# US 10,479,867 B2 · Method of producing super soft polyacrylate-urethane (PAU) core-shell copolymer dispersions by solvent free process

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- Number: US 10,479,867 B2
- Document ID: US10479867B2
- Status: Granted
- Kind: B2
- Application number: 15/708,247
- Filed: 2017-09-19
- Published: 2019-03-21
- Granted: 2019-11-19
- Earliest claimed: 2017-09-19
- Assignees: Ho Yu Textile Co., Ltd.
- Applicants: Da-Kong Lee; Chin-Jen Jwo; Wun-Syu Zeng
- Inventors: Da-Kong Lee; Chin-Jen Jwo; Wun-Syu Zeng
- Web page: https://patentgrep.com/patent/US10479867B2

## CPC

- C08G 81/024: {Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G}
- C08G 18/0866: {the dispersing or dispersed phase being an aqueous medium}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/348: {Hydroxycarboxylic acids}
- C08G 18/42: Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G 18/48: Polyethers
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/6625: {with compounds of group C08G18/34}
- C08G 18/722: {Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates}
- C08G 18/73: acyclic
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C09D 175/04: Polyurethanes
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

Method of producing super soft PAU core-shell copolymer dispersions is a solvent free process. The products have characteristics of both polyurethane and polyacrylate including being non-sticky, having a feeling of touching a peach when touching it by the hand, and having improved adhesion, tensile strength, and toughness.

## Claims

### Claim 1

A method of producing dispersions from acrylate monomers by a solvent free process comprising:
(a) synthesizing a solvent free polyurethane dispersion (PUD) in the amount of 40.0 wt % of the acrylate monomers as a seed emulsion;
(b) taking an initiator in the amount of 0.20 wt. %-0.60 wt. % of the acrylate monomers to dissolve in deionized water to obtain an initiator solution which is equally distributed into first, second and third parts;
(c) taking an emulsifier in the amount of 0.20 wt %-0.30 wt % of the acrylate monomers, polyoxyethylene alkyl ether ammonium sulfate in the amount of 0.20-0.30 wt. % of the acrylate monomer, and n-butyl acrylate (n-BA) as a soft monomer in the amount of 3.0-8.0 wt. % of the acrylate monomers to emulsify in the deionized water to obtain a first pre-emulsion acrylate;
(d) taking the emulsifier in the amount of 0.20 wt %-0.30 wt % of the acrylate monomers, the polyoxyethylene alkyl ether ammonium sulfate in the amount of 0.13 wt %-0.30 wt % of the acrylate monomers, the n-BA in the amount of 43.3 wt %-86.7 wt % of the acrylate monomers, and methyl methacrylate (MMA) as a hard monomer in the amount of 8.0 wt %-52.0 wt % of the acrylate monomers to emulsify in the deionized water to obtain a second pre-emulsion acrylate;
(e) pouring the solvent free PUD into a reaction vessel having a reaction temperature set at 70-90° C. and a rotational speed set at 300-500 rpm for reaction;
(f) adding the first pre-emulsion acrylate and the first part of the initiator solution to the reaction vessel for one to two hours;
(g) adding the second pre-emulsion acrylate and the second part of the initiator solution into the reaction vessel;
(h) after adding more than half of the second pre-emulsion acrylate, adding the third part of the initiator solution into the reaction vessel;
(i) increasing the reaction temperature up to 90-95° C.;
(j) maintaining the reaction temperature for one to two hours and turning off heating; and
(k) cooling the reaction vessel for one hour to produce a solid content of 40.0 wt % of solvent free super soft polyacrylate-urethane (PAU) core-shell copolymer dispersions, wherein a weight percentage ratio of polyacrylate (PA) and polyurethane (PU) is 25 wt %:100 wt % -100 wt %:100 wt %.

### Claim 2 (depends on 1)

The method of claim 1, wherein synthesizing the seed emulsion comprises:
(1) drying polyol at a temperature in vacuum for a period of time;
(2) placing both the dried polyol and 2,2-dimethylol butanoic acid (DMBA) in another reaction vessel to mix at 90° C. and rotate at a rotational speed 100 rpm until a mixture becomes transparent;
(3) adding diisocyanate having an isocyanate functional group (—NCO) to the mixture to react at 70-90° C. and a rotational speed of 50-100 rpm for 5-10 minutes until a —NCO terminated first prepolymer is formed;
(4) decreasing temperature of the —NCO terminated first prepolymer to 65° C.;
(5) adding a neutralizing agent to the —NCO terminated first prepolymer for neutralization and catalysis until a —NCO terminated second prepolymer is formed;
(6) adding the remaining diisocyanate having the isocyanate functional group to the —NCO terminated second prepolymer to form a —NCO terminated third prepolymer;
(7) adding deionized water to the third prepolymer to form a prepolymer dispersion; and
(8) adding a chain extension agent to the prepolymer dispersion to rotate at a range of 1,000 to 2,000 rpm for a chain extension for 1-3 hours until the solvent free PUD is produced;
wherein a mole ratio of the polyol to the DMBA is 0.57 to 9.11, and a molar percentage of the polyol to DMBA is 36.3%:63.7% to 90.1%:9.9%;
wherein a mole ratio of the diisocyanate having the isocyanate functional group to the mixture of the —NCO terminated first prepolymer is 1.08 to 1.12 and a molar percentage of the diisocyanate having the isocyanate functional group to the mixture of the —NCO terminated first prepolymer is 51.9%:48.1% to 52.9%:47.1%;
wherein a mole ratio of the —NCO terminated first prepolymer to the neutralizing agent is 0.38 to 1.56, and a molar percentage of the —NCO terminated first prepolymer to the neutralizing agent is 27.7%:72.3% to 61.0%:39.0%; and
wherein a mole ratio of the —NCO terminated second prepolymer to the diisocyanate having the isocyanate functional group is 0.14 to 0.63, and a molar percentage of the —NCO terminated second prepolymer to the diisocyanate having the isocyanate functional group is 12.2%:87.8% to 38.6%:61.4%.

### Claim 3 (depends on 2)

The method of claim 2, further comprising adding hydroxyethyl acrylate (HEA) to the —NCO terminated third prepolymer and agitating for two to four hours to form a —NCO terminated fourth prepolymer having a —C═C-functional group; and wherein a mole ratio of the —NCO terminated third prepolymer to the HEA is 0 to 2.0, and a molar percentage of the —NCO terminated third prepolymer to the HEA is 66.7% :33.3% to 100.0%:0%.

### Claim 4 (depends on 1)

The method of claim 1, wherein: adding the first pre-emulsion acrylate to the reaction vessel is at the speed of 0.40-0.70 mL/min, and adding of the KPS initiator solution to the reaction vessel is at a speed of 0.30-0.45 mL/min; adding the second pre-acrylate emulsion is at a speed of 1.00-1.20 mL/min and the second part of the initiator solution is at the speed of 0.10-0.30 mL/min; and adding the third part of the initiator solution is at a speed of 0.10-0.30 mL/min.

### Claim 5 (depends on 1)

The method of claim 1, wherein the acrylate monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, dodecyl 2-methylacylate, acrylic acid, methacrylic acid, 2-(dimethylamino)ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, glycidyl acrylate or glycidyl methacrylate.

### Claim 6 (depends on 1)

The method of claim 1, wherein the initiator solution is potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, organic peroxide, diacyl peroxide, peroxy acid, perester or azo compounds.

### Claim 7 (depends on 1)

The method of claim 1, wherein the emulsifier is sodium dodecyl benzene sulfonate, dioctyl sodium sulfosuccinate, sodium dodecyl diphenyl disalfonate, succinate polyoxyethylene alkyl phenol ether sulfonate half ester, succinate polyoxyethylene alkyl phenol ether sulfonate half ester, poly ehthylene oxide-b-propylene oxide or polyoxyethylene alxylphenol ether.

### Claim 8 (depends on 1)

The method of claim 1, wherein the super soft PAU core-shell copolymer dispersions have a shell of PUD and a core of polyacrylate dispersions.

### Claim 9 (depends on 8)

The method of claim 8, wherein the super soft PAU core-shell copolymer dispersions have a 500% modulus less than 6.0 MPa, and a tensile strength greater than 15.0 MPa.