CN105694644A - A preparing method of a bleed-resistant cation acrylate emulsion - Google Patents

Abstract

The invention relates to a preparing method of a bleed-resistant cation acrylate emulsion. The emulsion comprises a zinc-ammonium carbonate solution, fatty alcohol ether phosphate, a carboxyl-containing acrylic acid monomer, a hydroxy-containing acrylic acid monomer, an acrylic acid monomer for free radical polymerization, N-(2-methacryloyloxy ethyl) ethylene urea, a cation initiator, aqua ammonia, OP-10 and water. The emulsion comprises a transition metal-zinc complex bleed-resistant group so that the emulsion has double bleed-resistant functions. Waterborne woodenware seal primer prepared from the emulsion has excellent permeability, sealing performance, bleed resistance, adhesive force and waterproofness, an extremely good sanding property and an extremely good filling property. The emulsion is widely used for waterborne woodenware seal primer for various types of wood, waterborne seal primer for interior and exterior walls and other waterborne industrial primer.

Description

A kind of preparation method of impervious color cation acrylate emulsion

Technical field

The preparation method that the present invention relates to a kind of acrylic acid ester emulsion, refers more particularly to a kind of impervious color acrylic acid ester emulsion, belongs to synthetic resin technical field。

Background technology

In recent years, water-borne wood coating, because of its prominent environment-friendly advantage, health and safety, becomes a developing direction of woodwork coating。But in water-borne wood coating coating process, bleeding problem often occur, namely when the application of real color water-borne wood coating, particularly light or white coating, paint film is easy to change, affects paint film apparent property。Therefore, how effectively to solve problem above, become the important topic improving water-borne wood coating application universality。The base material of common easy bleeding mainly has: redwood, Cedrus deoclar (Roxb.) G. Don, walnut, husky Billy, Quercus acutissima Carr., density board, clamping plate etc.。

During water-borne wood coating application, the main cause of generation bleeding phenomenon is: aqueous woodware paint is a kind of special dispersion being disperse medium with water, when being coated on the wood surface with water-wet behavior, moisture very easily infiltrates through in timber, and contacts with the water solublity coloring matter in timber。These coloring matters can be dissolved in the water, and slowly spreads then as drying varniss process, and finally migrates to coating surface, forms yellow or brown mottle or makes the flavescence of whole paint film color deepen。It addition, from aqueous woodware paint membrane formation mechanism, polymer is scattered in water with spheroidal particle。In drying varniss process, there is series of physical chemical process along with moisture evaporation in these granules: particle packing, melts knot, polymer end of the chain diffusion etc., and ultimately form a continuous print paint film。Therefore coating initial is not fine and close, will necessarily there is gap between spheroidal particle, in timber pigment on ooze and provide passage。

Coloring matter in timber is primarily referred to as the plant pigment in wood extractive, mainly includes Polyphenols pigment and flavonoids；A lot of timber contain Polyphenols pigment, and vegatable tannin acid belongs to polyphenol derivatives, the distinctive polyphenol structure of tannin, are very easily oxidized to chromophoric group quinonyl, also easily produce conjugation condensed ring by coupling simultaneously and manifest color；Flavonoids is a kind of water-soluble natural pigment being widely present in plant, in light yellow or yellow, flavonoid molecule has two phenyl ring be connected with each other by central three carbochains to form, there is C6-C3-C6 basic framework, often having the substituent groups such as hydroxyl, methoxyl group, methyl, isopentene group, C4 position is often carbonyl, is the colour developing group of flavonoids, as the H on its phenyl ring is optionally substituted by a hydroxyl group formation phenolic hydroxyl group, then the phenolic hydroxyl group formed will become auxochrome makes compound colors deepen。

Currently used more impervious color processing method, adopts the seal coat using the seal coat of impervious color auxiliary agent, cation emulsion to prepare or impervious color auxiliary agent to mix the seal coat prepared with cation emulsion mostly。Therefore a kind of cation acrylic emulsion containing impervious color agent groups is developed necessary。

Summary of the invention

The present invention utilizes the characteristic of cation emulsion and the resistance to bleed of transition metal ions coordination compound, organically combined by both chemical bond modes, preparing a kind of impervious color cation acrylate emulsion, the aqueous wooden ware seal coat being made into this emulsion has dual resistance to bleed energy。Because cation acrylic emulsion has less surface tension, the permeability of ground is extremely strong, alkaline matter and temperature all can promote the cross-linking reaction of cation emulsion；Cation emulsion can form ionic bond with the tannic acid in timber and amount of grease class material molecule, and reaction forms that salt compounds is coated to be fixed on interface, thus realizing closing the purpose of tannic acid；Its functional group's amido can form hydrogen bond with the hydroxyl in the wood fiber, can produce good adhesive force；Additionally, the acidic-group in cationic polymer also can occur neutralize reaction and fix with the nicotine of scribble or humidity etc., it is achieved impervious Semu。So, the impervious color process of cation emulsion is based on the chemical reaction of wherein specific groups, it is possible to fixing for tannic acid can't live oozed by reacting。Tannic acid and Flavonoid substances in timber are very sensitive to transition metal ions, with transition metal ions generation complex reaction, can be effectively prevented on the pigment in base material and ooze。

In order to solve described technical problem, the present invention takes techniques below scheme: the present invention relates to a kind of impervious color cation acrylate emulsion, by weight percentage, it consists of: zinc carbonate ammonium salt solution 10～15%, fatty alcohol ether phosphate ester 1～5%, carboxylic acrylic monomers 3～8%, the acrylic monomers 10～20% of hydroxyl, the acrylic monomers 18～30% of radical polymerization, N-(2-methacryloxyethyl) ethylidene-urea 0.2～3%, cationic initiator 0.1～0.5%, ammonia 0.5～2%, OP-10 emulsifying agent 1～5%, deionized water 40～60 parts, sodium sulfoxylate formaldehyde 0.05～0.2%。

Described zinc carbonate ammonium salt solution consists of: zinc oxide 12～15%, ammonium carbonate 20～25%, ammonia 20～30%, deionized water 35～50%。

Described carboxylic acrylic monomers is the one of acrylic or methacrylic acid；The acrylic monomers of described hydroxyl is at least one of acrylic acid-2-hydroxyl ethyl ester, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxy butyl ester, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate, methacrylic acid-2-hydroxy butyl ester or N hydroxymethyl acrylamide；The acrylic monomers of described radical polymerization is the monomer of more than at least two of methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, acrylamide。

Described cationic initiator is the one in azo-bis-isobutyrate hydrochloride (AIBA) and azo two isobutyl imidazoline hydrochloride (AIBI)。

The present invention adds a small amount of sodium sulfoxylate formaldehyde, it is possible to significantly decrease the content of residual monomer in acrylate polymer emulsion。

The preparation method that the present invention proposes a kind of impervious color cation acrylate emulsion, its preparation method, comprise the steps:

A, preparation zinc carbonate ammonium salt solution: in the container with agitating device, add zinc oxide, ammonium carbonate and deionized water and stirring by formulation weight ratio, add ammonia mix homogeneously and obtain a settled solution；

B, in the reaction vessel being furnished with speed-adjustable stir device, return duct, Dropping funnel and thermometer, by formula ratio add fatty alcohol ether phosphate ester, 20～30% mix monomer, OP-10 emulsifying agent and 60～70% deionized water, it is heated to 60 DEG C to all dissolving, carry out emulsifying under high velocity agitation, obtain pre-emulsion；

C, it is filled with N₂, it is warmed up at 78～80 DEG C, under the stirring of certain speed, the cationic initiator aqueous solution (3% mass ratio) of dropping 20%, reacts 0.5～1h；

D, maintain the temperature at 80～82 DEG C, at the uniform velocity drip the mix monomer of upper remaining 70～80% and remaining 80% cationic initiator aqueous solution, after dripping off in 1.5～2hr, add zinc carbonate ammonium salt solution, and it is warmed up to 85 DEG C, add a small amount of sodium sulfoxylate formaldehyde, insulation reaction 0.5hr, cool to 60 DEG C, pH is adjusted to be 8.5～9.5 with ammonia, add remaining water, be cooled to 40 DEG C and filter and package, obtain solid content be 40 ± 2%, the anti-bleeding cation acrylate emulsion of particle diameter≤200nm。

The anti-bleeding cation acrylate emulsion that the present invention prepares, owing to containing the impervious color base group of transition metal Zn complex, having dual resistance to bleed energy。The aqueous wooden ware seal coat prepared by this emulsion has the permeability of excellence, closure, resistance to bleed, adhesive force and resistance to water, fabulous grinability and fillibility；It is widely used in the aqueous wooden ware seal coat of all kinds of timber, aqueous inner-outer wall seal coat and other water-based industrial paint priming paint。

Detailed description of the invention

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

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

Embodiment 1:

A, preparation zinc carbonate ammonium salt solution: in the container with agitating device, add 15 parts of zinc oxide, 20 parts of ammonium carbonate and 40 parts of deionized water and stirring, add 25 parts of ammonia mix homogeneously and obtain a settled solution；

B, in the reaction vessel being furnished with speed-adjustable stir device, return duct, Dropping funnel and thermometer, by formula ratio add fatty alcohol ether phosphate ester, 20～30% mix monomer, OP-10 emulsifying agent and 60～70% deionized water, it is heated to 60 DEG C to all dissolving, carry out emulsifying under high velocity agitation, obtain pre-emulsion；

C, it is filled with N₂, it is warmed up at 78～80 DEG C, under the stirring of certain speed, the cationic initiator aqueous solution (3% mass ratio) of dropping 20%, reacts 0.5～1h；

D, maintain the temperature at 80～82 DEG C, at the uniform velocity drip the mix monomer of upper remaining 70～80% and remaining 80% cationic initiator aqueous solution, after dripping off in 1.5～2hr, add zinc carbonate ammonium salt solution, and it is warmed up to 85 DEG C, add a small amount of sodium sulfoxylate formaldehyde, insulation reaction 0.5hr, cool to 60 DEG C, pH is adjusted to be 8.5～9.5 with ammonia, add remaining water, be cooled to 40 DEG C and filter and package, obtain solid content be 41.6%, particle diameter be the anti-bleeding cation acrylate emulsion of 168nm。

Embodiment 2, embodiment 3 preparation carry out with reference to the step in embodiment 1。

The key property of the anti-bleeding cation acrylate emulsion that the present invention is prepared, detects according to relevant national standard, and test result is as shown in table 2。

Table 2: anti-bleeding cation acrylate emulsion key property

The anti-bleeding cation acrylate emulsion that three embodiments are prepared makes aqueous wooden ware seal coat with cation acrylate emulsion (comparative example) on the market, detect according to relevant national standard, the film performance of seal coat is carried out contrast test, and test result is as shown in table 3。

Table 3: aqueous sealing primer film performance

Although the present invention has been explained in detail and has quoted as proof embodiment, but for those of ordinary skill in the art, it is clear that can various schemes, amendment and change that make as specified above, should be construed as being included within scope of the claims。

Claims (3)

1. an impervious color acrylic acid ester emulsion, it is characterized in that: by weight percentage, it consists of: zinc carbonate ammonium salt solution 10～15%, fatty alcohol ether phosphate ester 1～5%, carboxylic acrylic monomers 3～8%, the acrylic monomers 10～20% of hydroxyl, the acrylic monomers 18～30% of radical polymerization, N-(2-methacryloxyethyl) ethylidene-urea 0.2～3%, cationic initiator 0.1～0.5%, ammonia 0.5～2%, OP-10 emulsifying agent 1～5%, deionized water 40～60 parts, sodium sulfoxylate formaldehyde 0.05～0.2%；Described zinc carbonate ammonium salt solution consists of: zinc oxide 12～15%, ammonium carbonate 20～25%, ammonia 20～30%, deionized water 35～50%；Described carboxylic acrylic monomers is the one of acrylic or methacrylic acid；The acrylic monomers of described hydroxyl is at least one of acrylic acid-2-hydroxyl ethyl ester, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxy butyl ester, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate, methacrylic acid-2-hydroxy butyl ester or N hydroxymethyl acrylamide；The acrylic monomers of described radical polymerization is the monomer of more than at least two of methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, acrylamide。

2. an impervious color acrylic acid ester emulsion as claimed in claim 1, it is characterised in that: described cationic initiator is the one in azo-bis-isobutyrate hydrochloride (AIBA) and azo two isobutyl imidazoline hydrochloride (AIBI)。

3. the preparation method of an impervious color acrylic acid ester emulsion as claimed in claim 1, it is characterised in that: described preparation method, comprise the steps:

A, preparation zinc carbonate ammonium salt solution: in the container with agitating device, add zinc oxide, ammonium carbonate and deionized water and stirring by formulation weight ratio, add ammonia mix homogeneously and obtain a settled solution；

B, in the reaction vessel being furnished with speed-adjustable stir device, return duct, Dropping funnel and thermometer, by formula ratio add fatty alcohol ether phosphate ester, 20～30% mix monomer, OP-10 emulsifying agent and 60～70% deionized water, it is heated to 60 DEG C to all dissolving, carry out emulsifying under high velocity agitation, obtain pre-emulsion；

C, it is filled with N₂, it is warmed up at 78～80 DEG C, under the stirring of certain speed, the cationic initiator aqueous solution (3% mass ratio) of dropping 20%, reacts 0.5～1h；

D, maintain the temperature at 80～82 DEG C, at the uniform velocity drip the mix monomer of upper remaining 70～80% and remaining 80% cationic initiator aqueous solution, after dripping off in 1.5～2hr, add zinc carbonate ammonium salt solution, and it is warmed up to 85 DEG C, add a small amount of sodium sulfoxylate formaldehyde, insulation reaction 0.5hr, cool to 60 DEG C, pH is adjusted to be 8.5～9.5 with ammonia, add remaining water, be cooled to 40 DEG C and filter and package, obtain solid content be 40 ± 2%, the anti-bleeding cation acrylate emulsion of particle diameter≤200nm。