CN105693939B

CN105693939B - A kind of preparation method of the SMA modified cation acrylic acid ester emulsion of priming paint

Info

Publication number: CN105693939B
Application number: CN201410714322.2A
Authority: CN
Inventors: 许钧强; 康伦国; 姚东生; 阳京辉; 许钧峰
Original assignee: Shaoguan Union Chemical Co Ltd; Union Foshan Chemical Co Ltd
Current assignee: Shaoguan Union Chemical Co Ltd; Union Foshan Chemical Co Ltd
Priority date: 2014-11-28
Filing date: 2014-11-28
Publication date: 2019-03-29
Anticipated expiration: 2034-11-28
Also published as: CN105693939A

Abstract

The present invention relates to a kind of preparation methods of the SMA modified cation acrylic acid ester emulsion of priming paint, are mainly emulsified by the acrylic monomers of imidizate SMA quaternary amine, carboxylic acrylic monomers, the acrylic monomers of hydroxyl, free radical polymerization by cationic microgel；The SMA modified cation acrylic acid ester emulsion of priming paint produced by the present invention, due to importing imidizate SMA functional resin, temperature tolerance, alkali resistance, wearability, compatibility, water resistance and the excellent adhesive force of paint film can be effectively improved, and the partial size of lotion reaches nanoscale (≤150nm), therefore modified cation acrylate emulsion is a kind of nanometer micro-emulsion, with very strong permeability, it can react with alkaline matter, the film compactness of formation is high, closure is strong, can effectively improve film alkali burnout resistance and resistance to saltouing property；It is widely used in inner-outer wall seal coat, aqueous wooden ware seal coat, water-based ink, sizing agent, adhesive etc..

Description

A kind of preparation method of the SMA modified cation acrylic acid ester emulsion of priming paint

Technical field

The present invention relates to a kind of preparation methods of modified acrylate emulsion more particularly to a kind of SMA of priming paint to change Property cation acrylate emulsion.

Background technique

Common sealing acrylic priming paint is typically all that anionic lotion is modulated, the current country be widely used third Alkene acrylic copolymer emulsions generally use monomer of the methacrylic acid as enhancing adhesive force, but there are poor adhesive forces, alkali resistance Weak disadvantage；The emulsifier used is usually lauryl sodium sulfate and nonylphenol polyoxyethylenes ether, is produced using anion Lotion partial size it is relatively much bigger (general emulsion particle diameter be 0.1~10 μm), surface tension is very big, is difficult to penetrate into ground In the tiny pore in portion, so the density of surface of bottom material film can only be relied on to realize the effect of back cover；Propylene acid seal It closes priming paint membrane formation mechanism and belongs to physical film deposition, chemical reaction of becoming film cannot occur between macromolecule, only steamed according to itself moisture Hair, macromolecule micelle soften under the action of coalescing agent and then mutual extrusion forms a film, so paint film is not close, gap it is larger compared with More (good permeabilities)；Exactly the gas permeability of emulsion paint film also becomes the factor film defects such as the accumulation of salt in the surface soil occurs, saltouts, and drenches through water Afterwards, water penetration dissolves soluble-salt therein, while also having dissolved water soluble alkali, is partly dissolved object with dampening into paint film the inside Divide and migrates to surface of bottom material and CO₂Reaction generates salt, and with the continuous evaporation of moisture during migration, dissolved matter is constantly tied Partial crystallization goes out, if crystallization is easy for leading to falling off for paint film between paint film and ground, is formed if crystallizing in surface of the paint film general It alkali and saltouts.

There are lesser surface tension, basic species extremely strong to the permeability of ground using cation acrylic seal coat Matter and temperature can promote the cross-linking reaction of cation emulsion, so the new metope of strong basicity can be allowed to the effect that preferably forms a film Fruit plays better sealing process, improves the alkali resistance and resistance to saltouing property of film.

CN102050918B discloses a kind of emulsifier-free emulsion polymerization method of cationic polyacrylate finishing agent, using two Allyl dimethyl ammonium chloride make emulsifier, butyl acrylate and methyl methacrylate by emulsifier-free emulsion polymerization preparation sun from Sub- polyacrylate leather finishing agent, the latex particle size of lotion is about in 800nm or so；It is applied to leather finish technique In, wherein the tensile strength, water imbibition of leather, dry and wet rubbing fastness remove from office sample phase after covering with paint, lacquer, colour wash, etc. with commercially available cationic polyacrylate emulsion Closely, but elongation at break is improved.

CN103265655A discloses a kind of response type cationic polyacrylate emulsion and the preparation method and application thereof, belongs to In paper technology and printing packaging technical field；The 40~45% of total monomer amount are accounted for including styrene, butyl acrylate Zhan is always single The 40~45% of the scale of construction, acrylamide account for the 5~12% of total monomer amount, and diallyldimethylammonium chloride accounts for the 5 of total monomer amount ~12%, protecting colloid polyvinyl alcohol accounts for the 0.1~0.6% of total monomer amount, and hexadecyltrimethylammonium chloride accounts for total monomer amount 1~5%, alkyl phenol polyoxyethylene ether -10 accounts for the 1~5% of total monomer amount, allyloxy Nonyl pheno 5~9%, Initiator potassium persulfate 0.5~1.2%, prepares cationic polyacrylate emulsion；Response type cation polypropylene of the invention Acid esters lotion cream, has stability good, can improve paper strength and the effect of paper water resistant.

CN101475661B discloses the preparation of a kind of fluorine silicon/or oil modified acrylic ester copolymer cation emulsion, should Lotion is by alkyl acrylate and (methyl) alkyl acrylate, ethylene carbonate, including fragrant substituted olefine, function monomer: Such as N- alkylol acrylamides, (methyl) fluoroalkyl acrylate, vinyl/or acrylyl oxy-ethyl trialkoxy silane Or polymerizable acryloyloxyalkyl polyurethane, (methyl) acrylyl oxy-ethyl tri alkyl ammomium chloride or (methyl) acrylic acid diformazan Aminoethyl and crosslinking agent etc., in the presence of cationic surfactant and nonionic surfactant, carry out emulsion polymerization and ?.The cation emulsion is had excellent performance, and is widely used in paper products, plastics, the finishing agent and high-grade paint of leather.

Summary of the invention

Imidizate SMA quaternary amine is kind of a polymerizable cationic polymeric surfactant, with activated monomer such as benzene second Alkene, acrylic monomer have reactivity well；Using sun/nonionic mesization polymerization, it is functional to import imidizate SMA Resin, modified cation acrylate emulsion can effectively improve the temperature tolerance of paint film, alkali resistance, wearability, compatibility, water-fast Property and excellent adhesive force, and the partial size of lotion reaches nanoscale (≤150nm), therefore imidizate SMA cationic acrylamide Acid esters lotion is a kind of nanometer micro-emulsion, has very strong permeability, can react with alkaline matter, and the film of formation is fine and close Property it is high, closure is strong, can effectively improve film alkali burnout resistance and resistance to saltouing property.

In order to solve the problems, such as that techniques as described above, the present invention take following technical scheme: the present invention relates to a kind of priming paint SMA modified cation acrylic acid ester emulsion, consisting of: imidizate SMA quaternary amine 7~15%, carboxylic propylene Acid monomers 2~8%, the acrylic monomers 2~8% of hydroxyl, the acrylic monomers 20~40% of free radical polymerization, OP-10 cream Agent 1~4%, cationic initiator 0.2~0.6%, 50~65 parts of deionized water.

Wherein, the carboxylic acrylic monomers is one kind of acrylic or methacrylic acid；The hydroxyl Acrylic monomers be acrylic acid -2- hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid -2- hydroxy butyl ester, methacrylic acid -2- hydroxyl At least one of ethyl ester, Hydroxypropyl methacrylate, methacrylic acid -2- hydroxy butyl ester or N hydroxymethyl acrylamide；It is described Free radical polymerization acrylic monomers be methyl methacrylate, ethyl methacrylate, butyl acrylate, methacrylic acid Butyl ester, acrylonitrile, acrylamide or dimethylaminoethyl methacrylate at least two or more monomer.

The cationic initiator is azo-bis-isobutyrate hydrochloride (AIBA) and two isobutyl imidazoline hydrochloride of azo One of (AIBI).

The present invention proposes a kind of preparation method of the SMA modified cation acrylic acid ester emulsion of priming paint, preparation method, Include the following steps:

A, in the reaction vessel equipped with speed-adjustable stir device, return pipe, dropping funel and thermometer, acyl is added by formula ratio Imidization SMA quaternary amine, 20~30% mix monomer, OP-10 emulsifier and 60~80% deionized water, be heated to 60 DEG C It to whole dissolutions, is emulsified under high velocity agitation, obtains pre-emulsion；

B, it is filled with N₂, it is warming up at 80 DEG C, under the stirring of certain speed, 20% cationic initiator aqueous solution is added dropwise (3% mass ratio) reacts 0.5~1h；

C, it maintains the temperature at 81~83 DEG C, upper remaining 70~80% mix monomer and remaining 80% is at the uniform velocity added dropwise Ionic initiator aqueous solution after dripping off in 1.5~2hr, is warming up to 88 DEG C, and insulation reaction 0.5hr cools to 60 DEG C, adds Remaining water is cooled to 40 DEG C and filters and packages, and it is modified to obtain the SMA that solid content is 40 ± 2%, partial size≤150nm priming paint Cation acrylate emulsion.

The SMA modified cation acrylic acid ester emulsion of priming paint produced by the present invention, due to importing imidizate SMA function Property resin, can effectively improve temperature tolerance, alkali resistance, wearability, compatibility, water resistance and the excellent adhesive force of paint film, and The partial size of lotion reaches nanoscale (≤150nm), therefore modified cation acrylate emulsion is a kind of nanometer micro-emulsion, tool There is very strong permeability, can react with alkaline matter, the film compactness of formation is high, and closure is strong, can effectively improve painting The alkali burnout resistance of film and resistance to saltouing property；It is widely used in inner-outer wall seal coat, aqueous wooden ware seal coat, water-based ink, sizing Agent, adhesive etc..

Specific embodiment

Embodiment prepares material according to the component formula of table 1.

1: three embodiment component formula (mass parts) of table

Material name	Example 1	Example 2	Example 3
				Methyl methacrylate	20	19	20
Imidizate SMA quaternary amine	8.6	9.5	10
				Butyl acrylate	6.8	7.2	6.4
Methacrylic acid	2.4	-	2.4
				Acrylic acid	-	2.4	-

Acrylic acid -2- hydroxyl ethyl ester	-	2.8	-
				N hydroxymethyl acrylamide	2.6	-	2.4
Emulsifier op-10	2.0	2.0	2.0
				AIBA	-	-	0.3
AIBI	0.3	0.3	-
				Deionized water	57.3	56.8	56.5

Embodiment 1:

A, in the reaction vessel equipped with speed-adjustable stir device, return pipe, dropping funel and thermometer, 8.6 parts of acyl Asias are added Amination SMA quaternary amine, 25% mix monomer, 2 parts of OP-10 emulsifiers and 70% deionized water, be heated to 60 DEG C to whole Dissolution, is emulsified under high velocity agitation, obtains pre-emulsion；

B, it is filled with N₂, it is warming up at 80 DEG C, under the stirring of certain speed, 2 parts of AIBI aqueous solution (3% mass is added dropwise Than), react 0.5~1h；

C, it maintains the temperature at 81~83 DEG C, upper remaining 75% mix monomer and remaining 8 parts of AIBI is at the uniform velocity added dropwise Aqueous solution after dripping off in 1.5~2hr, is warming up to 88 DEG C, and insulation reaction 0.5hr cools to 60 DEG C, adds remaining water, cold But filtered and packaged to 40 DEG C, obtain solid content be 40.7%, partial size≤128nm, pH value 5.0 priming paint the modified sun of SMA from Sub- acrylic acid ester emulsion.

The preparation of embodiment 2, embodiment 3 is carried out referring to the step in embodiment 1.

To the basic performance of the SMA modified cation acrylic acid ester emulsion of priming paint produced by the present invention, according to national phase Pass standard is detected, and test result is as shown in table 2.

Table 2: the SMA modified cation acrylic acid ester emulsion performance of priming paint

The SMA modified cation acrylic acid ester emulsion and cation third on the market of priming paint made from three embodiments Film is made in olefin(e) acid ester lotion (comparative example), is detected according to relevant national standard, compares test to film performance, surveys Test result is as shown in table 3.

Table 3: cation acrylate emulsion film performance

Although the present invention has described it in detail and cited embodiments, but for those of ordinary skill in the art, show Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.

Claims

1. a kind of preparation method of the SMA modified cation acrylic acid ester emulsion of priming paint, it is characterised in that: the preparation side Method includes the following steps:

A), in the reaction vessel equipped with speed-adjustable stir device, return pipe, dropping funel and thermometer, it is sub- that acyl is added by formula ratio Amination SMA quaternary amine, 20~30% mix monomer, OP-10 emulsifier and 60~80% deionized water, be heated to 60 DEG C extremely All dissolutions, are emulsified under high velocity agitation, obtain pre-emulsion；

B), it is filled with N₂, it is warming up at 80 DEG C, under the stirring of certain speed, 20% cationic initiator aqueous solution is added dropwise, instead Answer 0.5~1h；

C), maintain the temperature at 81~83 DEG C, be at the uniform velocity added dropwise remaining 70~80% mix monomer and it is remaining 80% sun from Sub- initiator solution after dripping off in 1.5~2h, is warming up to 88 DEG C, and insulation reaction 0.5h cools to 60 DEG C, adds remainder Deionized water, be cooled to 40 DEG C and filter and package, obtain the SMA that solid content is 40 ± 2%, priming paint described in partial size≤150nm Modified cation acrylic acid ester emulsion；

The mix monomer by one of carboxylic acrylic monomers, hydroxyl at least one of acrylic monomers, Methyl methacrylate or ethyl methacrylate or butyl acrylate or butyl methacrylate or acrylonitrile or acrylamide Or the monomer mixture of at least two compositions in dimethylaminoethyl methacrylate；

Wherein, by weight percentage, material composition are as follows: imidizate SMA quaternary amine 7~15%, carboxylic acrylic acid Monomer 2~8%, the acrylic monomers 2~8% of hydroxyl, methyl methacrylate or ethyl methacrylate or acrylic acid fourth At least two monomers in ester or butyl methacrylate or acrylonitrile or acrylamide or dimethylaminoethyl methacrylate 20~40%, OP-10 emulsifier 1~4%, cationic initiator 0.2~0.6%, deionized water 50~65%；

The cationic initiator is two isobutyl imidazoline hydrochloride of azo-bis-isobutyrate hydrochloride or azo；The cation draws Hair agent aqueous solution is the 3.0% cationic initiator aqueous solution contained admittedly.

2. preparation method according to claim 1, it is characterised in that: the carboxylic acrylic monomers be acrylic acid, One of methacrylic acid.

3. preparation method according to claim 1, it is characterised in that: the acrylic monomers of the hydroxyl is acrylic acid- 2- hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid -2- hydroxy butyl ester, 2-hydroxyethyl methacry-late, methacrylic acid -2- hydroxyl At least one of propyl ester, methacrylic acid -2- hydroxy butyl ester, N hydroxymethyl acrylamide.