CN1624009A - Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof - Google Patents
Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof Download PDFInfo
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- CN1624009A CN1624009A CN 200410051550 CN200410051550A CN1624009A CN 1624009 A CN1624009 A CN 1624009A CN 200410051550 CN200410051550 CN 200410051550 CN 200410051550 A CN200410051550 A CN 200410051550A CN 1624009 A CN1624009 A CN 1624009A
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Abstract
A hydroxyacrylic acid emulsion with micro gel core structure is prepared through copolymerization of vinylsilane coupling agent on acrylate monomer to obtain hydrophobic micro gel cores, copolymerization of hydroxyvinyl monomer on acrylate monomer on the surface of said core to become hydrophilic shell, and preparing emulsion. A process for preparing water-soluble dual-component polyurethane used for paint is also disclosed.
Description
Technical field
The present invention relates to a kind of preparation method with hydroxyl acrylic emulsion of microgel nuclear structure.
The invention still further relates to the hydroxyl acrylic emulsion with microgel nuclear structure of described method preparation.
The invention still further relates to described hydroxyl acrylic emulsion and be used to prepare a kind of method of double-component waterborne polyurethane of the high crosslink density that is specially adapted to fields such as coating, hide finishes, fabric treating, tackiness agent with microgel nuclear structure.
Background technology
Microgel is a kind of polymer microballoon of intramolecular crosslinking, and its molecular structure is between branched macromolecule and macro network polymkeric substance.A micro-gel particles is a macromole, and this macromolecular chain is limited at and carries out intramolecular crosslinking in certain zone and form reticulated structure.Microgel is added in the coating and goes, and can effectively improve the rheological of paint composition, makes coating have good pseudo-plasticity and thixotropy, thereby makes coating have good sag resistance when spraying.Therefore, make can the accord with one's environment trend of protection of coating, develop towards the direction of high solids content, low solvent evaporates.In addition, it also can improve appearance of coat and the pigment dispersion in coating etc.The coating of preparation has good processing characteristics, mechanical property and excellent weather resistance, is mainly used in the preparation high-grade paint or coating is carried out modification.
As far back as 1934, people such as Staudinger just synthesized the product of this intramolecular crosslinking.1948, Schulze and Crouch found that soluble part viscosity after gelation of styrene/butadiene copolymers sharply descends.The method for preparing microgel has emulsion polymerization, dispersion copolymerization method, solution polymerization process and precipitation polymerization method.Because each emulsion particle is isolated mutually in the letex polymerization, this just helps at each reaction microcell, be to carry out polyreaction in the emulsion particle and form crosslinking structure, this crosslinking structure is limited in single emulsion particle scope inside, a final emulsion particle promptly becomes a polymer microgel particle, thus letex polymerization be at present the most frequently used also be the polymerization process of effective synthetic microgel.
The preparation of microgel has many patent reports, as US3, and 880,796, US4,025,474, US4,055,607, US4,075,141 etc.At present acroleic acid microgel is in suitable system, adopts the polyfunctionality monomer to carry out radical polymerization, perhaps adopts polyfunctionality monomer and two functionality monomer to carry out radical copolymerization and make.Polyfunctionality monomer commonly used has Vinylstyrene, Ethylene glycol dimethacrylate, tetramethylene dimethacrylate, Viscoat 295, diallyl terephthalate, isonitrile urea acid triacrylate etc.This class microgel is in preparation process, along with constantly carrying out of reaction, because the effect of factors such as cross-linked network, spatial obstacle, part have neither part nor lot in two keys of intramolecular crosslinking emulsion particle surface residual activity point is increased, running foul of each other between emulsion particle causes the generation of crosslinked coalescence.Simultaneously because the increase of crosslinking degree, it is more fine and close that the emulsion particle structure becomes, the bonding force of emulsifying agent molecule and emulsion particle reduces, make emulsion particle its surperficial emulsifying agent under thermal motion or mechanical force be easy to come off, like this when emulsion particle collides mutually, because the moment desorb of emulsifying agent makes and is easier to coalescence between emulsion particle, the reason of this two aspect all causes stability decreases in the building-up process, and the solids constituent of product is on the low side.
Silane coupling agent is developed as the treatment agent of glass fibre in the glass filament reinforced plastics the earliest.The general formula of silane coupling agent is: Y (CH
2) nSiX
3[n=0～3, X is a hydrolysable group; Y is an organo-functional group].According to the difference of organo-functional group, silane coupling agent can be divided into amine, vinyl-based, epoxies, esters of acrylic acid, sulfydryl class, ureas etc.The general formula of vinyl silicane coupling agent is: CH
2=CH (CH
2)
nSiX
3X is chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group etc. normally, generates silanol [Si (OH) during these group hydrolysis
3], silanol can become the Si-O-Si key from polycondensation, again can with the hydroxyl combination on ground or the pigment (M), form stable Si-O-M key, and vinyl can carry out copolymerization with acrylic ester monomer.
Vinyl silicane coupling agent contains three hydrolyzable siloxane groupss, and the silicone functionalities partial concn when polyreaction in the emulsion particle is higher, is easy to carry out intramolecular crosslinking.The hydrolysis of siloxanes, condensation reaction rate are subjected to the influence of factors such as vinyl silicane coupling agent monomeric species, pH value, temperature.At the hydroxyl acrylic emulsion preparatory phase,, can effectively control the cross-linking density of microgel particle by selecting suitable polymerization technique and vinyl silicane coupling agent kind.Simultaneously, the low surface energy organic silicon oxygen alkane that the vinyl silicane coupling agent condensation forms tends to be distributed in the inside of emulsion particle, by the choose reasonable emulsifying agent, can obtain particle diameter less than 80nm, solid part at the hydroxyl acrylic more than 40% with microgel nuclear structure.
Summary of the invention
The objective of the invention is to problem at the prior art existence, provide a kind of and make linking agent with vinyl silicane coupling agent, preparation method with hydroxyl acrylic emulsion of microgel nuclear structure, earlier vinyl silicane coupling agent and acrylic ester monomer are carried out copolymerization, obtain having the nuclear of microgel structure, carry out the copolymerization of hydroxyl vinyl monomer and acrylic ester monomer on the nuclear surface then, form the shell of enrichment hydroxyl, obtain having the hydroxyl acrylic emulsion of microgel nuclear structure.
The object of the invention is to provide the hydroxyl acrylic emulsion with microgel nuclear structure of described method preparation.The hydroxyl acrylic emulsion of this microgel nuclear structure owing to have the vinyl silicane coupling agent generation hydrolytic condensation of high functional group number, carries out intramolecular crosslinking, and the emulsion particle inside that obtains has high crosslink density.The emulsion particle shell is partly with many reactive hydroxyls, and these groups can cooperate with multi-functional solidifying agent, can obtain having the network polymer of non-homogeneous structure.Behind the film-forming, in the nuclear with microgel structure was embedded in and films, this was mixed with handstone in concrete, gave the performances such as tensile strength, resistance to impact shock, water tolerance, thermotolerance, weather resisteant and photostabilization of filming with excellence.
The present invention also aims to provide described hydroxyl acrylic emulsion to be used to prepare a kind of method of double-component waterborne polyurethane of the high crosslink density that is specially adapted to fields such as coating, hide finishes, fabric treating, tackiness agent with microgel nuclear structure.
The present invention adopts the thermal initiation system, and the preparation seed emulsion adopts semi-continuous polymerzation technology then earlier, and preparation contains the stratum nucleare of microgel structure and the shell of hydroxyl respectively, can obtain the hydroxyl acrylic emulsion with microgel nuclear structure of the present invention.
Preparation method with hydroxyl acrylic emulsion of microgel nuclear structure of the present invention comprises the steps:
(1) preparation of seed
Water, emulsifying agent are added in the reactor, under violent stirring, add (methyl) alkyl acrylate, thiazolinyl carboxylic acid, vinyl aromatic compounds and vinyl silicane coupling agent, be warming up to 60～90 ℃, add initiator solution, reaction 20～40min, emulsion is obvious blue light and promptly gets seed emulsion;
Described each constituent mass umber is as follows:
60～130 parts in water
3～8 parts of emulsifying agents
1～10 part of (methyl) alkyl acrylate
0～5 part of thiazolinyl carboxylic acid
1～10 part of vinyl aromatic compounds
0.5～5 part of vinyl silicane coupling agent
2～6 parts of initiator solutions (concentration is 1% quality);
(2) He preparation
Mixture with (methyl) alkyl acrylate, vinyl aromatic compounds, vinyl silicane coupling agent, thiazolinyl carboxylic acid, diethyl ethylenically unsaturated monomers, water, emulsifying agent, and initiator solution, splash into simultaneously respectively in 1～3h in the seed emulsion that (1) obtain, temperature of reaction maintains 60～90 ℃ hours;
Described each constituent mass umber is as follows:
0～60 part in water
0～3 part of emulsifying agent
20～80 parts of (methyl) alkyl acrylates
0～5 part of thiazolinyl carboxylic acid
1～10 part of vinyl aromatic compounds
0.5～5 part of vinyl silicane coupling agent
0.1～2 part of divinyl base class unsaturated monomer
(concentration is 0～40 part of 1% quality to initiator solution;
(3) preparation of shell
Mixture with (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, thiazolinyl carboxylic acid, water, emulsifying agent, and initiator solution, in 2～5 hours, splash in the reactor simultaneously respectively, temperature of reaction maintains 60～90 ℃, reaction finishes insulation 1～2 hour, promptly gets solid content and be 30～50% the hydroxyl acrylic emulsion with microgel nuclear structure; Described each constituent mass umber is as follows:
0～60 part in water
0～3 part of emulsifying agent
20～80 parts of (methyl) alkyl acrylates
10～30 parts of (methyl) acrylic acid hydroxy alkyl esters
0.5～5 part of thiazolinyl carboxylic acid
1～10 part of vinyl aromatic compounds
0～40 part of initiator solution (concentration is 1% quality);
Described (methyl) alkyl acrylate, the alkyl carbon atoms number is C1～C15, can be one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid n-octyl, the Isooctyl acrylate monomer;
Described (methyl) acrylic acid hydroxy alkyl ester, the alkyl carbon atoms number is C1～C15, can be one or more mixtures in vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-2-hydroxy butyl ester, vinylformic acid-5-hydroxy pentane ester, the vinylformic acid-own ester of 6-hydroxyl, 2-hydroxyethyl methacrylate, the methacrylic acid-2-hydroxypropyl acrylate;
Described thiazolinyl carboxylic acid, alkyl carbon atoms number are C1～C15, can be one or more mixtures in vinylformic acid, methacrylic acid, the methylene-succinic acid;
Described vinyl aromatic compounds is vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, one or more mixtures in the 4-dimethyl styrene.
Described vinyl silicane coupling agent is one or more mixtures in vinyltrimethoxy silane, vinyl methoxyl group diethoxy silane, vinyltriethoxysilane, vinyl oxyethyl group diisopropoxy silane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, the γ-methacryloxypropyl three isopropoxy silane;
Described divinyl base class unsaturated monomer is one or more mixtures in Vinylstyrene, Ethylene glycol dimethacrylate, dimethacrylate triglycol ester, TriMethylolPropane(TMP) methacrylic ester, the dimethacrylate TEG ester;
Described initiator is persulphate such as Potassium Persulphate or ammonium persulphate, azo class such as Diisopropyl azodicarboxylate etc.
Described emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent, wherein anionic emulsifier has long hydrophobic alkyl chain, hydrophilic segment both can be carboxylate salt, sulfonate, vitriol, phosphoric acid salt, also can be the mixture of they and polyethoxye.Wherein anionic emulsifier has: a kind of and several mixture in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl diphenyl ether disodium sulfonate salt, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, oxyethyl group phenolic ether sodium sulfate, alkyl amido sodium vinyl sulfonate, allyl ethers hydroxyl sulfoacid sodium, the phenolic ether phosphoric acid ester.Nonionic emulsifying agent has one or more mixtures in fatty alcohol-polyoxyethylene ether, the poly-ethoxy Vinyl Ether of nonyl phenol, polyoxyethylene octylphenol ether, oxyethyl group propoxy-edge section Fatty Alcohol(C12-C14 and C12-C18), the Isosorbide Dinitrate.
The present invention makes linking agent with vinyl silicane coupling agent, and preparation has the hydroxyl acrylic emulsion of microgel nuclear structure.This emulsion is pieced together usefulness with polyisocyanates, only need carry out the shallow-layer crosslinking curing, dried coating film speed is fast, obtain the dual-component aqueous polyurethane of high crosslink density, not only glued membrane has excellent mechanical property, sticking power, weathering resistance, contamination resistance, wear resistance and ventilation property, and required polyisocyanate curing agent consumption is few, and production cost of products is low.
The method that the hydroxyl acrylic emulsion that the present invention has a microgel nuclear structure is used to prepare dual-component aqueous polyurethane comprises the steps:
(1) above-mentioned hydroxyl acrylic emulsion joins stirring tank, under 200～1000rpm agitation condition, film coalescence aid, defoamer and thickening material is slowly joined in the hydroxyl acrylic emulsion, stirs 10～30min.
(2) the hydrophilically modified polyisocyanates solidifying agent is slowly joined in the hydroxyl acrylic emulsion, add quantitative water to suitable working viscosity behind stirring 5～15min.
Described each constituent mass umber is as follows:
100 parts of hydroxyl acrylic emulsions
10～40 parts in solidifying agent
0～5 part of film coalescence aid
0.05～0.5 part of defoamer
0.1～1 part of thickening material
Above-mentioned solidifying agent can be the nonionic polyethers and or the polyisocyanates of anionic hydrophilic modification, as VPLS2150BA, VPLS2306, VPLS2319, the VPLS2336 of Bayer company, the WT-2102 of Rhodia company, the AQ210 of NPU company etc.
Above-mentioned film coalescence aid can be pure ether solvent, as ethylene glycol ethyl ether, ethylene glycol monobutyl ether, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, one or more mixtures of dipropylene glycol methyl ether.
Above-mentioned defoamer can be TEGO-800, TEGO-805, TEGO-810, TEGO-815, the TEGO-825 of TEGO company, also can be one or more mixtures such as BYK-019, BYK-020 of BYK company.
Above-mentioned thickening material can be cellulose-type such as Natvosol, the mixture of one or more among alkali swelling acrylate type such as RM-2020 and polyurethane associative thickener such as the SN-612.
Hydroxyl acrylic emulsion and resulting dual-component aqueous polyurethane thereof with microgel nuclear structure of the present invention compared with prior art has the following advantages:
1, preparation method of the present invention is linking agent with the vinyl silicane coupling agent, and cross-linking density is big, and solid part is high;
2, the emulsion that obtains of preparation method of the present invention has nucleocapsid structure, and the nuclear part is hydrophobic siloxanes, and shell partly contains the strong hydroxyl of wetting ability, and shell can play shielding effect to interparticle silicone condensation reaction;
3, the present invention obtains emulsion and has nucleocapsid structure, and the nuclear part be the microgel structure, and shell partly is used for film forming curing, and the double-component waterborne polyurethane that obtains is the cross-linking density height not only, and production cost is low;
4, the microgel structure that has of the emulsion that obtains of the present invention can prevent sag resistance, the thickness of filming and the outward appearance of high solid coating when the vertical surface application, improves paint solidification speed;
5, the present invention adds the thiazolinyl carboxylic acid monomer, obtains the polymer segment of carboxylate-containing, can improve the stable dispersion of emulsion particle in water, reduces the emulsifying agent consumption, has improved the water tolerance of filming.
6, the present invention when polymerization, introduce divinyl unsaturated monomer as linking agent, overcome between nucleocapsid because the problem of phase separation that the polarity difference is produced.
7, the present invention adopts hungry dropping mode in the preparation emulsion particle shell stage, helps the polymerization of shell monomers on the nuclear surface.
8, the stability of emulsion polymerization that obtains of the present invention is good, can stablize and store more than 1 year.
9, preparation method of the present invention introduces the vinylic organosiloxane monomer in the nuclear part, hydrolysis-condensation reaction takes place in it in polymerization process, the softish microgel structure that forms, the siloxanes that remains hydrolytic condensation not is in film process, hydrolysis-condensation reaction further takes place, both be beneficial to and be lowered into film temperature, helped improving the sticking power of filming with base material.
10, the emulsion of the present invention's preparation, with water to replace organic solvent, the emulsion of preparation is nontoxic, and is nonflammable, helps environment protection, and the dual-component aqueous polyurethane excellent performance with its preparation can replace two-pack solvent borne polyurethane coating fully.
11, Fa Ming the emulsion that obtains is compared similar hydroxyl acrylic emulsion, the two component polyurethane that obtains is filmed and is had more superior water tolerance, solvent resistance, wear resistance, thermotolerance, sticking power, shock resistance and tensile strength, is widely used in aqueous woodware paint, exterior coating, aqueous adhesive, fabric-treating agent, hide finishes etc.
Embodiment
Embodiment 1-2
Set of monomers becomes methyl methacrylate, butyl acrylate, methacrylic acid, hydroxyethyl methylacrylate, vinylic organosiloxane, dimethacrylate triglycol ester, and its component is filled a prescription as table 1:
Table 1 has microgel nuclear structure hydroxyl acrylic emulsion and forms
Form embodiment 1 embodiment 2
The I bottoms
Deionized water 50g 124g
CO436 2.05g 5.83g
NP-9 0.40g 1.13g
The II monomer mixture
Methyl methacrylate 2.8g 2.8g
Butyl acrylate 3.2g 3.2g
γ-methacryloxy
Propyl trimethoxy silicane 1.2g 1.2g
The III initiator solution
Potassium Persulphate 0.04g 0.14g
Deionized water 5g 5g
IV drips mixture
Deionized water 36g-
CO43 0.77g -
NP-9 0.14g -
Methyl methacrylate 15g 15g
Butyl acrylate 11.7g 11.7g
Methacrylic acid 1.8g 1.8g
γ-methacryloxy
Propyl trimethoxy silicane 0.8g 0.8g
Dimethacrylate triglycol ester 0.3g 0.3g
V drips mixture
Deionized water 38g-
CO436 3.01g -
NP-9 0.5gg -
Methyl methacrylate 35g 35g
Butyl acrylate 27.1g 27.1g
Hydroxyethyl methylacrylate 12.2g 12.2g
Mercaptoethanol 0.35g 0.35g
The VI initiator solution
Potassium Persulphate 0.32g 0.22g
Deionized water 20g 20g
The VII initiator solution
Potassium Persulphate 0.04g 0.04g
Deionized water 10g 10g
NP-9 - 0.5g
The VIII ammonia solution
Ammoniacal liquor (28%) 8g 8g
Deionized water 5g 5g
In the 500ml four-hole bottle of thermometer, whipping appts and condenser is housed, add component I and intensification, when treating that a bottle interior temperature rises to 70 ℃, add component I I, III and prepare seed, treat that system temperature rises to 75 ± 1 ℃ and when stablize, behind the dropping component I V, begins to drip component V in 2 hours, dripped off in 4 hours, component VI dripped off in 6 hours.After mix monomer drips, add component VII, continue insulation cooling after 1 hour.Add component VIII, regulating the pH value is 7.5～8.5, and the cold filtration discharging promptly gets the hydroxyl acrylic emulsion with microgel nuclear structure.
Embodiment 3
Set of monomers becomes methyl methacrylate, butyl acrylate, methacrylic acid, hydroxyethyl methylacrylate, vinyl silicane coupling agent, dimethacrylate triglycol ester, and its component is filled a prescription as table 2:
Table 2 has microgel nuclear structure hydroxyl acrylic emulsion and forms
Form embodiment 3
The I bottoms
Deionized water 124g
CO436 5.83g
NP-9 1.13g
The II monomer mixture
Methyl methacrylate 2.8g
Butyl acrylate 2.2g
γ-methacryloxypropyl
Trimethoxy silane 1.2g
The III initiator solution
Potassium Persulphate 0.04g
Deionized water 5g
IV drips mixture
Methyl methacrylate 15g
Butyl acrylate 11.7g
Methacrylic acid 1.8g
γ-methacryloxypropyl
Trimethoxy silane 0.8g
Dimethacrylate triglycol ester 0.3g
AIBN 0.1g
V drips mixture
Methyl methacrylate 35g
Butyl acrylate 27.1g
Hydroxyethyl methylacrylate 12.2g
Mercaptoethanol 0.35g
AIBN 0.22g
The VI ammonia solution
Ammoniacal liquor (28%) 8g
Deionized water 5g
In the 500ml four-hole bottle of thermometer, whipping appts and condenser is housed, add component I and intensification, when treating that a bottle interior temperature rises to 70 ℃, add component I I, III and prepare seed, treat that system temperature rises to 75 ± 1 ℃ and when stablizing, after in 2 hours, dripping component I V, begin to drip component V, in 4 hours, drip off.After the monomer mixing drips, continue insulation cooling after 1 hour.Add component VI, regulating the pH value is 7.5～8.5, and the cold filtration discharging promptly gets the hydroxyl acrylic emulsion with microgel nuclear structure.
Embodiment 4
Set of monomers becomes methyl methacrylate, vinylbenzene, Isooctyl acrylate monomer, methacrylic acid, hydroxyethyl methylacrylate, vinyl silicane coupling agent, dimethacrylate triglycol ester, and its component is filled a prescription as table 3:
Table 3 has microgel nuclear structure hydroxyl acrylic emulsion and forms
Form embodiment 4
The I bottoms
Deionized water 124g
A-102 3.42g
TX-100 2.34g
The II monomer mixture
Vinylbenzene 3.7g
Isooctyl acrylate monomer 1.3g
Vinyltriethoxysilane 1.5g
The III initiator solution
Potassium Persulphate 0.04g
Deionized water 5g
IV drips mixture
Methyl methacrylate 13g
Vinylbenzene 5g
Isooctyl acrylate monomer 3.7g
Methacrylic acid 1.5g
Vinyltriethoxysilane 2.5g
Vinylstyrene 0.55g
AIBN 0.1g
V drips mixture
Methyl methacrylate 25g
Vinylbenzene 19g
Isooctyl acrylate monomer ester 18.1g
Hydroxyethyl acrylate 16.3g
AIBN 0.22g
The VI ammonia solution
Ammoniacal liquor (28%) 8g
Deionized water 5g
In the 500ml four-hole bottle of thermometer, whipping appts and condenser is housed, add component I and intensification, when treating that a bottle interior temperature rises to 70 ℃, add component I I, III and prepare seed, treat that system temperature rises to 75 ± 1 ℃ and when stablizing, after in 2 hours, dripping component I V, begin to drip component V, in 4 hours, drip off.After the monomer mixing drips, continue insulation cooling after 1 hour.Add component VI, regulating the pH value is 7.5～8.5, and the cold filtration discharging promptly gets the hydroxyl acrylic emulsion with microgel nuclear structure.
Embodiment 5
With the hydroxyl acrylic emulsion among the embodiment 1, add thickening material (Acrysol RM8), film coalescence aid (dipropylene glycol butyl ether) and defoamer (Byk023) respectively, after stirring 15min under the 300rpm rotating speed, the solidifying agent that adds example 2 respectively stirs 5min, adds an amount of water and adjusts to that to obtain double-component waterborne polyurethane emulsion formulations composition after the required viscosity as shown in table 4.The pot-life of product is 3～6h, and wet-film thickness is 200um, and build is 50um, and surface drying time is 1～2h, and doing solid work is 2～3h, and rheological is good.
Table 4 dual-component aqueous polyurethane prescription
Form mass fraction
100 parts of hydroxyl acrylic emulsions in the example 1
0.42 part of Acrysol RM8
0.13 part of Byk023
2.0 parts of dipropylene glycol butyl ether
23 parts of Wt-2102
Water is an amount of
Embodiment 6
With the hydroxyl acrylic emulsion among the embodiment 3, add thickening material (SN-612), film coalescence aid (propylene glycol butyl ether) and defoamer (TEGO-805) respectively, after stirring 15min under the 300rpm rotating speed, add solidifying agent (VPLS2319) and stir 5min, add and obtain the double-component waterborne polyurethane emulsion after an amount of water is adjusted to required viscosity, prescription is formed as shown in table 3.The pot-life of product is 3～6h, and wet-film thickness is 150～200um, and build is 40～70um, and surface drying time is 1～2h, and doing solid work is 2～3h, and rheological is good.
Table 5 dual-component aqueous polyurethane prescription
Form mass fraction
100 parts of hydroxyl acrylic emulsions in the example 3
0.25 part of SN-612
0.2 part of TEGO-805
2.0 parts of propylene glycol butyl ether
29 parts of VPLS2319
Water is an amount of
Embodiment 7
With the hydroxyl acrylic emulsion in the example 4, add thickening material (Acrysol RM8) and defoamer (Byk023) respectively, after stirring 15min under the 300rpm rotating speed, solidifying agent (AQ210) stirs 5min respectively, add and obtain the double-component waterborne polyurethane emulsion after an amount of water is adjusted to suitable viscosity, prescription is formed as shown in table 6.The pot-life of product is 3～6h, and wet-film thickness is 150～200um, and build is 40～70um, and surface drying time is 1～2h, and doing solid work is 2～3h, and rheological is good.
Table 6 dual-component aqueous polyurethane prescription
Form mass fraction
100 parts of hydroxyl acrylic emulsions in the example 4
0.42 part of Acrysol RM8
0.13 part of Byk023
27 parts of AQ210
Water is an amount of
Claims (7)
1, a kind of preparation method with hydroxyl acrylic emulsion of microgel nuclear structure is characterized in that comprising the steps:
(1) preparation of seed
Water, emulsifying agent are added in the reactor, add (methyl) alkyl acrylate, thiazolinyl carboxylic acid, vinyl aromatic compounds and vinyl silicane coupling agent when stirring, be warming up to 60～90 ℃, add initiator solution, reaction 20～40min, emulsion is obvious blue light and promptly gets seed emulsion;
Described each constituent mass umber is as follows:
60～130 parts in water
3～8 parts of emulsifying agents
1～10 part of (methyl) alkyl acrylate
0～5 part of thiazolinyl carboxylic acid
1～10 part of vinyl aromatic compounds
0.5～5 part of vinyl silicane coupling agent
2～6 parts of initiator solutions (concentration is 1% quality);
(2) He preparation
Mixture with (methyl) alkyl acrylate, vinyl aromatic compounds, vinyl silicane coupling agent, thiazolinyl carboxylic acid, diethyl ethylenically unsaturated monomers, water, emulsifying agent, and initiator solution, splash into simultaneously respectively in 1～3h in the seed emulsion that (1) obtain, temperature of reaction maintains 60～90 ℃ hours;
Described each constituent mass umber is as follows:
0～60 part in water
0～3 part of emulsifying agent
20～80 parts of (methyl) alkyl acrylates
0～5 part of thiazolinyl carboxylic acid
1～10 part of vinyl aromatic compounds
0.5～5 part of vinyl silicane coupling agent
0.1～2 part of divinyl base class unsaturated monomer
0～40 part of initiator solution (concentration is 1% quality);
(3) preparation of shell
Mixture with (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, thiazolinyl carboxylic acid, water, emulsifying agent, and initiator solution, in 2～5 hours, splash in the reactor simultaneously respectively, temperature of reaction maintains 60～90 ℃, reaction finishes insulation 1～2 hour, promptly gets solid content and be 30～50% the hydroxyl acrylic emulsion with microgel nuclear structure; Described each constituent mass umber is as follows:
0～60 part in water
0～3 part of emulsifying agent
20～80 parts of (methyl) alkyl acrylates
10～30 parts of (methyl) acrylic acid hydroxy alkyl esters
0.5～5 part of thiazolinyl carboxylic acid
1～10 part of vinyl aromatic compounds
0～40 part of initiator solution (concentration is 1% quality);
The alkyl carbon atoms number of described (methyl) alkyl acrylate is C1～C15; The alkyl carbon atoms number of described (methyl) acrylic acid hydroxy alkyl ester is C1～C15; The alkyl carbon atoms number of described thiazolinyl carboxylic acid is C1～C15; Described vinyl aromatic compounds is vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, one or more mixtures in the 4-dimethyl styrene; Described vinyl silicane coupling agent is one or more mixtures in vinyltrimethoxy silane, vinyl methoxyl group diethoxy silane, vinyltriethoxysilane, vinyl oxyethyl group diisopropoxy silane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, the γ-methacryloxypropyl three isopropoxy silane; Described divinyl base class unsaturated monomer is one or more mixtures in Vinylstyrene, Ethylene glycol dimethacrylate, dimethacrylate triglycol ester, TriMethylolPropane(TMP) methacrylic ester, the dimethacrylate TEG ester; Described initiator is Potassium Persulphate or ammonium persulphate; Described emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent.
2, the preparation method with hydroxyl acrylic emulsion of microgel nuclear structure according to claim 1 is characterized in that described (methyl) alkyl acrylate is one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid n-octyl, the Isooctyl acrylate monomer.
3, the preparation method with hydroxyl acrylic emulsion of microgel nuclear structure according to claim 1 is characterized in that described (methyl) acrylic acid hydroxy alkyl ester is one or more mixtures in vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-2-hydroxy butyl ester, vinylformic acid-5-hydroxy pentane ester, the vinylformic acid-own ester of 6-hydroxyl, 2-hydroxyethyl methacrylate, the methacrylic acid-2-hydroxypropyl acrylate.
4, the preparation method with hydroxyl acrylic emulsion of microgel nuclear structure according to claim 1 is characterized in that described thiazolinyl carboxylic acid is one or more mixtures in vinylformic acid, methacrylic acid, the methylene-succinic acid.
5, the preparation method with hydroxyl acrylic emulsion of microgel nuclear structure according to claim 1 is characterized in that described anionic emulsifier is one or more mixtures in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl diphenyl ether disodium sulfonate salt, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, oxyethyl group phenolic ether sodium sulfate, alkyl amido sodium vinyl sulfonate, allyl ethers hydroxyl sulfoacid sodium, the phenolic ether phosphoric acid ester; Nonionic emulsifying agent is one or more mixtures in the poly-ethoxy Vinyl Ether of fatty alcohol-polyoxyethylene ether, nonyl phenol, polyoxyethylene octylphenol ether, oxyethyl group propoxy-edge section Fatty Alcohol(C12-C14 and C12-C18), the Isosorbide Dinitrate.
6, the hydroxyl acrylic emulsion with microgel nuclear structure of the described method preparation of claim 1.
7, the described hydroxyl acrylic emulsion with microgel nuclear structure of claim 6 is used to prepare the method for dual-component aqueous polyurethane, it is characterized in that comprising the steps:
(1) above-mentioned hydroxyl acrylic emulsion is joined stirring tank, under 200～1000rpm agitation condition, film coalescence aid, defoamer and thickening material are slowly joined in the hydroxyl acrylic emulsion, stir 10～30min;
(2) the hydrophilically modified polyisocyanates solidifying agent is slowly joined in the hydroxyl acrylic emulsion, add entry behind stirring 5～15min and reach working viscosity;
Described each constituent mass umber is as follows:
100 parts of hydroxyl acrylic emulsions with microgel nuclear structure
10～40 parts in solidifying agent
0～5 part of film coalescence aid
0.05～0.5 part of defoamer
0.1～1 part of thickening material
Described solidifying agent is the polyisocyanates of nonionic polyethers and/or anionic hydrophilic modification; One or more mixtures in described film coalescence aid ethylene glycol ethyl ether, ethylene glycol monobutyl ether, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, the dipropylene glycol methyl ether; Described thickening material is one or more the mixture among Natvosol, RM-2020, the SN-612.
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Assignee: Zhongshan Daoqum Chemical Group Co., Ltd. Assignor: South China University of Technology Contract fulfillment period: 2006.12.1 to 2011.12.31 contract change Contract record no.: 2008440000446 Denomination of invention: Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof Granted publication date: 20061101 License type: Exclusive license Record date: 20081128 |
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