK3479- 47.79 2.67 2.50 44.87 2217 1.30 12.55 7.41 022 GK3479- 45.06 5.40 2.50 47.76 2298 1.27 17.73 10.46 021 GK3479- 42.38 8.08 2.50 46.11 2296 1.28 21.53 12.70 020 .sup.a by GPC with polystyrene standards .sup.b by H.sup.1 NMR

Comparative Example 3

Synthesis of Random Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA) by free radical polymerization

(31) GK3365-133

(32) In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, 50.00 g of sec-Butanol (Mw 74.12 g/mol) is purged with N2 for 30 minutes and heated to 100 C. A pre-mixed feed of A 5.00 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol), B 88.54 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and C 6.46 g of tert-butyl Peroxy-2-ethylhexanoate (tBpOEH, Mw 216.32 g/mol) is fed to the reactor over 3 hours. After the completion of the feed, the reaction continues to react for a further 3 hours. The solvent is distilled off at 100 C. and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and .sup.1H-NMR (in CDCl.sub.3).

(33) TABLE-US-00003 wt % F B A C Mn .sup.a wt. % in Product (g of nBA) (g of TFOA) (g of tBpOEH) (g/mol) PDI .sup.a TFOA .sup.b polymer .sup.b GK3365- 88.54 5.00 6.46 2065 1.56 5.35 2.95 133 GK3365- 83.54 10.00 6.46 2072 1.56 10.69 5.90 134 GK3365- 78.54 15.00 6.46 2043 1.50 16.04 8.85 135 GK3365- 88.54 5.00 3.00 2604 1.70 5.35 2.95 136

Inventive Example 4

Synthesis of a Linear B-A-B Block-Copolymer of n-Butyl Acrylate (nBA, A-block) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, B-block)

(34) Synthesis of A (Interior) Block

(35) ##STR00006##

(36) In a 5000 mL glass reactor with overhead mechanical stirrer, condenser, metering pumps, computerized temperature control and data acquisition, the following A-blocks-precursors are synthesized.

(37) GK3023-389 (75 Units)

(38) 2165.22 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 80.00 g of the initiator compound NOR 2 (342.48 g/mol) are mixed together, purged with N2 and reacted for 1.5 h at 115 C. A feed of 1624.54 g of nBA was fed to the reactor over 5 hours. At 125 C., the reaction continues for a further 2 h. Residual monomer is distilled off at 105 C. and 20 mbar.

(39) Yield: 50.29%; GPC (THF, PS-Standard, Mn=10740 g/mol, PDI=1.19, viscous liquid)

(40) GK3023-287 (15 Units)

(41) 2944.4 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 180 g of NOR 2 (342.48 g/mol) are mixed together, purged with N2 and reacted for 3.5 h at 115 C. Residual monomer is distilled off at 105 C. and 20 mbar.

(42) Yield: 28.84%; GPC (THF, PS-Standard, Mn=2172 g/mol, PDI=1.25, viscous liquid)

(43) GK3023-010 (35 Units)

(44) In a 2000 mL glass reactor with overhead mechanical anchor stirrer, condenser and metering pumps 561.36 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 50.00 g of NOR 2 (342.48 g/mol) are mixed together, purged with N2 and reacted for 2 h at 115 C. A feed of 748.48 g of nBA is fed to the reactor over 6 hours. At 120 C., the reaction continues for a further 6 h. Residual monomer is distilled off at 105 C. and 20 mbar.

(45) Yield: 49.67%; GPC (THF, PS-Standard, Mn=7739 g/mol, PDI=1.14, viscous liquid)

(46) Coupling to Synthesize Difunctional A-Blocks

(47) ##STR00007##

(48) In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, F g of Poly-nBA precursors (see table) and G g of tolylene-2,4-diisocyanate (TDI, Mw 174.16 g/mol) are mixed together and purged with N2 for 30 minutes. The inner temperature is raised to 60 C. and a few drops of dibutyltin dilaurate (DBTL, Mw 631.56, 10% solution in butyl acetate) are added. The coupling reaction continues for 4 hours at 60 C. The polymer is characterized by GPC (THF and with PS-Standards and .sup.1H-NMR (in CDCl.sub.3).

(49) TABLE-US-00004 F (g of G Mn .sup.a Description A-block Poly- A (g (g/ (units of nBA: Product nBA block) TDI) mol) PDI .sup.a units of TFOA) .sup.b GK3041-283 GK3023-389 1200 11.00 17592 1.21 NOR-BA(150)-NOR GK3479-061 GK3023-010 120 2.39 8947 1.17 NOR-BA(70)-NOR GK3479-062 GK3023-287 100 4.79 4186 1.13 NOR-BA(30)-NOR
Synthesis of B Block

(50) ##STR00008##

(51) In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, H g of di-functional poly nBA (see table) and I g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl Acrylate (TFOA, Mw 418.15 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128 C. Residual monomer is distilled off at 105 C. and 20 mbar. The polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of TFOA is negative) and .sup.1H-NMR (in CDCl.sub.3).

(52) TABLE-US-00005 A-block wt % F Idealized Poly- H I Yield Mn .sup.a wt. % in Description Product nBA (g of A block) (g TFOA) (%) (g/mol) PDI .sup.a TFOA .sup.b polymer .sup.b (TFOA:nBA:TFOA) .sup.b 3479- GK3041- 40.00 5.02 95.02 14434 1.40 6.49 3.83 2.93:150:2.93 072 283 3479- GK3041- 40.00 8.36 91.92 16021 1.40 10.02 5.91 4.89:150:4.89 073 283 3479- GK3041- 40.00 1.67 99.53 16734 1.24 3.55 2.10 0.98:150:0.98 074 283 3479- GK3041- 30.00 7.52 83.87 15757 1.36 4.67 2.75 5.86:150:5.86 075.sup.c 283 3479- GK3479- 30.00 7.53 81.23 8445 1.45 1.59 0.94 2.79:70:2.79 067 061 3479- GK3479- 30.00 15.06 83.84 9071 1.47 20.59 12.15 5.59:70:5.59 068.sup.d 061 3479- GK3479- 15.00 8.36 94.04 4749 1.39 31.72 18.71 2.79:30:2.79 065 062 3479- GK3479- 20.00 3.72 94.70 3815 1.44 10.96 6.47 0.93:30:0.93 066 062 .sup.a by GPC with polystyrene standards .sup.b based on solids content .sup.cPolymerized with a maximum temperature of 115 C. in 1 hour. .sup.dPolymerized with a maximum temperature of 115 C. in 22 hours.

Inventive Example 5

Synthesis of a Linear A-B Block-Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NNFHA)

(53) Synthesis of A Block

(54) ##STR00009##

(55) The same A-blocks as those described in Example 1 are used as the starting block for the chain extension with NFHA monomer.

(56) Synthesis of B Block

(57) ##STR00010##

(58) In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, A g of Poly-nBA (see table) and B g of 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA, Mw 318.13 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 8 hours at 128 C. Residual monomer is distilled off at 105 C. and 20 mbar. The polymer is characterized by GPC (THF and with PS-Standards; note: the refractive index of NFHA is negative) and .sup.1H-NMR (in CDCl.sub.3).

(59) TABLE-US-00006 Description A-block wt % F (units of Poly- A B Yield Mn .sup.a wt. % in nBA:units Product nBA (g of A block) (g NFHA) (%) (g/mol) PDI .sup.a NFHA .sup.b polymer .sup.b of NFHA) .sup.b GK3479- GK3023- 10.00 10.60 92.25 2803 1.22 29.78 45.78 10:4.24 143 360 GK3479- GK3023- 15.00 9.54 91.54 2496 1.21 19.29 32.24 10:2.39 144 360 GK3479- GK3023- 20.00 7.85 89.70 2281 1.24 13.12 23.12 10:1.51 186 360 GK3479- GK3023- 20.00 4.24 88.60 2057 1.25 6.10 11.46 10:0.65 185 360 GK3479- GK3023- 30.00 14.00 91.55 3664 1.25 14.20 26.79 20:3.31 183 264 GK3479- GK3023- 30.00 9.54 92.36 3386 1.26 11.74 22.72 20:2.66 184 264 GK3479- GK3023- 30.00 8.75 93.49 5620 1.18 6.49 13.87 35:2.43 181 335 GK3479- GK3023- 30.00 5.96 93.06 5405 1.18 3.37 7.48 35:1.22 182 335 GK3479- GK3023- 35.00 11.13 94.43 11084 1.28 8.55 18.35 75:7.01 145 387 GK3479- GK3023- 50.00 11.82 95.24 11016 1.3 7.09 15.50 75:5.72 179 387 GK3494- GK3023- 50.00 7.95 96.20 98040 1.29 9.07 4.81 75:3.11 50 387 GK3479- GK3023- 50.00 7.03 95.43 2803 1.22 3.80 8.67 75:2.96 180 387 .sup.a by GPC with polystyrene standards .sup.b by H.sup.1 NMR

Comparative Example 6

Synthesis of a Linear, Low Polydispersity, Random Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA)

(60) GK3479-202

(61) ##STR00011##

(62) In a 5-necked 100 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, C 50.86 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol), D 9.70 g of 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA, Mw 318.13 g/mol) and E 3.00 g of NOR 1 (317.48 g/mol) are mixed together, purged with N2 for 30 minutes and polymerized for 3-4 hours at 125 C. Residual monomer is distilled off at 95 C. and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and .sup.1H-NMR (in CDCl.sub.3).

(63) TABLE-US-00007 wt % F C D E Yield Mn .sup.a wt. % in Product (g of nBA) (g of NFHA) (g NOR1) (%) (g/mol) PDI .sup.a NFHA .sup.b polymer .sup.b GK3479- 50.86 9.70 3.00 50.79 2786 1.25 21.01 11.14 202 GK3479- 54.07 6.48 3.00 51.94 2896 1.19 17.39 9.22 203 GK3479- 57.35 3.20 3.00 49.08 2847 1.23 12.36 6.55 204 GK3479- 50.86 9.70 0.95 49.75 8146 1.18 19.62 10.40 205 GK3479- 54.07 6.48 0.95 51.24 8189 1.19 18.96 10.05 206 GK3479- 57.35 3.20 0.95 52.87 8552 1.21 5.36 2.84 207 .sup.a by GPC with polystyrene standards .sup.b by H.sup.1 NMR

Comparative Example 7

Synthesis of Random Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA) by Free Radical Polymerization

(64) GK3365-207

(65) In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, 50.00 g of sec-Butanol (Mw 74.12 g/mol) is purged with N2 for 30 minutes and heated to 100 C. A pre-mixed feed of A 5.00 g of 3,3,4,4,5,5,6,6,6-Nonafluorhexyl Acrylate (NFHA, Mw 318.13 g/mol), B 88.54 g of n-Butyl Acrylate (nBA, Mw 128.7 g/mol) and 6.46 g of tert-butyl Peroxy-2-ethylhexanoate (tBpOEH, Mw 216.32 g/mol) is fed to the reactor over 3 hours. After the completion of the feed, the reaction continues to react for a further 3 hours. The solvent is distilled off at 100 C. and 10 mbar. The polymer is characterized by GPC (THF and with PS-Standards) and .sup.1H-NMR (in CDCl.sub.3).

(66) TABLE-US-00008 wt % F B A Yield Mn .sup.a wt. % in Product (g of nBA) (g of NFHA) (%) (g/mol) PDI .sup.a NFHA .sup.b polymer .sup.b GK3365- 88.54 5.00 6.46 1656 1.59 5.35 2.84 207 GK3365- 83.54 10.00 6.46 1666 1.60 10.69 5.67 208 GK3365- 78.54 15.00 6.46 1699 1.61 16.04 8.50 209 GK3365- 73.54 20.00 6.46 1606 1.65 21.38 11.33 210 GK3365- 88.54 5.00 2.00 2501 2.16 5.35 2.84 211 GK3365- 83.54 10.00 2.00 2318 1.92 10.69 5.67 212

Inventive Example 8

Synthesis of a Linear A-B Block-Copolymer of n-Butyl Acrylate (nBA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluor-1-octene (TFO)

(67) Synthesis of A Block

(68) ##STR00012##

(69) The same A-blocks as those described in Example 1 are used as the starting block for the chain extension with TFO monomer.

(70) Synthesis of B Block

(71) ##STR00013##

(72) In a 5-necked 200 mL Sulfier flask with an overhead stirrer, thermometer, cooler and septum, A g of Poly-nBA (see table), B g of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluor-1-octene (TFO, Mw 346.09 g/mol) and C g of toluene are mixed together, purged with N2 for 30 minutes and polymerized for 6 hours at reflux (106-110 C.). Residual monomer and solvent is distilled off at 120 C. and 20 mbar to >99%. The polymer is characterized by a mass balance of the distillate.

(73) TABLE-US-00009 wt % F A-block A B C wt. % in Product Poly-nBA (g of A block) (g TFO) (g Toluene) TFO polymer GM0800- GK3023-360 30.00 69.22 30.00 17.81 12.64 0012 GM0800- GK3023-360 25.00 115.36 25.00 17.81 12.64 0013
III. Application Examples
Static Surface Tension:

(74) Static surface tension is measured using an OCA 20 (Dataphysics) at concentrations from 1-10 w % in xylene using the hanging-drop method.

(75) TABLE-US-00010 TABLE 1.1 Static surface tension surface surface tension tension Example (mN/m) (mN/m) type conc (w %) w % TFOA 10 1 comparative Xylol 28.62 28.62 (blank) GK3479/022 12.6 28.45 28.98 GK3479/021 17.7 27.83 29.03 GK3479/020 21.5 27.1 28.93 inventive GK3479/047 3.7 28.22 28.98 GK3479/042 10.2 20.76 25.93 GK3494/026 14.9 18.55 21.29 GK3494/027 24.9 18.34 19.62

(76) At comparable amounts of TFOA w % (GK3479/022 as a comparative example and GK3479-042 as an inventive example), a much lower static surface tension in xylene are clearly observed (28.98 mN/m and 25.93 mN/m respectively at 1 w % in xylene).

(77) Dynamic Surface Tension:

(78) (i) With block B containing fluorinated (meth)acrylic ester derived units

(79) Dynamic surface tension is measured using a bubble pressure tensiometer (Sita) at concentrations of 0.25% 0.5 w % in the A component of a solventbased 2K-PU. Bubble life times are measured from 80 msec up to 10 sec.

(80) A component 2K PU:

(81) TABLE-US-00011 TABLE 2.1 2K-PU Component A Weight 0.25 wt % 0.5 wt % Raw material Identity in g. Additive Additive Macrynal Acrylic 89.0 SM510/60LG resin solution Butyl acetate Solvent 11.0 Efka 2018N 8.0 Formulation 108.0 7.38 7.36 Additive 0.025 0.05 Sample size 7.405 7.41

(82) Efka 2018N is a commercially available defoamer.

(83) At a very short bubble life time, a clear advantage (lower dynamic surface tension values) could be observed looking at same w % F-Monomer and 0.5 w % addition levels.

(84) TABLE-US-00012 Inventive examples GK3479/047 GK3479/042 GK3494/026 GK3494/027 DST at 73.1 63.3 56.2 55.2 80 ms, 0.5 w % addition level w % TFOA 3.7 10.2 14.9 24.9

(85) TABLE-US-00013 Comparative examples GK3479/022 GK3479/021 GK3479/020 Efka 3600 GK3365/135 DST at 80 ms, 0.5 74.7 70.8 64.9 72.8 65.1 w % addition level w % TFOA 12.6 17.7 21.5 14.2 16 (ii) with Block B Containing Fluorinated Alpha-Olefin Derived Units

(86) Dynamic surface tension is measured using a bubble pressure tensiometer (Sita) at concentrations of 0.1% 1.0 w % in the A component of a solventbased 2K-PU. Bubble life times are measured from 80 msec up to 10 sec. In the following test series the commercial leveling additive EFKA 3600N is used a reference.

(87) A component 2K PU:

(88) TABLE-US-00014 TABLE 2.1 2K-PU Component A Weight 0.25 wt % Raw material Identity in g. Additive Macrynal Acrylic 89.0 SM510/60LG resin solution Butyl acetate Solvent 11.0 Formulation 100.0 19.95 Additive 0.05 Sample size 20.00

(89) At a very short bubble life time, a clear advantage (lower dynamic surface tension values) could be observed compared to the commercial benchmark at 0.25 w % addition levels.

(90) TABLE-US-00015 Inventive examples GM800-012 GM800-013 DST at 80 ms, 0.25 72.4 70.9 w % addition level

(91) TABLE-US-00016 Comparative examples Efka 3600N DST at 80 ms, 0.25 w % addition level 80.3

(92) The results are also shown in FIG. 1.

(93) Anticratering Test:

(94) The formulation, according to table 3.1, is treated for about one hour on the roll bench and finally shaken by hand until homogenous. The amount of component A indicated in table 3.2 is added in 20 ml glass jar with the appropriate amount of component B. The sample is immediately shaken by hand until homogenous and applied on a PET foil. A draw down of the mixture with 75 m wire bar at speed 20 mm/sec is prepared. The sample is checked for craters and haze on the panels after drying over night.

(95) TABLE-US-00017 TABLE 3.1 2K-PU Component A 0.1 0.25 0.5 0.75 1 wt % wt % wt % wt % wt % Weight Addi- Addi- Addi- Addi- Addi- Raw material Identity in g. tive tive tive tive tive Macrynal Acrylic 89.0 SM510/60LG resin solution Butyl acetate Solvent 10.5 Tinstab BL 277 Di-n- 0.5 1% in Butyl Butyltin acetate dilaurate Efka 2018N 8.0 Formulation 108.0 7.39 7.38 7.36 7.35 7.33 Additive 0.01 0.025 0.05 0.075 0.1 Sample size 7.40 7.405 7.41 7.425 7.43

(96) TABLE-US-00018 TABLE 3.2 2K-PU Component B 0.1 0.25 0.5 0.75 1 wt % wt % wt % wt % wt % Addi- Addi- Addi- Addi- Addi- Raw material Identity blank tive tive tive tive tive Desmodur Hardener 2.60 2.60 2.59 2.59 2.57 2.57 N75 (Resin) Component 7.40 7.40 7.405 7.41 7.425 7.43 A Sample size 10 10 10 10 10 10

(97) Mixing ratio: A:B=100:35 (36 round)

(98) TABLE-US-00019 TABLE 3.3 Anticrater performance in 2K-PU 0.1 wt % 0.25 wt % 0.5 wt % 1.0 wt % Examp. wt % Gloss Gloss Gloss Gloss Type Sample TFOA Craters 20 Crat. 20 Crat. 20 Crat. 20 comparative Blank.sup.a 8 158 GK3479/ 21.5 1 165 1 93.7 1 164 1 80.2 020 GK3479/ 17.7 4 165 1 162 1 125 1 118 021 GK3479/ 12.6 8 165 8 98.1 8 125 2 109 022 inventive GK3494/ 24.9 n/a 150 2 105 3 122 3 143 027 GK3494/ 14.9 2 163 3 136 3 92 3 150 026 GK3479/ 10.2 3 148 2 127 1 155 1 93.7 042 GK3479/ 3.7 8 163 4 163 2 128 2 148 047 comparative GK3365/ 16.1 2 158 7 138 7 157 4 123 135 GK3365/ 10.7 8 164 5 158 3 152 1 162 134 GK3365/ 5.3 8 163 6 130 3 163 2 159 133 .sup.aBlank contains no additive. 1 indicates no craters and 8 indicates many craters.