Poss modified polyacrylate fluoride-free waterproof agent and preparation method thereof

Patent metadata

Field	Value
Publication number	US-2021324116-A1
Application number	US-202117196004-A
Country	US
Kind code	A1
Filing date	Mar 9, 2021
Priority date	Apr 21, 2020
Publication date	Oct 21, 2021
Grant date	—

Abstract

A POSS modified polyacrylate fluorine-free waterproofing agent includes following components: 1-10 wt % of a functionalized POSS monomer, 2-20 wt % of methyl methacrylate, 3-26 wt % of butyl acrylate, 1-10 wt % of a long-chain acrylate monomer, 0.5-3.5 wt % of an initiator, 0.5-4 wt % of a reactive cationic emulsifier, and 50-80 wt % of deionized water. A method of preparing a POSS modified polyacrylate fluorine-free waterproofing agent is also disclosed.

First claim

What is claimed is:

1 . A POSS modified polyacrylate fluorine-free waterproofing agent consisting of following components:
1-10 wt % of a functionalized POSS monomer, 2-20 wt % of methyl methacrylate, 3-26 wt % of butyl acrylate, 1-10 wt % of a long-chain acrylate monomer, 0.5-3.5 wt % of an initiator, 0.5-4 wt % of a reactive cationic emulsifier, and 50-80 wt % of deionized water.

2 . The POSS modified polyacrylate fluorine-free waterproofing agent according to claim 1 , wherein the functionalized POSS monomer has the following structure:

R is propyl, isobutyl, or octyl, and R′ is vinyl, methacryloxypropyl, or a methacrylate group.

3 . The POSS modified polyacrylate fluorine-free waterproofing agent according to claim 1 , wherein the long-chain acrylate monomer is lauryl acrylate, hexadecyl acrylate, stearyl acrylate, or a mixture thereof.

4 . The POSS modified polyacrylate fluorine-free waterproofing agent according to claim 1 , wherein the initiator is 2,2′-azobis(2-methylpropionamidine) dihydrochloride or azobisisopropylamidine hydrochloride.

5 . The POSS modified polyacrylate fluorine-free waterproofing agent according to claim 1 , wherein the reactive cationic emulsifier is methacryloxyethyl dimethyl cetyl ammonium bromide, methyl acryloyloxyethyl dimethyl dodecyl ammonium bromide, or methacryloyloxyethyl dimethyl decyl ammonium bromide.

6 . A method of preparing a POSS modified polyacrylate fluorine-free waterproofing agent consisting of the following steps:
(1) mixing a functionalized POSS monomer, methyl methacrylate, butyl acrylate, a long-chain acrylate, methyl acryloyloxyethyl dimethyl dodecyl ammonium bromide, and deionized water in a weight ratio of 1.2:23:34:1.8:2.0:140 to obtain a pre-emulsion, the functionalized POSS monomer having the following formula:
(SiO 1.5 ) 8 R 7 (CH 2 ) 3 OOCC(CH 3 )CH 2 , R═—C 8 H 17 ;

(2) mixing 30% of the pre-emulsion obtained in step (1) with a methyl acryloyloxyethyl dimethyl dodecyl ammonium bromide aqueous solution in a reactor, the methyl acryloyloxyethyl dimethyl dodecyl ammonium bromide aqueous solution including methyl acryloyloxyethyl dimethyl dodecyl ammonium bromide and deionized water in a weight ratio of 1:60; stirring at 50° C. and a speed of 250 r/min; (3) preparing a 2,2′-azobis(2-methylpropionamidine) aqueous solution that includes 2,2′-azobis(2-methylpropionamidine) and deionized water in a weight ratio of 1:9; adding 35% of the 2,2′-azobis(2-methylpropionamidine) aqueous solution to the reactor and stirring for 20 minutes; (4) adding remaining 70% of the pre-emulsion obtained in step (1) and remaining 65% of the 2,2′-azobis(2-methylpropionamidine) aqueous solution to reactor in 90 minutes at 70° C., and stirring at 70° C. for 120 minutes; and (5) lowering to room temperature to obtain the POSS modified polyacrylate fluorine-free waterproofing agent as an emulsion.

7 . A method of preparing a POSS modified polyacrylate fluorine-free waterproofing agent consisting of the following steps:
(1) weighing the following raw materials according to mass percentage: a functionalized POSS monomer 1-10%, methyl methacrylate 2-20%, butyl acrylate 3-26%, a long-chain acrylic monomer 1-10%, an initiator 0.5-3.5%, a reactive cationic emulsifier 0.5-4%, deionized water 50-80%, the sum of the above components being 100%; (2) mixing 40-80% of the reactive cationic emulsifier weighed in step 1 and all of the functionalized POSS monomer, methyl methacrylate, butyl acrylate, and the long-chain acrylate weighed in step (1), and deionized water to obtain a pre-emulsion mixture; and then emulsifying the pre-emulsion mixture by high-speed stirring to prepare a pre-emulsion; (3) mixing remaining 20-60% of the reactive cationic emulsifier weighed in step 1 with an appropriate amount of deionized water to prepare a reactive cationic emulsifier aqueous solution; mixing the initiator weighed in step 1 with an appropriate amount of deionized water to prepare an initiator aqueous solution; mixing 20%-50% of the pre-emulsion prepared in step (2), 20%-50% of the initiator aqueous solution and the reactive cationic emulsifier aqueous solution, into a reactor equipped with an agitator and a condenser to obtain a reaction mixture; and stirring the reaction mixture at 40° C.-70° C. for 20 min-40 min; and (4) adding remaining 50%-80% of the pre-emulsion and remaining 50%-80% of the initiator aqueous solution simultaneously into the reaction mixture at 65-90° C. in 60-180 min; stirring the reaction mixture at 65-90° C. for 90-180 min; and lowering the temperature of the reaction mixture to room temperature to obtain the POSS modified polyacrylate fluorine-free waterproofing agent as an emulsion.

8 . The method for preparing POSS modified polyacrylate fluorine-free waterproofing agent according to claim 7 , wherein the pre-emulsion mixture is stirred at 300-700 r/min to obtain the pre-emulsion.

9 . The method for preparing POSS modified polyacrylate fluorine-free waterproofing agent according to claim 7 , wherein a mass ratio of the reactive cationic emulsifier and deionized water in the reactive cationic emulsifier aqueous solution in step (3) is 1:35.5-110.

10 . The method for preparing POSS modified polyacrylate fluorine-free waterproofing agent according to claim 7 , wherein a mass ratio of the initiator to deionized water in the initiator aqueous solution in step (3) is 1:8-12.

Assignees

• Zhou Jianhua
• Wang Lin
• Li Yan
• Chen Xiaoyu
• Univ Shaanxi Science & Tech

Inventors

• Zhou Jianhua
• Wang Lin
• Li Yan
• Chen Xiaoyu

Classifications

• C09D143/04

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C08F4/04

  Azo-compounds · CPC title

• C08F2/44

  Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers · CPC title

• C08F2/28

  cationic · CPC title

• C09D183/10 Primary

  Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00) · CPC title