Summary of the invention
The present invention not only is intended to solve the general relatively poor problem of water-based hydroxyl acrylic resin water tolerance, has also further overcome when acid number is identical, uses the weak point of the existing package stability difference of resin of single stage method dropwise addition of acrylic acid monomer preparation.
The present invention realizes like this, it is a kind of water-based hydroxyl acrylic resin of cyanacrylate modification, its feed composition comprises: acrylic monomer, styrene monomer, allyl monomer, strong solvent, initiator, solubility promoter and neutralizing agent, it is characterized in that described acrylic monomer is the monomeric mixture of Acrylic Acid Monomer and acrylic acid derivative; Described allyl monomer is a cyanacrylate; Described strong solvent is a tertiary monocarboxylic acid derivatives active solvent; Described initiator is the peroxide initiator; Described solubility promoter is the mixture of pure ether solvent and petrolic solvent; Described neutralizing agent is the amine neutralizing agent, and in mass parts, the proportioning of each feed composition is as follows:
The feed composition mass parts
Acrylic Acid Monomer 20~70;
Styrene monomer 15~35;
Allyl monomer 1~3;
Strong solvent 10~50;
Initiator 1~5;
Solubility promoter 10~30;
Neutralizing agent 1~10.
Acrylic monomer described here is the monomeric mixture of Acrylic Acid Monomer and acrylic acid derivative, and Acrylic Acid Monomer is selected from one or both in vinylformic acid, the methacrylic acid; The acrylic acid derivative monomer is selected from one or more the mixture in methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate and the Rocryl 410.That is to say, in the acrylic acid or the like raw material, except the active higher acrylic monomer of selective polymerization, also comprised the acrylic acid derivative of hydroxyl, like this can so that to hydroxyl acrylic aqueous dispersion wetting ability and stability are preferably arranged.
The present invention has also selected styrene monomer for use in the synthetic raw material, this is because styrene monomer has excellent dryness, hardness, gloss, fullness ratio, chemoresistance and water tolerance after the cold coating film forming.Between the styrene monomer that is suitable for is selected from-a kind of in the vinyl toluene, p-methylstyrene, vinylbenzene or their mixture.
The strong solvent of selecting for use among the present invention is the tertiary monocarboxylic acid derivative, can be selected from a kind of in tertiary carbonic acid glycidyl ester, the tertiary ethylene carbonate or their mixture.Be good with tertiary carbonic acid glycidyl ester especially wherein.The effect of tertiary monocarboxylic acid group provides low viscosity and good pigment wettability, the compatibility with non-polar solvent, good anti-UV, excellent chemical resistant properties, height hydrophobic nature and crosslinked sterically hindered protection; And that oh group can provide is crosslinked, interlayer adheres to and with the compatibility of polarity coating.In resin of the present invention, introduce tertiary carbonic acid glycidyl ester (Shell Co. Ltd, Cardura E-10p) some excellent performances can be provided,, improve acid resistance and outdoor weather resisteant simultaneously as high solvent compatibility and low viscosity.
According to the present invention, what the initiation of resin polymerization process was adopted is peroxide initiator, and suitable superoxide is selected from a kind of in peroxidized t-butyl perbenzoate, peroxidation two tert-pentyls or their mixture.For this reaction system, selecting for use is that the high-temperature initiator peroxidized t-butyl perbenzoate is particularly suitable.
The solubility promoter that uses in this building-up reactions is the mixture of pure ether solvent and petrolic solvent, optional a kind of in butyl glycol ether, propylene glycol butyl ether of alcohol ether solvent or their mixture, petrolic solvent can be selected from a kind of among S-100, the S-200 or their mixture.A preferable scheme is to select for use butyl glycol ether and S-100 solvent complex, when two kinds of solvent burden ratios are 1: 1, and accounts for 15 of total solids quality~18% o'clock for best, and the at this moment synthetic resin viscosity that obtains is moderate, the good stability of resin after the emulsification.
The present invention compared with prior art, a key character is: the present invention has introduced allyl monomer in the polymerizable acrylic monomer process, is good with cyanacrylate (Triallyl isocyanurate, be called for short TAIC) especially wherein.Its structure is as follows:
This is a kind of fragrant heterocyclic multi-functional olefinic monomer that contains, and is mainly used in multi-purpose linking agent and properties-correcting agent.TAIC has three allyl functionality, has the general general character of aliphatics alkene, can participate in multiple addition reaction, homopolymerization and copolyreaction, Prins reaction etc.Performance is very stable at normal temperatures, and under superoxide caused, TAIC was than the easier polymerization reaction take place of other allyl group, and it can make polymer properties be improved, and comprises mechanical property, thermotolerance, water tolerance and weathering resistance etc.
The cyanacrylate of Jia Ruing can carry out radical polymerization with Acrylic Acid Monomer in the present invention, the water-based hydroxyl acrylic resin is carried out modification, because it contains the structure of three special allyl functionality, can form macromolecular dendritic structure after the copolymerization, increased the molecular weight of resin, improved resin and aliphatic isocyanates solidified cross-linking density, the performance of filming is improved, particularly water tolerance is significantly improved.The addition of TAIC is that 1~3% of total solids quality is advisable, when add solid amount 2.5% the time, to improved performance the best of acrylic resin.
Preparation method according to water-based hydroxyl acrylic resin of the present invention is characterised in that, when synthetic resins vinylformic acid is divided into the dropping of two steps, that is: the first step is that all monomers except that Acrylic Acid Monomer and the Acrylic Acid Monomer of part and the mixture of initiator are dripped polymerization; Second step was remaining Acrylic Acid Monomer to be mixed with a part of initiator once more drip.Concrete steps comprise:
(1) add solubility promoter and strong solvent in the reactor that stirring rake, thermometer and condenser are housed, logical nitrogen stirs and is warming up to 150~155 ℃;
(2) under this temperature, drip first mix monomer, comprise part propylene acid mono and whole acrylic acid derivative monomer, styrene monomer, allyl monomer and part initiator, wherein, Acrylic Acid Monomer accounts for 80~90 quality % of its total amount, initiator accounts for 77~84 quality % of its total amount, the dropping time is 4~5h, insulation 0.3~0.6h also is cooled to about 145 ℃, add the second endorsement body, comprise remaining Acrylic Acid Monomer and part initiator, wherein, Acrylic Acid Monomer accounts for 10~20 quality % of its total amount, initiator accounts for 5~8 quality % of its total amount, the dropping time is 10~15min, adds remaining initiator then rapidly, is 11~16 quality % of total amount of initiator, insulation 1.5~2.5h makes prepolymer;
(3) above-mentioned prepolymer is cooled to 70~75 ℃, add neutralizing agent in three batches lentamente, first is 20~30 quality % of total amount, second batch is 30~40 quality % of total amount, the 3rd batch is 30~40 quality % of total amount, in the stirring and behind 20~40min, slowly drips deionized water emulsification, the dropping time is about 1.5~2.5h, fully stirs 0.5~1.5h discharging then.
Water-based hydroxyl acrylic resin according to the present invention's preparation can be dispersed into water-base resin well in water, this mainly is by in the carboxyl on the molecular chain and salify, this resin more approaches dispersion, when identical acid number, it is relatively poor that single stage method drips the prepared resin wetting ability of mix monomer, package stability is bad, easily layering, and adopt two-step approach dropwise addition of acrylic acid monomer of the present invention, wherein the vinylformic acid of second step dropping directly has been connected on the end group of molecular chain carboxylic group, make in the more carboxyl and salify, increase the wetting ability of resin, also improved the package stability of resin.When the monomer consumption of carboxyl group is very few, mixed water-based hydroxyl acrylic resin can contain the visible small-particle, show that the resin wetting ability is not enough, and when this type of monomer is too much, though obtain the finely dispersed water-based hydroxyl acrylic resin of oyster white, but after use cured with isocyanates film forming, blushing is arranged, this is because very good wetting ability causes moisture to shed from paint film, but also can directly have influence on the water tolerance of paint film, therefore, the monomeric consumption of carboxyl group is that 8~15% of synthesizing formula component total mass is advisable, after the at this moment prepared water-based hydroxyl acrylic resin film forming, and over-all properties the best.
Acrylic resin of the present invention be by in the amine and side chain on the carboxyl salify and be scattered in the water, the amine neutralizing agent that is suitable for is selected from one or more the mixture in dimethylethanolamine, trolamine and the ammoniacal liquor, and what comparatively be suitable for is dimethylethanolamine.Degree of neutralization is expressed by pH value, and pH value directly influences the performance of viscosity change, package stability and paint film.When being neutralized to PH and being 7.5~8.5, modest viscosity, be uniformly dispersed, gloss of film is good, fullness ratio is good.
By as seen above-mentioned, water-based hydroxyl acrylic resin according to the cyanacrylate modification of the present invention preparation, its advantage is: emulsion particle diameter is little, preparation technology's simple and stable, the product period of storage is long, at room temperature can with the crosslinked film forming of water-based isocyanate solidifying agent, have good film-forming properties, excellent in water resistance, chemical proofing, can be widely used in car repair, high-grade water-borne wood coating and industrial coating.The typical performance of water-borne acrylic resin of the present invention is as shown in table 1:
The typical characteristics of table 1 cyanacrylate modified water-soluble Hydroxylated acrylic resin
Test item typical case performance
Appearance milky white is slightly transparent
Solid content, % 40~45
Viscosity, mPas 500~2000
PH value 7.5~8.5
Particle diameter, nm 100~200
Molecular weight distribution 1.7~2.4
Embodiment
Below by embodiment the present invention is described in further detail, but the present invention is in no way limited to these embodiment.
Embodiment 1
The raw material that preparation cyanacrylate modified water-soluble Hydroxylated acrylic resin is used is formed as shown in table 2.
Table 2 preparation cyanacrylate modified water-soluble Hydroxylated acrylic resin is formed with raw material
Component |
Quality (g) |
Tertiary carbonic acid glycidyl ester |
25.7 |
Butyl glycol ether |
8 |
The S-100 solvent |
8 |
Vinylformic acid |
9 |
Butyl acrylate |
7.2 |
Hydroxyethyl methylacrylate |
9.8 |
Methyl methacrylate |
17.1 |
Vinylbenzene |
19.1 |
Cyanacrylate |
1.35 |
Peroxidized t-butyl perbenzoate |
2.44 |
Dimethylethanolamine |
2.6 |
Deionized water |
93.6 |
Concrete preparation method is as follows: tertiary carbonic acid glycidyl ester, butyl glycol ether and S-100 solvent are added be equipped with in the 500ml four-hole boiling flask of thermometer, whipping appts and condenser, feed the drying nitrogen protection, start stirring and be warming up to 150~155 ℃; Begin to drip first mix monomer then, comprise: vinylformic acid, butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, cyanacrylate and peroxidized t-butyl perbenzoate, vinylformic acid 7.7g wherein, peroxidized t-butyl perbenzoate 2.05g, drip off in about 4.5h, insulation 0.5h also is cooled to about 145 ℃; Add the second endorsement body, comprising: vinylformic acid 1.3g and peroxidized t-butyl perbenzoate 0.13g, about 15min drips off, and adds peroxidized t-butyl perbenzoate 0.26g immediately, and temperature remains on 145~150 ℃, insulation 2h, the survey acid number is 24mgKOH/g; Material is cooled to 70~75 ℃, according to acid number, adding degree of neutralization in three batches lentamente and be 50% dimethylethanolamine neutralizes, fully stir 30min, drip deionized water and carry out emulsification, about 2h adds, and adds an amount of 10% dimethyl ethanol amine aqueous solution adjusting pH value and viscosity (amount of the dimethylethanolamine of Shi Yonging is not calculated in the total amount of dimethylethanolamine) herein, fully stirs the discharging of 30~40min after-filtration.
The water-based hydroxyl acrylic resin solids content of above-mentioned cyanacrylate modification is 45%, and pH value is 8.2, and emulsion particle diameter is 100~200nm, and viscosity (rotational viscosimeter NDJ-1) is 1300mPas, molecular weight distribution 2.0; Be mixed with baked paint with this resin and melamine resin Cymel303 (the special company of cyanogen produces), this system is toasted down at 120 ℃ and just can be solidified in 30 minutes, is applicable to single-component industrial baking coating.
Embodiment 2
The raw material for preparing cyanacrylate modified water-soluble Hydroxylated acrylic resin is in this example formed as shown in table 3.As different from Example 1, improve the amount of cyanacrylate in the material component in this example, reduced acrylic acid amount.
Table 3 preparation cyanacrylate modified water-soluble Hydroxylated acrylic resin is formed with raw material
Component |
Quality (g) |
Tertiary carbonic acid glycidyl ester |
25.7 |
Butyl glycol ether |
8 |
The S-100 solvent |
8 |
Vinylformic acid |
8.75 |
Butyl acrylate |
7.2 |
Hydroxyethyl methylacrylate |
9.8 |
Methyl methacrylate |
17.1 |
Vinylbenzene |
19.1 |
Cyanacrylate |
1.8 |
Peroxidized t-butyl perbenzoate |
2.44 |
Dimethylethanolamine |
2.8 |
Deionized water |
108 |
Concrete preparation method is as follows: tertiary carbonic acid glycidyl ester, butyl glycol ether and S-100 solvent are added be equipped with in the 500ml four-hole boiling flask of thermometer, whipping appts and condenser, feed the drying nitrogen protection, start stirring and be warming up to 150~155 ℃; Begin to drip first mix monomer then, comprise: vinylformic acid, butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, cyanacrylate and peroxidized t-butyl perbenzoate, vinylformic acid 7.45g wherein, peroxidized t-butyl perbenzoate 2.05g, drip off in about 4.5h, insulation 0.5h also is cooled to about 145 ℃; Add the second endorsement body, comprising: vinylformic acid 1.3g and peroxidized t-butyl perbenzoate 0.13g, about 15min drips off, and adds peroxidized t-butyl perbenzoate 0.26g immediately, and temperature remains on 145~150 ℃, insulation 2h, the survey acid number is 22mgKOH/g; Material is cooled to 70~75 ℃, according to acid number, adding degree of neutralization in three batches lentamente and be 50% dimethylethanolamine neutralizes, fully stir 30min, drip deionized water and carry out emulsification, about 2h adds, and adds an amount of 10% dimethyl ethanol amine aqueous solution adjusting pH value and viscosity (amount of the dimethylethanolamine of Shi Yonging is not calculated in the total amount of dimethylethanolamine) herein, fully stirs the discharging of 30~40min after-filtration.
The water-based hydroxyl acrylic resin solids content of above-mentioned cyanacrylate modification is 42%, and pH value is 8.4, and emulsion particle diameter is 100~200nm, and viscosity (rotational viscosimeter NDJ-1) is 1800mPas, molecular weight distribution 2.4; The aqueous double-component polyurethane finish paint that is mixed with this resin and aliphatic polymeric isocyanate Bayhydur3100 (Beyer Co., Ltd's product), solidify the back paint film and have good gloss and chemical proof, particularly behind the consumption that has improved cyanacrylate, the water tolerance of paint film is significantly improved, this system can be applicable to car refinishing paint, and performance is as shown in table 4.
Table 4 coating property of embodiment 2 cyanacrylate modified water-soluble Hydroxylated acrylic resin systems
Project |
Detected result |
Outward appearance |
Surface free of pinholes and particle |
60 ° of gloss, % |
95 |
Pencil hardness |
2H |
Impact kgcm |
50 |
Snappiness, mm |
1 |
Sticking power, level |
0 |
Drawing test, mm |
6 |
Water tolerance (25 ± 1 ℃), h |
72h does not have considerable change |
Chemical proofing, 3% sulfuric acid, 2% sodium hydroxide, 5% acetic acid |
15min appearance color no change |
Embodiment 3
Compare with embodiment 1, improved the amount of cyanacrylate and initiator peroxidized t-butyl perbenzoate in this example, the raw materials used composition of preparation resin is as shown in table 5.
Table 5 preparation cyanacrylate modified water-soluble Hydroxylated acrylic resin is formed with raw material
Component |
Quality (g) |
Tertiary carbonic acid glycidyl ester |
25.7 |
Butyl glycol ether |
8 |
The S-100 solvent |
8 |
Vinylformic acid |
9 |
Butyl acrylate |
7.2 |
Hydroxyethyl methylacrylate |
9.8 |
Methyl methacrylate |
17.1 |
Vinylbenzene |
19.1 |
Cyanacrylate |
2.3 |
Peroxidized t-butyl perbenzoate |
3.2 |
Dimethylethanolamine |
2.8 |
Deionized water |
105 |
Concrete preparation method is as follows: tertiary carbonic acid glycidyl ester, butyl glycol ether and S-100 solvent are added be equipped with in the 500ml four-hole boiling flask of thermometer, whipping appts and condenser, feed the drying nitrogen protection, start stirring and be warming up to 150~155 ℃; Begin to drip first mix monomer then, comprise: vinylformic acid, butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, cyanacrylate and peroxidized t-butyl perbenzoate, vinylformic acid 7.7g wherein, peroxidized t-butyl perbenzoate 2.45g, drip off in about 4.5h, insulation 0.5h also is cooled to about 145 ℃; Add the second endorsement body, comprising: vinylformic acid 1.3g and peroxidized t-butyl perbenzoate 0.25g, about 15min drips off, and adds peroxidized t-butyl perbenzoate 0.5g immediately, and temperature remains on 145~150 ℃, insulation 2h, the survey acid number is 24mgKOH/g; Material is cooled to 70~75 ℃, according to acid number, adding degree of neutralization in three batches lentamente and be 50% dimethylethanolamine neutralizes, fully stir 30min, drip deionized water and carry out emulsification, about 2h adds, and adds an amount of 10% dimethyl ethanol amine aqueous solution adjusting pH value and viscosity (amount of the dimethylethanolamine of Shi Yonging is not calculated in the total amount of dimethylethanolamine) herein, fully stirs the discharging of 30~40min after-filtration.
The water-based hydroxyl acrylic resin solids content of above-mentioned cyanacrylate modification is 43%, and pH value is 8.3, and emulsion particle diameter is 100~200nm, and viscosity (rotational viscosimeter NDJ-1) is 950mPas; Molecular weight distribution 1.7; This example is compared with embodiment 2, do not increased the amount of cyanacrylate again reducing acrylic acid while, resin viscosity is increased, therefore increased the amount of initiator in this example, make molecular weight distribution more even, so just, can obtain the resin of high-solid lower-viscosity, and the increase of cyanacrylate has further improved water tolerance.
Table 6 uses the water tolerance of different amount cyanacrylate gained resins to compare
Cyanacrylate, % |
1.5 |
2.0 |
2.5 |
Water tolerance, h |
72h slightly bubbles, loss of gloss |
72h does not have considerable change |
96h does not have considerable change |