CN104130375B - Polyacrylate modified watersoluble closed type isocyanate curing agent and preparation method thereof - Google Patents

Polyacrylate modified watersoluble closed type isocyanate curing agent and preparation method thereof Download PDF

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Publication number
CN104130375B
CN104130375B CN201410374348.7A CN201410374348A CN104130375B CN 104130375 B CN104130375 B CN 104130375B CN 201410374348 A CN201410374348 A CN 201410374348A CN 104130375 B CN104130375 B CN 104130375B
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methyl
hydroxyl
polyacrylate
polyisocyanates
curing agent
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CN104130375A (en
Inventor
庄振宇
许飞
胡中
陈卫东
张汉青
祝宝英
朱柯
马吉康
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CNOOC Energy Technology and Services Ltd
CNOOC Changzhou EP Coating Co Ltd
CNOOC Changzhou Paint and Coatings Industry Research Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Changzhou EP Coating Co Ltd
CNOOC Changzhou Paint and Coatings Industry Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C08G18/6233—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols the monomers or polymers being esterified with carboxylic acids or lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Material Composition (AREA)

Abstract

The present invention relates to a kind of polyacrylate modified watersoluble closed type isocyanate curing agent and preparation method thereof, this curing agent is the performed polymer of the semiclosed thing of polyisocyanates and the polyacrylate formation of hydroxyl, neutralized, emulsification obtains, and the mol ratio of NCO Yu OH is 1～1.15:1；Hydroxyl polyacrylate be with 10～50wt% solvent as bed material, by other monomer containing vinyl structure of carboxylic to 5～15% vinyl monomer, 2～20% ε caprolactone modification vinyl monomer, 5～70% containing primary hydroxyl containing primary hydroxyl or the acrylate monomer of secondary hydroxyl, 1～10%, 0.1～5% chain-transferring agent and 0.05～3% the mixture of initiator instill bed material prepare；Sealer used by the semiclosed thing of polyisocyanates processed is 1.05～1.5:1 with the mol ratio of polyisocyanates.Curing agent is good with matrix resin mixing, curing efficiency is high, low cost, pliable and tough and shock resistance.

Description

Polyacrylate modified watersoluble closed type isocyanate curing agent and preparation method thereof
Technical field
The present invention relates to a kind of polyacrylate modified watersoluble closed type isocyanate curing agent and preparation method thereof.
Background technology
Aqueous polyurethane is widely used in coating, ink and adhesive field due to the combination property of its excellence. Aqueous polyurethane is broadly divided into one-component and two kinds of systems of double-component.Single-component water-based polyurethane easy construction, but chemical resistance Can Shortcomings；Double-component waterborne polyurethane is typically solid by aqueous hydroxyl polyacrylate dispersion and aqueous polyisocyanates Agent forms, and resin crosslinks reaction in film forming procedure, and therefore, coating performance is excellent.But, double-component waterborne polyurethane Need now with the current in use, there is working life, be unfavorable for construction.In order to solve the property that double-component waterborne polyurethane system exists Energy and the contradiction of application property, the most many companies are prepared for enclosed type aqueous polyisocyanate curing agent, are added into aqueous In hydroxyl polyacrylate dispersion, obtain the water paint of one-component.In work progress, make closing many by baking Isocyanates deblocking crosslinks reaction with aqueous hydroxyl polyacrylate dispersion, solves the lance of performance and application property Shield.But, regrettably, the blocked polyisocyanate being currently used for double-component waterborne polyurethane system generally exists following 3 Individual problem: 1. price is high.The blocked polyisocyanate curing agent of main flow is mainly modified by HDI trimer in the market Obtaining, price is higher, adds the cost of corresponding coating；2. consistency problem.When Blocked Isocyanate Curing Agents and hydroxyl During based polyacrylic acid ester mixed with resin, the problem often producing compatibility, cause respective coatings performance existing defects；3. solidify Efficiency is low.During curing of coatings, when blocked isocyanate unseals, after a part of isocyanates crosslinks reaction, same Isocyanate groups remaining in individual curing agent molecule moves more difficulty due to steric reasons, it is difficult to hydroxyl polypropylene Acid esters crosslinks reaction, causes curing efficiency to reduce.
Summary of the invention
First purpose of the present invention is: provide one can with the aqueous good mixing of hydroxyl polyacrylate dispersion, There is the polyacrylate modified watersoluble closed type isocyanate curing agent of the low cost of more excellent curing efficiency.
The technical scheme realizing first purpose of the present invention is: a kind of polyacrylate modified watersoluble closed type isocyanates Curing agent, it is characterised in that it is that the semiclosed thing of polyisocyanates mixes with the polyacrylate of hydroxyl, exists at catalyst Under, add the performed polymer that thermal response obtains, more neutralized, emulsify, except obtain after solvent, wherein, the semiclosed thing of polyisocyanates In the mol ratio of hydroxyl of polyacrylate of NCO and hydroxyl be 1～1.15:1；
Described hydroxyl polyacrylate is with 10～50wt% solvents as bed material, by 5～15wt% carboxylic ethene The ε containing primary hydroxyl containing primary hydroxyl or the acrylate monomer of secondary hydroxyl, 1～10wt% of base class monomer, 2～20wt%-oneself in Ester modified vinyl monomer, 5～70wt% other containing monomer of vinyl structure, 0.1～5wt% chain-transferring agent and 0.05～ The mixture of 3wt% initiator, is added drop-wise in solvent bed material carry out what radical polymerization prepared, and above-mentioned each raw material dosage sum is 100wt%, wherein, the 6-caprolactone modified vinyl monomer containing primary hydroxyl it there is CH2=CRCOOCH2CH2O[CO(CH2)5O]nH structure formula, R=H or CH in formula3, n=1～6 or n=10；
The semiclosed thing of described polyisocyanates is to make sealer with hydrogen-containing compound to close polyisocyanates, closes Agent is (1.05～1.5) with the mol ratio of polyisocyanates: 1.
Above-mentioned polyacrylate modified watersoluble closed type isocyanate curing agent, it is used for preparing hydroxyl polyacrylate Raw material in, carboxylic vinyl monomer is one or more in (methyl) acrylic acid, itaconic acid；Containing primary hydroxyl or secondary The acrylate monomer of hydroxyl is (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl In one or more；Other monomer containing vinyl structure is (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) butyl acrylate, (methyl) propyl acrylate, acrylic acid-2 Octyl Nitrite, (methyl) n-octyl, acrylic acid benzyl One or more in ester, styrene.
Above-mentioned polyacrylate modified watersoluble closed type isocyanate curing agent, it is used as the hydrogeneous chemical combination of described sealer Thing be methyl alcohol, ethanol, propyl alcohol, butanol, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, Methyl ethyl ketoxime, acetyl oxime, methyl-isobutyl oxime, epsilon-caprolactams, butyrolactam, 3-methylpyrazole, 3,5-dimethyl pyrazole Azoles, 3-methyl-5-ethylpyrazol, 3-ethyl-5-propylpyrazol, 3-ethyl-5-isopropylpyrazol, 3-ethyl-5-butyl pyrazoles, One or more in 3-ethyl-5-t-butylpyrazol, phenol, parachlorophenol, o-nitrophenol；Described polyisocyanates is different Isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride-diisocyanate, phenylenedimethylidyne two are different Cyanate, tetramethyl xylylene diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,5-naphthalene two One or more in isocyanates, poly methylene poly phenyl poly isocyanate.
Second object of the present invention is: provides a kind of process stabilizing, convenient to operate prepare polyacrylate modified water The method of property Blocked Isocyanate Curing Agents.
The technical scheme realizing second purpose of the present invention is: a kind of above-mentioned polyacrylate modified watersoluble closed type is different The preparation method of cyanate curing agent, it is characterised in that concrete preparation process is as follows:
1. the semiclosed thing of polyisocyanates is prepared
Using polyisocyanates and solvent as bed material, dripping sealer between 50～80 DEG C, wherein solvent accounts for reactant The 5～30wt% of gross mass, sealer is 1.05～1.5:1 with the mol ratio of polyisocyanates, and sealer dripped in 2 hours Complete, at 50～80 DEG C, it is incubated 3～5 hours till isocyanate content is constant after completion of dropwise addition, discharging obtains many isocyanides The semiclosed thing of acid esters；
2. the polyacrylate of hydroxyl is prepared
By the mixture of all monomers, chain-transferring agent and initiator, uniformly it is added drop-wise in solvent carry out radical polymerization , concrete operations are as follows:
With 10～50wt% solvents as bed material, at 50～80 DEG C by 5～15wt% carboxylic vinyl monomers, 2 ～20wt% is ethene improved containing the 6-caprolactone containing primary hydroxyl of primary hydroxyl or the acrylate monomer of secondary hydroxyl, 1～10wt% Other monomers containing vinyl structure of base monomer, 5～70wt%, 0.1～5wt% chain-transferring agent and 0.05～3wt% initiator It is mixed and stirred for uniform mixture, was uniformly added drop-wise in solvent in 3～5 hours, protect at 50～80 DEG C after completion of dropwise addition The polyacrylate of 2～4 hours prepared hydroxyls of temperature, above-mentioned each raw material dosage sum is 100wt%；
3. polyacrylate modified watersoluble closed type isocyanate curing agent is prepared
The polyacrylate of the hydroxyl that 2. the semiclosed thing of polyisocyanates step 1. prepared prepares with step mixes, Wherein, the mol ratio of the hydroxyl of the polyacrylate of the NCO in the semiclosed thing of polyisocyanates and hydroxyl be 1～ 1.15:1, adds the catalysis accounting for the semiclosed thing of polyisocyanates with the polyacrylate gross mass 0.001～1.5wt% of hydroxyl Agent, is warming up to 60～80 DEG C and closes, and is incubated 5 hours, obtains polyacrylate modified watersoluble closed different at 60～80 DEG C Cyanate performed polymer, adds the most wherein and accounts for the nertralizer of this performed polymer gross mass 3～8wt% and be neutralized, 200 turns/ The agitator stirring of point rotating speed is lower to add the deionized water of performed polymer gross mass 1～3 times and emulsifies, then decompression distillation is extracted out molten After agent, obtain polyacrylate modified watersoluble closed type isocyanate curing agent.
In the preparation method of above-mentioned polyacrylate modified watersoluble closed type isocyanate curing agent, step 1. in, use Make the hydrogen-containing compound of described sealer be methyl alcohol, ethanol, propyl alcohol, butanol, glycol monoethyl ether, ethylene glycol monoethyl ether, the third two Alcohol monomethyl ether, dihydroxypropane single-ether, methyl ethyl ketoxime, acetyl oxime, methyl-isobutyl oxime, epsilon-caprolactams, butyrolactam, 3- Methylpyrazole, 3,5-dimethyl pyrazole, 3-methyl-5-ethylpyrazol, 3-ethyl-5-propylpyrazol, 3-ethyl-5-isopropyl pyrrole One or several in azoles, 3-ethyl-5-butyl pyrazoles, 3-ethyl-5-t-butylpyrazol, phenol, parachlorophenol, o-nitrophenol Kind；Described polyisocyanates is that IPDI, hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride-two are different Cyanate, XDI, tetramethyl xylylene diisocyanate, toluene di-isocyanate(TDI), diphenylmethyl One or more in alkane diisocyanate, 1,5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate；Described solvent For one or more of acetone or butanone.
In the preparation method of above-mentioned polyacrylate modified watersoluble closed type isocyanate curing agent, step 2. in, institute State carboxylic vinyl monomer for one or more in (methyl) acrylic acid, itaconic acid；Containing primary hydroxyl or secondary hydroxyl Acrylate monomer is in (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl Plant or several；6-caprolactone modified vinyl monomer containing primary hydroxyl it there is CH2=CRCOOCH2CH2O[CO(CH2)5O]nH ties Structure formula, wherein R=H or CH3, n=1～6 or 10；Other monomer containing vinyl structure is (methyl) methyl acrylate, (first Base) ethyl acrylate, (methyl) butyl acrylate, (methyl) propyl acrylate, acrylic acid-2 Octyl Nitrite, (methyl) propylene One or more in acid n-octyl, benzyl acrylate, styrene；Described solvent is one or more of acetone or butanone；Institute Stating chain-transferring agent is n-butyl mercaptan, isobutyl mercaptan, positive hexyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, Alpha-Methyl benzene One or more in ethylene dimerization body；Described initiator be azodiisobutyronitrile, AMBN, ABVN, One or more in azo-bis-iso-dimethyl, azo dicyclohexyl formonitrile HCN, dibenzoyl peroxide.
In the preparation method of above-mentioned polyacrylate modified watersoluble closed type isocyanate curing agent, step 3. in, institute It is the one in triethylamine, triethylene diamine, dibutyl tin laurate, stannous octoate with catalyst；Nertralizer used is ammonia Water, triethanolamine, triethylamine, N, the one in N-dimethylethanolamine, 2-amino-2-methyl-1-propanol.
The solution have the advantages that: the polyacrylate modified watersoluble closed type isocyanate curing agent of the present invention is to use Special hydroxyl polyacrylate closes what the semiclosed thing of polyisocyanates obtained.With existing water-based polyurethane curing agent phase Ratio, has the advantage that
1. low cost, compatibility is good.
Owing to the curing agent of the present invention is to use the lower-cost semiclosed thing of polyacrylate modified polyisocyanates to obtain The polyacrylate modified isocyanate curing agent arrived, curing agent phase watersoluble closed with existing polyisocyanate trimer Ratio, the cost of product substantially reduces；Polyacrylate segment is included, this segment and current water in curing agent molecule of the present invention The structure of the property normally used matrix resin of polyurethane coating the most aqueous hydroxyl polyacrylate dispersion is similar, therefore the two has Well compatibility so that the outward appearance of coating significantly improves；
2. the film after solidification has high-flexibility, good impact resistance, excellent hydrolysis, chemical resistance.
When preparing hydroxyl polyacrylate, vinyl monomer used includes that the appropriate 6-caprolactone containing primary hydroxyl changes Sex ethylene base monomer.After prepared hydroxyl polyacrylate and the semiclosed thing of polyisocyanates react, at curing agent Molecule introduces the submissiveest caprolactone segment so that the coating after curing agent and solidification has similar with caprolactone Advantage, i.e. high-flexibility, good impact resistance, excellent hydrolysis, chemical resistance；
3. the curing efficiency of blocked isocyanate is improved.
Owing to curing agent molecule containing the submissiveest caprolactone segment, when there is curing reaction, with caprolactone chain The blocked isocyanate group that section connects has higher mobility and reactivity, can improve the solidification of blocked isocyanate Efficiency, reduces the usage amount of curing agent；
4. the curing agent prepared by the present invention, while improving crosslink density, does not affect the pliability of coating after solidification.
The present invention can by adjusting the quantity suitable vitrification point of acquisition being used various vinyl monomer, such must To different flexible curing agent.
The preparation method process stabilizing of technical solution of the present invention, curing agent constant product quality convenient to operate, prepared.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, but is not limited to this.
Embodiment and comparative example raw materials are unless otherwise indicated commercially available industrial goods, can be purchased by commercial channel ?.
The polyacrylate modified watersoluble closed type isocyanate curing agent of the present invention be the semiclosed thing of polyisocyanates with The polyacrylate mixing of hydroxyl, in the presence of a catalyst, adds the performed polymer that thermal response obtains, more neutralized, emulsify, except molten Obtain after agent, wherein, the hydroxyl of the polyacrylate of the NCO in the semiclosed thing of polyisocyanates and hydroxyl Mol ratio is 1～1.15:1.
(1) the semiclosed thing of polyisocyanates is prepared
The present invention prepares the method for the semiclosed thing of polyisocyanates: using polyisocyanates and solvent as bed material, 50 ～between 80 DEG C, drip sealer, wherein solvent accounts for the 5～30wt% of reactant gross mass, and sealer rubs with polyisocyanates Your ratio is 1.05～1.5:1, and sealer dripped off in 2 hours, after completion of dropwise addition at 50～80 DEG C insulation 3～5 hours until Till isocyanate content is constant, discharging obtains the semiclosed thing of polyisocyanates, and its structural formula is as follows:
OCN-R1-NHCO-R2
R1For aromatic series or aliphatic alkyl or phenyl, R2For sealer residue.
1. embodiment 1 and each raw material dosage of embodiment 2 are shown in Table 1.
Table 1
2. the concrete operations of the semiclosed thing of embodiment 1 polyisocyanates (A1) are prepared
Using 30.86 grams of IPDIs and 10 grams of solvent butanone as bed material, at 60 DEG C, drip 12.70 grams Sealer methyl ethyl ketoxime, sealer is 1.05:1 with the mol ratio of polyisocyanates, drips off, 60 after completion of dropwise addition in 2 hours It is incubated discharging in 5 hours at DEG C, obtains the semiclosed thing of polyisocyanates (A1), save backup.
3. the concrete operations of the semiclosed thing of embodiment 2 polyisocyanates (A2) are prepared
The concrete operations of preparation are same as in Example 1, and difference is: by 12.70 grams of sealer methyl ethyl ketoximes of embodiment 1 With 14.02 grams of sealers 3,5-dimethyl pyrazole is replaced, is obtained the semiclosed thing of polyisocyanates (A2), save backup.
(2) polyacrylate of hydroxyl is prepared
The method of the polyacrylate that the present invention prepares hydroxyl is: mixing all monomers, chain-transferring agent and initiator Compound, is uniformly added drop-wise in solvent carry out what radical polymerization prepared, and concrete operations are as follows:
With 10～50wt% solvents as bed material, at 50～80 DEG C by 5～15wt% carboxylic vinyl monomers, 2 ～20wt% is ethene improved containing the 6-caprolactone containing primary hydroxyl of primary hydroxyl or the acrylate monomer of secondary hydroxyl, 1～10wt% Other monomers containing vinyl structure of base monomer, 5～70wt%, 0.1～5wt% chain-transferring agent and 0.05～3wt% initiator It is mixed and stirred for uniform mixture, was uniformly added drop-wise in solvent in 3～5 hours, protect at 50～80 DEG C after completion of dropwise addition The polyacrylate of 2～4 hours prepared hydroxyls of temperature, above-mentioned each raw material dosage sum is 100wt%, gathering of prepared hydroxyl The structural formula of acrylate is as follows:
R3,R6,R8For H or CH3；R4For C1～C18Alkyl；R5For H or CH3Or CH2COOH；
R7For containing primary hydroxyl or secondary hydroxyl alkyl；
A, b, c, d are integer between 1～1000；N is 1～6 or 10.
1. each raw material dosage of embodiment 3 is shown in Table 2.
Table 2
2. the concrete operations of the polyacrylate (B) of embodiment 3 hydroxyl are prepared
With 60 grams of butanone as bed material, at 75 DEG C by 12 grams of acrylic acid, 12.5 grams of hydroxyethyl methacrylates, 10 grams PCLFA2D (the 6-caprolactone modified vinyl monomer containing primary hydroxyl), 40 grams of methyl methacrylates, 22.5 grams of acrylic acid fourths Ester, 2 grams of chain-transferring agents (dimer of AMS) and 1 gram of azodiisobutyronitrile are mixed and stirred for uniform mixture, Uniformly it was added drop-wise in solvent in 3 hours, after completion of dropwise addition, at 80 DEG C, is incubated 4 hours, prepare the polyacrylate of hydroxyl (B), save backup.
(3) polyacrylate modified watersoluble closed type isocyanate curing agent is prepared
The present invention prepares the method for polyacrylate modified watersoluble closed type isocyanate curing agent:
Semiclosed for polyisocyanates thing is mixed with the polyacrylate of hydroxyl, wherein, the semiclosed thing of polyisocyanates In the mol ratio of hydroxyl of polyacrylate of NCO and hydroxyl be 1～1.15:1, add and account for polyisocyanates Semiclosed thing and the catalyst of the polyacrylate gross mass 0.001～1.5wt% of hydroxyl, be warming up to 60～80 DEG C and seal Close, at 60～80 DEG C, be incubated 5 hours, obtain polyacrylate modified watersoluble closed Isocyanate prepolymers body, the most wherein Addition accounts for the nertralizer of this performed polymer gross mass 3～8wt% and is neutralized, and adds under the agitator of 200 revs/min of rotating speeds stirs After the deionized water of performed polymer gross mass 1～3 times emulsifies, then solvent is extracted in decompression distillation out, obtain polyacrylate modified Watersoluble closed type isocyanate curing agent, its structural formula is as follows:
R1For aromatic series or aliphatic alkyl or phenyl, R2For sealer residue；
R3,R6,R8For H or CH3；R4For C1～C18Alkyl；R5For H or CH3Or CH2COOH；
R7For containing primary hydroxyl or secondary hydroxyl alkyl；
For nertralizer；A, b, c, d are integer between 1～1000；N is 1～6 or 10.
1. each raw material dosage of embodiment 4 and 5 is shown in Table 3.
Table 3
2. the concrete operations of the polyacrylate modified watersoluble closed type isocyanate curing agent (D1) of embodiment 4 are prepared
The 53.56 grams of semiclosed thing of polyisocyanates (A1) (containing remaining NCO group 0.132 mole) that embodiment 1 is prepared Mix with the polyacrylate B (hydroxyl 0.125 mole) of hydroxyl, the wherein isocyanide in the semiclosed thing of polyisocyanates (A1) Perester radical is 1.06:1 with the mol ratio of the hydroxyl of the polyacrylate (B) of hydroxyl, adds the catalyst dibutyltin cinnamic acid of 0.1 gram Dibutyl tin (for the 0.047wt% of A1+B gross mass), liter high-temperature, to 80 DEG C, is incubated 5 hours, the most wherein at 80 DEG C Adding 12 grams of nertralizer triethylamines (for the 5.6wt% of A1+B gross mass) to be neutralized, the agitator at 200 revs/min of rotating speeds stirs Mixing 250 grams of deionized waters of lower addition (for 1.17 times of A1+B gross mass) to emulsify, be warming up to 70 DEG C, decompression distillation is extracted out molten After agent, obtain polyacrylate modified watersoluble closed type isocyanate curing agent (D1).
3. the concrete operations of the polyacrylate modified watersoluble closed type isocyanate curing agent (D2) of embodiment 5 are prepared
Substantially the same manner as Example 4, difference is the semiclosed thing of polyisocyanates prepared by 54.88 grams of embodiments 2 (A2) substitute (A1) (containing remaining NCO group 0.132 mole), finally give the solidification of water polyacrylic acid blocked isocyanate Agent (D2).
(4) embodiment 6 prepares the watersoluble closed type isocyanate curing agent (D0) of comparative example
1. the polyacrylate (B0) of comparative example hydroxyl is prepared
With the maximum difference of embodiment 3 formula it is: be provided without the 6-caprolactone modified vinyl monomer containing primary hydroxyl, But use the hydroxyethyl methacrylate of equimolar ratio to replace 10 grams of PCL FA2D (6-caprolactone modification second containing primary hydroxyl Alkenyl monomer), the most altogether add 16.27 grams of hydroxyethyl methacrylates, concrete formula is shown in Table 4.
Table 4
The concrete operations of the polyacrylate (B0) of preparation comparative example hydroxyl are same as in Example 3.
2. the watersoluble closed isocyanate curing agent (D0) of comparative example is prepared
Raw material dosage is substantially the same manner as Example 5, and difference is: with the polyacrylate of 160 grams of comparative example hydroxyls (B0) replace the polyacrylate (B) of the hydroxyl that embodiment 3 prepares, be specifically shown in Table 5.
Table 5
The concrete operations of the watersoluble closed isocyanate curing agent (D0) of preparation comparative example are same as in Example 5.
(5) single-component water-based polyurethane coating is prepared
For investigating the curing agent impact on coating property, use the polyacrylate modified watersoluble closed type isocyanide of the present invention Acid esters curing agent D1 and D2 (embodiment 4 and 5 prepares) and the watersoluble closed type isocyanate curing agent D0 (embodiment 6 of comparative example Prepare) make curing agent and hydroxy acryl acid ester dispersion and additive by the formula ratio of table 6, each component mix and blend (is coated with Material 1,2, stirs 5 minutes；Coating 3 stirs 10 minutes) prepare coating 1, coating 2 and coating 3 respectively, in above-mentioned 3 coating The ratio of NCO/OH is all set as 1.2.
Table 6
Note: CTW6026 solids content 35wt%, hydroxy radical content is 0.86wt% (relative to hard resin), and CNOOC is normal State environmental protection coating material Co., Ltd produces, factory site: Changzhou Yulong Road, Jiangsu Province 2, postcode 213014；
Defoamer BYK025, levelling agent BYK331 are Germany's BYK Products.
(6) detection coating property
The coating 1～3 utilizing above-mentioned preparation prepares model by spraying application, by the model after spraying, places in room temperature After 10 minutes, the model of coating 1 toasts 20 minutes at 150 DEG C, and the model of coating 2 and coating 3 was 130 DEG C of bakings 20 minutes, respectively The build of model is 20 microns, for detection.
Detection method and testing result are shown in Table 7.
Table 7
Detection project Detection method Coating 1 Coating 2 Coating 3
Paint film appearance Range estimation Flat smooth Flat smooth Flat smooth
Gloss (60 °) GB/T9754-2007 95.3 96.5 92.9
Adhesive force ,≤level GB/T9286-1998 1 1 1
Pencil hardness GB/T6739-2006 2H 2H 2H
Shock resistance, >= GB/T1732-1993 50 50 35
Pliability, level GB/T1731-1993 1 1 2
Resistance to water (72h) GB/T1733-1993 Without exception Without exception Without exception
Alcohol resistance (24h) GB/T9274-1988 Without exception Without exception Without exception
Resistance to methyl ethyl ketone rubs, secondary GB/T23989-2009 ＞ 150 ＞ 150 ＞ 100
From table 7 testing result, use the polyacrylate modified watersoluble closed type isocyanate curing agent of the present invention (embodiment 4,5 prepares) has good compatibility with aqueous hydroxy acryl acid ester dispersion, and both mix and require time for Short (about 5 minutes), can effectively improve production efficiency.The paint coatings flat smooth prepared, has good after coating crosslinking Gloss, excellent adhesive force and higher hardness.Due to the curing agent D0 of coating 3 (contrast coating), in the preparation, used contain Without 6-caprolactone modified vinyl segment in the molecular structure of the polyacrylate (B0) of hydroxyl, therefore, its respective coatings Shock resistance and pliability be below the coating 1 and 2 with curing agent of the present invention, it was demonstrated that is preparing the polyacrylic acid of hydroxyl The effect introducing the 6-caprolactone modified vinyl monomer containing primary hydroxyl during ester (B) is obvious.

Claims (5)

1. a polyacrylate modified watersoluble closed type isocyanate curing agent, it is characterised in that it is polyisocyanates half Closure mixes with the polyacrylate of hydroxyl, in the presence of a catalyst, adds the performed polymer that thermal response obtains, more neutralized, Emulsification, except obtain after solvent, wherein, the polyacrylate of the NCO in the semiclosed thing of polyisocyanates and hydroxyl The mol ratio of hydroxyl be 1～1.15:1；
Described hydroxyl polyacrylate is with 10～50wt% solvents as bed material, carboxylic vinyl-based by 5～15wt% Monomer, 2～20wt% change containing the 6-caprolactone containing primary hydroxyl of primary hydroxyl or the acrylate monomer of secondary hydroxyl, 1～10wt% Other monomer containing vinyl structure of sex ethylene base monomer, 5～70wt%, 0.1～5wt% chain-transferring agent and 0.05～3wt% The mixture of initiator, is added drop-wise in solvent bed material carry out what radical polymerization prepared, and above-mentioned each raw material dosage sum is 100wt%, wherein, the 6-caprolactone modified vinyl monomer containing primary hydroxyl it there is CH2=CRCOOCH2CH2O[CO(CH2)5O]nH structure formula, R=H or CH in formula3, n=1～6 or n=10；In the raw material preparing hydroxyl polyacrylate, containing carboxylic The vinyl monomer of base is one or more in (methyl) acrylic acid, itaconic acid；Containing primary hydroxyl or the acrylic acid of secondary hydroxyl Ester monomer is the one or several in (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl Kind；Other monomer containing vinyl structure is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid fourth In ester, (methyl) propyl acrylate, acrylic acid-2-ethyl caproite, (methyl) n-octyl, benzyl acrylate, styrene One or more；
The semiclosed thing of described polyisocyanates is to make sealer with hydrogen-containing compound to close polyisocyanates, sealer with The mol ratio of polyisocyanates is (1.05～1.5): 1；As the hydrogen-containing compound of described sealer be methyl alcohol, ethanol, propyl alcohol, Butanol, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, methyl ethyl ketoxime, acetyl oxime, methyl Isobutyl group oxime, epsilon-caprolactams, butyrolactam, 3-methylpyrazole, 3,5-dimethyl pyrazole, 3-methyl-5-ethylpyrazol, 3-ethyl-5-propylpyrazol, 3-ethyl-5-isopropylpyrazol, 3-ethyl-5-butyl pyrazoles, 3-ethyl-5-t-butylpyrazol, One or more in phenol, parachlorophenol, o-nitrophenol；Described polyisocyanates be IPDI, 1, Hexamethylene-diisocyanate, 4,4 '-dicyclohexyl methyl hydride-diisocyanate, XDI, durol diformazan Group diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, polymethylene are many One or more in polyphenyl polyisocyanate.
2. a preparation method for the polyacrylate modified watersoluble closed type isocyanate curing agent described in claim 1, its Being characterised by, concrete preparation process is as follows:
1. the semiclosed thing of polyisocyanates is prepared
Using polyisocyanates and solvent as bed material, dripping sealer between 50～80 DEG C, wherein solvent accounts for the total matter of reactant The 5～30wt% of amount, sealer is 1.05～1.5:1 with the mol ratio of polyisocyanates, and sealer dripped off in 2 hours, drips Being incubated 3～5 hours till isocyanate content is constant at 50～80 DEG C after adding end, discharging obtains polyisocyanates half Closure；
2. the polyacrylate of hydroxyl is prepared
By the mixture of all monomers, chain-transferring agent and initiator, uniformly it is added drop-wise in solvent carry out what radical polymerization prepared, Concrete operations are as follows:
With 10～50wt% solvents as bed material, at 50～80 DEG C by 5～15wt% carboxylic vinyl monomers, 2～ 20wt% contains primary hydroxyl or the 6-caprolactone modified vinyl containing primary hydroxyl of the acrylate monomer of secondary hydroxyl, 1～10wt% Other monomer containing vinyl structure of monomer, 5～70wt%, 0.1～5wt% chain-transferring agent and 0.05～3wt% initiator mix Merge the mixture stirred, be uniformly added drop-wise in solvent in 3～5 hours, at 50～80 DEG C, after completion of dropwise addition, be incubated 2 ～the polyacrylate of 4 hours prepared hydroxyls, above-mentioned each raw material dosage sum is 100wt%；
3. polyacrylate modified watersoluble closed type isocyanate curing agent is prepared
The polyacrylate of the hydroxyl that 2. the semiclosed thing of polyisocyanates step 1. prepared prepares with step mixes, its In, the mol ratio of the hydroxyl of the polyacrylate of the NCO in the semiclosed thing of polyisocyanates and hydroxyl be 1～ 1.15:1, adds the catalysis accounting for the semiclosed thing of polyisocyanates with the polyacrylate gross mass 0.001～1.5wt% of hydroxyl Agent, is warming up to 60～80 DEG C and closes, and is incubated 5 hours, obtains polyacrylate modified watersoluble closed different at 60～80 DEG C Cyanate performed polymer, adds the most wherein and accounts for the nertralizer of this performed polymer gross mass 3～8wt% and be neutralized, 200 turns/ The agitator stirring of point rotating speed is lower to add the deionized water of performed polymer gross mass 1～3 times and emulsifies, then decompression distillation is extracted out molten After agent, obtain polyacrylate modified watersoluble closed type isocyanate curing agent.
The preparation method of polyacrylate modified watersoluble closed type isocyanate curing agent the most according to claim 2, its Be characterised by, step 1. in, the hydrogen-containing compound as described sealer is methyl alcohol, ethanol, propyl alcohol, butanol, ethylene glycol list Methyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, methyl ethyl ketoxime, acetyl oxime, methyl-isobutyl oxime, ε-oneself Lactams, butyrolactam, 3-methylpyrazole, 3,5-dimethyl pyrazole, 3-methyl-5-ethylpyrazol, 3-ethyl-5-propyl group Pyrazoles, 3-ethyl-5-isopropylpyrazol, 3-ethyl-5-butyl pyrazoles, 3-ethyl-5-t-butylpyrazol, phenol, parachlorophenol, One or more in o-nitrophenol；Described polyisocyanates be IPDI, hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride-diisocyanate, XDI, tetramethyl xylylene diisocyanate, first In phenylene diisocyanate, methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate One or more；Described solvent is one or more of acetone or butanone.
The preparation method of polyacrylate modified watersoluble closed type isocyanate curing agent the most according to claim 2, its Be characterised by, step 2. in, described carboxylic vinyl monomer is the one or several in (methyl) acrylic acid, itaconic acid Kind；Acrylate monomer containing primary hydroxyl or secondary hydroxyl is (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (first Base) one or more in hy-droxybutyl；6-caprolactone modified vinyl monomer containing primary hydroxyl it there is CH2= CRCOOCH2CH2O[CO(CH2)5O]nH structure formula, wherein R=H or CH3, n=1～6 or 10；Other list containing vinyl structure Body is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) propyl acrylate, propylene One or more in acid-2-Octyl Nitrite, (methyl) n-octyl, benzyl acrylate, styrene；Described solvent is third One or more of ketone or butanone；Described chain-transferring agent be n-butyl mercaptan, isobutyl mercaptan, positive hexyl mercaptan, n-dodecyl mercaptan, One or more in tertiary lauryl mercaptan, AMS dimer；Described initiator is azodiisobutyronitrile, azo In diisoamyl nitrile, ABVN, azo-bis-iso-dimethyl, azo dicyclohexyl formonitrile HCN, dibenzoyl peroxide One or more.
The preparation method of polyacrylate modified watersoluble closed type isocyanate curing agent the most according to claim 2, its Be characterised by, step 3. in, used catalyst is in triethylamine, triethylene diamine, dibutyl tin laurate, stannous octoate One；Nertralizer used is ammoniacal liquor, triethanolamine, triethylamine, N, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol In one.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115526A (en) * 2011-01-04 2011-07-06 中科院广州化学有限公司 Extinction acrylic resin for anodic electrophoresis and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115526A (en) * 2011-01-04 2011-07-06 中科院广州化学有限公司 Extinction acrylic resin for anodic electrophoresis and preparation method thereof

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