Acrylated semi-crystalline hyperbranched polyurethane oligomer and preparation method thereof

1. A method for preparing an acrylated semi-crystalline hyperbranched polyurethane oligomer, comprising forming a hydroxy-terminated hyperbranched polyurethane, and modifying the hydroxy-terminated hyperbranched polyurethane in a two-step process, wherein the two-step process includes the following steps:

forming a long carbon chain with a carbon atom number higher than 10 or a benzene ring or a naphthalene ring at a portion of the terminal hydroxyl groups of the hydroxy-terminated hyperbranched polyurethane to obtain a semi-crystalline hyperbranched intermediate possessing residual terminal hydroxyl groups, and

making a modification to the residual terminal hydroxyl groups of the hydroxy-terminated hyperbranched polyurethane with methacrylic and/or acrylic double bonds to form an acrylated semi-crystalline hyperbranched polyurethane oligomer.

2. The method according to claim 1 , wherein the two-step process includes

the first step of

dissolving the hydroxy-terminated hyperbranched polyurethane in a solvent,

adding with stirring, a compound (I) containing a functional group reactive with a portion of the terminal hydroxyl groups of the hydroxyl-terminated hyperbranched polyurethane and a long carbon chain having a carbon atom number higher than 10 or a benzene ring or a naphthalene ring in a certain proportion, wherein said certain proportion refers to the molar reaction ratio of the compound (I) with a long carbon chain or a benzene ring or a naphthalene ring to the terminal hydroxyl groups of the hydroxy-terminated hyperbranched polyurethane, and is presented by the value X meeting the inequation 0<x<1, and

reacting the hydroxy-terminated hyperbranched polyurethane with the compound (I) at a temperature ranging from about 30° C. to about 120° C. for about 8 hours to about 48 hours in the presence of a catalyst to provide a polyurethane intermediate having residual hydroxyl terminal groups; and

the second step of

dissolving the intermediate in a solvent,

adding dropwisely, with stirring an unsaturated capping compound (II) containing a functional group reactive with hydroxyl in a molar amount equivalent to that of the terminal hydroxyl groups of the intermediate formed from the first reaction step,

reacting the intermediate and the compound (II) at a temperature ranging from about 30° C. to about 120° C. for about 2 hours to about 20 hours in the presence of a catalyst and a polymerization inhibitor, and then

washing with water to remove by-products.

3. The method according to claim 2 , wherein the compound (I) containing a functional group reactive with hydroxyl and a long carbon chain with a carbon atom number higher than 10 or a benzene ring or a naphthalene ring includes monoacyl chloride, monoisocyanate, or monocarboxylic acid.

4. The method according to claim 3 , wherein the chemical formula of the monoacyl chloride is RCOCl, wherein R is an alkyl containing more than 10 carbons or phenyl or naphthyl; the chemical formula of the monoisocyanate is RNCO, wherein R is an alkyl containing more than 10 carbons or phenyl or naphthyl; and the chemical formula of the monocarboxylic acid is RCOOH, wherein R is an alkyl containing more than 10 carbons or phenyl or naphthyl.

5. The method according to claim 4 , wherein the monoacyl chloride includes undecanoyl chloride, dodecanoyl chloride, tetradecanoyl chloride, hexadecanoyl chloride, or benzoyl chloride; the monoisocyanate includes undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, or phenyl isocyanate; and the monocarboxylic acid includes undecanoic acid, palmitic acid, stearic acid, or benzoic acid.

6. The method according to claim 2 , wherein the unsaturated compound (II) containing a functional group reactive with hydroxyl includes acrylic anhydride, methacrylic anhydride; acrylic acid, methacrylic acid; acryloyl chloride or methacryloyl chloride.

7. The method according to claim 1 , wherein the method for forming the hydroxy-terminated hyperbranched polyurethane includes the following steps:

dissolving a polyhydroxyamine monomer in a solvent,

adding a difunctional isocyanate monomer at a temperature ranging from about −5° C. to about 10° C. to provide a first reaction mixture,

maintaining the temperature of the first reaction mixture at about −5° C. to about 10° C. for about 1 hour to about 15 hours,

adding a catalyst to provide a second reaction mixture,

heating the second reaction mixture at a temperature ranging from about 50° C. to about 90° C. for about 12 hours to about 48 hours, and

the resulting reaction being precipitated, filtered, and dried to provide the hydroxy-terminated hyperbranched polyurethane.

8. The method according to claim 7 , wherein the polyhydroxyamine includes diethanolamine, dipropanolamine, dibutanolamine, dipentanolamine, N,N-dihydroxyphenethyl-3-amine, dihydroxymethylaminoethane, trihydroxymethylaminomethane, or N-methyl-d-glucosamine.

9. The method according to claim 7 , wherein the difunctional isocyanate monomer includes tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, or isophorone diisocyanate.

10. The method according to claim 2 or 7 , wherein the solvent includes dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethyl acetamide, toluene, dioxane, ethyl acetate, N-methylpyrrolidinone, butanone, xylene, or tetrahydrofuran.

11. An acrylated semi-crystalline hyperbranched polyurethane oligomer obtained by the method according to claim 1 , characterized in that the acrylated semi-crystalline hyperbranched polyurethane oligomer has a methacrylic and/or acrylic double bond at a portion of the terminals and a long carbon chain with a carbon atom number higher than 10 or a benzene ring or a naphthalene ring at the residual terminals.