CN102532404A - High-water-resistance acrylate emulsion and preparation method thereof - Google Patents

Abstract

The invention provides a high-water-resistance acrylate emulsion. The emulsion comprises the following raw materials in percentage by weight: 20%-25% of styrene, 15%-20% of butyl acrylate, 3%-5% of methyl methacrylate, 1%-3% of acrylic acid, 1%-2% of organic silicon monomer, 1%-2% of mixed emulsifying agent, 0.5% of sodium bicarbonate, 0.5% of initiator and the balance of water. According to the invention, in the emulsion polymerization process, a reaction type emulsifying agent is adopted to carry out a polymerization reaction, and the emulsifying agent is polymerized to a large molecule chain in the polymerization process, thereby reducing the transfer of the emulsifying agent in a paint film, reducing the water adsorption rate of the paint film and improving water resistance; through adopting a nucleus-shell polymerization process, a shell polymerization part is subjected to copolymerization modification with organic silicon, so that a hydrophobic structure is formed on the surface of a latex particle, thereby improving the water resistance after film formation finally; and through the synergistic effect of the two methods, the water resistance of the prepared emulsion is greatly improved and the prepared emulsion can be widely applied to production and preparation of paints for inner and outer walls.

Description

A kind of enhanced water resistance acrylic ester emulsion and preparation method thereof

Technical field

The present invention relates to the synthetic field of macromolecular material, be specially a kind of enhanced water resistance acrylic ester emulsion that is mainly used in trade sales coating, the present invention also comprises this preparing acrylate emulsion method.

Background technology

Trade sales coating is very fast with the acrylic emulsion development in recent years, and is along with aqueous architectural coating obtains increasing application in life, also increasingly high to the acrylic emulsion performance demands.Process the problem that trade sales coating generally can face the water resistance difference by ordinary method synthetic acrylic emulsion, this is because emulsion can be applied to stronger emulsifying agent of some wetting abilities and hydrophilic monomer in the preparation process.These hydrophilic component can show very strong water-absorbent at coating surface; More particularly at the inner small-molecular emulsifier of paint film; Can absorbing moisture again with after water contacts, cause phenomenons such as paint film occurs turning white, bubbles even comes off along with the time moves to the surface.Therefore, how improving the water resistance behind the emulsion film forming, be not only the important topic in the synthetic field of coating emulsion, is a research direction of current emulsion polymerization technology.

Summary of the invention

Technical problem to be solved by this invention provides a kind of enhanced water resistance acrylic ester emulsion and preparation method thereof, the water tolerance after the raising coating emulsion film forming.

Technical problem of the present invention adopts following technical proposals to solve:

A kind of enhanced water resistance acrylate paint emulsion is characterized in that being prepared from following raw material and proportioning:

Vinylbenzene: 20%～25%, Bing Xisuandingzhi: 15%～20%, TEB 3K 3%～5%, vinylformic acid 1%～3%, an organosilane monomer 1%～2%, blending emulsifiers 1%～2%, sodium hydrogencarbonate 0.5%, initiator 0.5%, surplus is a water.

Described initiator is ammonium persulphate or Sodium Persulfate.

Described an organosilane monomer is γ-An Bingjisanyiyangjiguiwan (KH550) or γ-An Bingjisanjiayangjiguiwan (KH551).

The quality proportioning of each emulsifying agent is in the described blending emulsifiers: nonionic emulsifying agent: anionic emulsifier: reactive emulsifier=1:2:1～2.

Described anionic emulsifier is sodium lauryl sulphate (K12); Said nonionic emulsifying agent is OP-10; Said reactive emulsifier is: allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) or hydroxyethyl methacrylate propyl sulfonic acid sodium (HMPS).

Preparation technology's flow process of aforesaid propylene acid esters coating emulsion is following:

(1) 10% of water inventory with the initiator dissolving during usefulness was filled a prescription, and processed initiator solution, subsequent use;

(2) will fill a prescription in the blending emulsifiers total amount 60% with prescription in water inventory 40%, whole sodium hydrogencarbonate, and vinylformic acid, Bing Xisuandingzhi; Vinylbenzene, the methyl methacrylate polymerization monomer carries out high speed dispersion, the preparation pre-emulsion; Pre-emulsion is divided into A, two parts of B, the A:B weight ratio is 2:1; In B, adding an organosilane monomer mixes

(3) will fill a prescription in the blending emulsifiers total amount 40%; 50% of water inventory drops into reaction kettle in the prescription; Be warmed up to 80-85 ℃; Slowly add pre-emulsion A that configures and 6/10 of the initiator solution that configures, drip pre-emulsion B and 3/10 of the initiator solution that configures then, all pre-emulsions added at 3-3.5 hour;

(4) add 1/10 of the initiator solution that configures after, keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate emulsion viscosity, pack discharging at 90 ℃.

Major technique characteristics of the present invention are following:

1, in the process of letex polymerization, adopt the emulsifying agent of response type to carry out polyreaction, emulsifying agent participates in being aggregated on the macromolecular chain in polymerization process, has reduced the migration of emulsifying agent in paint film, has reduced the water-intake rate of paint film, has improved water tolerance.

2, through adopting the technology of nuclear-shell polymerization, adopt organosilicon to carry out modification by copolymerization, make the emulsion particle surface form a kind of hydrophobic structure, improved the water tolerance after the final film forming at the shell polymeric part.

Through the synergy of these two kinds of methods, can make the water tolerance behind the prepared emulsion film forming obtain very big raising, can be widely used in the production preparation of coating for internal and external wall.

Embodiment

Embodiment 1

Vinylbenzene 20g, Bing Xisuandingzhi 20g, TEB 3K 5g, vinylformic acid 1g, an organosilane monomer KH550 1g, blending emulsifiers 2g (op-10 0.4g, K12 0.8g, AHPS 0.8g), sodium hydrogencarbonate 0.5g, ammonium persulphate 0.5g, deionized water 50g.

(1) 0.5g ammonium persulphate and 5g water are mixed with initiator solution.（5mL）

(2) in the 200mL four-hole bottle, blending emulsifiers and 20g water, the 0.5g sodium hydrogencarbonate of 1.2g mixed; Add polymerization single polymerization monomers such as vinylformic acid 3g, Bing Xisuandingzhi 20g, vinylbenzene 20g, TEB 3K 5g then and carry out high speed dispersion; Preparation monomer pre-emulsion; Pre-emulsion is divided into A, and two parts of B (the A:B weight ratio is 2:1) add an organosilane monomer KH550 1g and mix in B.

(3) with the 0.8g blending emulsifiers; The water of 25g drops in the 200mL four-hole bottle; Be warmed up to 80-85 ℃, successively slowly drip pre-emulsion A and the pre-emulsion B that configures, drip initiator solution 4.5mL (always 90% of amount of initiator) simultaneously and carry out polyreaction; Whole process maintains the temperature at 80-85 ℃, and pre-emulsion and initiator all added about about 3-3.5 hour.

(4) add initiator solution 0.5mL (total amount of initiator 10%), keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate the emulsion pH value to 7-8, filter, pack with ammoniacal liquor at 90 ℃.

Embodiment 2

Vinylbenzene: 25g, Bing Xisuandingzhi: 15g, TEB 3K 3g, vinylformic acid 3g, an organosilane monomer KH551 2g, blending emulsifiers 1g (op-10 0.2g, K12 0.4g, HMPS 0.4g), sodium hydrogencarbonate 0.5g, Sodium Persulfate 0.5g, deionized water 50g.

Reaction process is following:

(1) 0.5g ammonium persulphate and 5g water are mixed with initiator solution (5mL).

(2) in the 200mL four-hole bottle, blending emulsifiers and 20g water, the 0.5g sodium hydrogencarbonate of 0.8g mixed, add the vinylformic acid of formula ratio then, Bing Xisuandingzhi; Vinylbenzene; Polymerization single polymerization monomers such as TEB 3K carry out high speed dispersion, and preparation monomer pre-emulsion is divided into A with pre-emulsion; Two parts of B (the A:B weight ratio is 2:1) add 1g KH-550 and mix in B.

(3) with the 1.2g blending emulsifiers; The water of 25g drops in the 200mL four-hole bottle; Be warmed up to 80-85 ℃, successively slowly drip pre-emulsion A and the pre-emulsion B that configures, drip initiator solution 4.32mL (always 90% of amount of initiator) simultaneously and carry out polyreaction; Whole process maintains the temperature at 80-85 ℃, and pre-emulsion and initiator all added about about 3-3.5 hour.

(4) add initiator 0.5mL (total amount of initiator 10%), keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate the emulsion pH value to 7-8, filter, pack with ammoniacal liquor at 90 ℃.

The above is merely and the present invention relates to the part instance; Other relate to instance because length is limit the present invention; Can not list one by one; In every case according to know-why of the present invention above instance is done equivalent modifications or proportioning variation in prescription given to this invention and technology, all within protection scope of the present invention.

Claims (6)

1. enhanced water resistance acrylate paint emulsion is characterized in that being prepared from following raw material and proportioning:

Vinylbenzene: 20%～25%, Bing Xisuandingzhi: 15%～20%, TEB 3K 3%～5%, vinylformic acid 1%～3%, an organosilane monomer 1%～2%, blending emulsifiers 1%～2%, sodium hydrogencarbonate 0.5%, initiator 0.5%, surplus is a water.

2. a kind of high water-resisting type acrylic ester emulsion according to claim 1 is characterized in that described initiator is ammonium persulphate or Sodium Persulfate.

3. a kind of high water-resisting type acrylic ester emulsion according to claim 1 is characterized in that described an organosilane monomer is γ-An Bingjisanyiyangjiguiwan (KH550) or γ-An Bingjisanjiayangjiguiwan (KH551).

4. a kind of high water-resisting type acrylic ester emulsion according to claim 1 is characterized in that the quality proportioning of each emulsifying agent in the described blending emulsifiers is: nonionic emulsifying agent: anionic emulsifier: reactive emulsifier=1:2:1～2.

5. according to claim 1 or 4 described a kind of enhanced water resistance acrylic ester emulsions, it is characterized in that described anionic emulsifier is sodium lauryl sulphate (K12); Said nonionic emulsifying agent is OP-10; Said reactive emulsifier is: allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) or hydroxyethyl methacrylate propyl sulfonic acid sodium (HMPS).

6. the described a kind of enhanced water resistance preparing acrylate emulsion method of claim 1 is characterized in that by following prepared:

(1) 10% of water inventory with the initiator dissolving during usefulness was filled a prescription, and processed initiator solution, subsequent use;

(2) will fill a prescription in the blending emulsifiers total amount 60% with prescription in water inventory 40%, whole sodium hydrogencarbonate, and vinylformic acid, Bing Xisuandingzhi; Vinylbenzene, the methyl methacrylate polymerization monomer carries out high speed dispersion, the preparation pre-emulsion; Pre-emulsion is divided into A; Two parts of B, the A:B weight ratio is 2:1, in B, adds an organosilane monomer and mixes;

(3) will fill a prescription in the blending emulsifiers total amount 40%; 50% of water inventory drops into reaction kettle in the prescription; Be warmed up to 80-85 ℃; Slowly add pre-emulsion A that configures and 6/10 of the initiator solution that configures, drip pre-emulsion B and 3/10 of the initiator solution that configures then, all pre-emulsions added at 3-3.5 hour;

(4) add 1/10 of the initiator solution that configures after, keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate emulsion viscosity, pack discharging at 90 ℃.