CN102432775A - Preparation method of waterborne polyurethane-polyacrylate composite latex - Google Patents
Preparation method of waterborne polyurethane-polyacrylate composite latex Download PDFInfo
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- CN102432775A CN102432775A CN2011102622617A CN201110262261A CN102432775A CN 102432775 A CN102432775 A CN 102432775A CN 2011102622617 A CN2011102622617 A CN 2011102622617A CN 201110262261 A CN201110262261 A CN 201110262261A CN 102432775 A CN102432775 A CN 102432775A
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- polyurethane
- waterborne polyurethane
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- polyacrylate
- compounded latex
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 50
- 239000004816 latex Substances 0.000 title claims abstract description 49
- 229920000126 latex Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 claims abstract description 51
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 230000000903 blocking effect Effects 0.000 claims description 32
- 239000000839 emulsion Substances 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000004945 emulsification Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- 235000019394 potassium persulphate Nutrition 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 6
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical group CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- -1 acrylic ester Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 102100026735 Coagulation factor VIII Human genes 0.000 description 5
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 241000237502 Ostreidae Species 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000020636 oyster Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of waterborne polyurethane-polyacrylate composite latex, which comprises the following steps: firstly, vinyl-terminated waterborne polyurethane is synthesized to be used as an emulsifier and a seed phase for vinyl emulsion polymerization, and then a polyacrylate molecular chain is introduced onto the molecules of the waterborne polyurethane through chemical bonds through emulsion polymerization reaction, so that the waterborne polyurethane-polyacrylate composite latex with a core-shell structure is prepared. The method has the advantages of wide range of selectable acrylate monomers, low price, simple synthesis reaction and easy preparation of a composite structure with two different polymer chains.
Description
Technical field
The present invention proposes a kind of preparation method of waterborne polyurethane-polyacrylate compounded latex, and it is by aqueous polyurethane and two kinds of chemically composited forming of compositions process of water polyacrylic acid, relates to the synthesis technical field of polymkeric substance and material.
Technical background
From the needs to environment protection and Sustainable development and human health, aqueous polyurethane has been widely used in fields such as coating and paint.Can demonstrate excellent elasticity, rub resistance and lower temperature resistance after the aqueous polyurethane film forming, but its water tolerance and chemical resistance are relatively poor.For water tolerance and the chemical resistance that improves aqueous polyurethane, common way is to mix them with polyacrylic ester, and this is because polyacrylic ester has excellent weathering resistance, water tolerance and chemical resistant properties, and the price of polyacrylic ester is more cheap relatively simultaneously.But, because macroface occurring than missionary society, the consistency of these two kinds of polymkeric substance separates, simply these two kinds of various polymerization thing dispersion liquids are mixed the degradation that will cause film.Solving these two kinds of inconsistent methods of various polymerization thing is to introduce vinylformic acid or vinyl polymer or be grafted in the aqueous polyurethane chain; Make these two kinds of various polymerization chains combine closely and form a kind of composite emulsion, can give full play to urethane and polyacrylic ester characteristic separately simultaneously.The route of synthesizing cross-linked type composite emulsion has a lot, such as the graft copolymerization on the polyacrylic ester chain of seeded emulsion polymerization, latex interpenetrating polymerization, cross-couplings and urethane.Seeded emulsion polymerization be the urethane of water-based as acrylic monomer polymeric seed phase, through letex polymerization, polyacrylate grafting on polyurethane chain.The prerequisite of this synthetic route is that urethane can be emulsified into stable colloidal solid, and acrylic monomer can carry out the polymerization of the concurrent lactogenesis liquid of swelling in aqueous polyurethane then.Can access cross-linking type PUA composite emulsion at last through this way.With respect to other method, seed emulsion polymerization is easy and simple to handle and be widely used in the industrial production.Existing used for water color ink emulsion is that water-soluble is good inadequately on the one hand; On the other hand, a lot of emulsions are to add the tensio-active agent emulsive, and the emulsion-stabilizing phase had only about half a year; And add tensio-active agent can not film forming (participation adhesive attraction), the sticking power and the moisture-proof that influence printing ink are wiped.
Summary of the invention
The objective of the invention is to, propose a kind of preparation method of waterborne polyurethane-polyacrylate compounded latex, it is that water-soluble is good inadequately on the one hand that the present invention is intended to solve existing used for water color ink emulsion; On the other hand, a lot of emulsions are to add the tensio-active agent emulsive, and the emulsion-stabilizing phase had only about half a year, and add tensio-active agent can not film forming, influence the sticking power and the moisture-proof wiping problem of printing ink.
The present invention has adopted following technical scheme:
A kind of preparation method of waterborne polyurethane-polyacrylate compounded latex, it may further comprise the steps: steps A: synthesis of vinyl end-sealed type aqueous polyurethane; Step B: utilize ethenyl blocking type aqueous polyurethane to synthesize the waterborne polyurethane-polyacrylate composite emulsion,
Wherein, said steps A specifically comprises:
Steps A 1: with end hydroxy polyether, dimethylol propionic acid and 1, the 4-butyleneglycol mixes and is dissolved in and forms mixing solutions in the organic solvent;
Steps A 2: under 40 ~ 65 ℃, catalyzer, diisocyanate cpd and acetone are splashed in the mixing solutions;
Steps A 3: be warmed up to 65 ℃～95 ℃ after dropwising, and under this temperature, reacted 3 hours～5 hours, make diisocyanate terminated type polyurethane;
Steps A 4: in diisocyanate terminated type polyurethane, add vinyl monomer, under 60～80 ℃, proceed to react 1.5 hours～2.5 hours, obtain the ethenyl blocking type polyurethane;
Steps A 5: under 30～50 ℃,, be reflected at 15 minutes～accomplish in 30 minutes with triethylamine neutralization of ethylene base end-sealed type urethane;
Steps A 6: add a certain amount of zero(ppm) water in the ethenyl blocking type polyurethane that is neutralized, at room temperature high speed dispersion obtained ethenyl blocking type aqueous polyurethane in 30 minutes～60 minutes.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, said step B specifically comprises:
Step B1: adopt the semi-continuous emulsion polymerizing method, ethenyl blocking type aqueous polyurethane is mixed with the load weighted acrylic ester monomer of calculating and stirs carry out preparatory emulsification and obtain preparatory emulsification;
Step B2: get 8%～10 % of the preparatory emulsification weight part that obtains among the step B1 and the initiator of 8%～10 % weight part and join in the reactor drum, logical N
2Protection, 60 ℃～85 ℃ down reactions 15 minutes～30 minutes, said initiator is a Potassium Persulphate, the total consumption of initiator is 1%～3% of the monomeric weight of all participation polyreactions;
Step B3: added in the reactor drum reaction to remaining preparatory emulsification and Potassium Persulphate respectively 3 hours～5 hours, obtain the waterborne polyurethane-polyacrylate compounded latex.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, said end hydroxy polyether is cetomacrogol 1000, W 166 1000 or PTMG 1000.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex; Wherein, said organic solvent is a polar solvent, selects acetone, N for use; N-diformamide or N-Methyl pyrrolidone, consumption of organic solvent for the weight that adds whole raw materials used before the organic solvent and 10%～15%.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, said catalyzer is butyl(tetra)titanate, dibutyl tin laurate or titanium isopropylate, catalyst consumption is 0.5%～1% of a vulcabond weight.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, said diisocyanate cpd is tolylene diisocyanate or isophorone diisocyanate.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, said vinyl monomer is vinylbenzene, TEB 3K, methylacrylic acid second fat, methyl acrylate or Bing Xisuandingzhi.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, the addition of said triethylamine is so that the pH value of neutralization back system is a standard for 6-7.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, the structural formula of said ethenyl blocking type polyurethane is following:
In the formula, R
1For
Or
R
2Be cetomacrogol 1000 and W 166 1000 and PTMG 1000.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, said waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is a urethane, examines to be polyacrylic ester.
Compared with prior art, the present invention has following unusual effect:
It utilizes the synthetic aqueous polyurethane carries out letex polymerization as acrylic ester monomer emulsifying agent and seed mutually; Be incorporated into the polyacrylic ester molecular chain in the molecular structure of aqueous polyurethane through chemical bond; Prepare the waterborne polyurethane-polyacrylate compounded latex of nucleocapsid structure, the alternative acrylic ester monomer scope of this method is big, cheap, building-up reactions is simple, be easy to prepare the composite structure of two kinds of polymkeric substance.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, clear and definite, below with reference to embodiment to further explain of the present invention.
Waterborne polyurethane-polyacrylate compounded latex preparation method provided by the invention carries out according to the following steps:
Steps A: synthesis of vinyl end-sealed type aqueous polyurethane, its concrete grammar is:
Steps A 1: with end hydroxy polyether, dimethylol propionic acid and 1, the 4-butyleneglycol mixes and is dissolved in and forms mixing solutions in the organic solvent;
Wherein, said end hydroxy polyether, dimethylol propionic acid and 1, the amount of 4-butyleneglycol is to confirm according to the molecular weight real-time measuring data of end hydroxy polyether.Said end hydroxy polyether is cetomacrogol 1000 or W 166 1000, PTMG 1000.Said organic solvent is a polar solvent, selects acetone or N for use, N-diformamide, N-Methyl pyrrolidone, consumption of organic solvent for the weight that adds whole raw materials used before the organic solvent and 10%～15%.
Steps A 2: under 40 ~ 65 ℃, catalyzer, diisocyanate cpd and acetone are splashed in the mixing solutions;
Wherein, the amount of said catalyzer, diisocyanate cpd and acetone determines in real time that according to catalyzer and the solubleness of vulcabond in acetone its speed that splashes into mixing solutions wants slow, observes while drip.Said catalyzer is butyl(tetra)titanate, dibutyl tin laurate, titanium isopropylate, and catalyst consumption is 0.5%～1% of a vulcabond weight.Said diisocyanate cpd is tolylene diisocyanate (TDI) or isophorone diisocyanate (IPDI).
Steps A 3: be warmed up to 65 ℃～95 ℃ after dropwising, and under this temperature, reacted 3 hours～5 hours, make diisocyanate terminated type polyurethane;
Steps A 4: in diisocyanate terminated type polyurethane, add vinyl monomer, under 60～80 ℃, proceed to react 1.5 hours～2.5 hours, obtain the ethenyl blocking type polyurethane;
Wherein, said vinyl monomer is vinylbenzene, TEB 3K, methylacrylic acid second fat, methyl acrylate or Bing Xisuandingzhi, methylacrylic acid-beta-hydroxy ethyl ester.According to the addition that the molecular weight requirement and the film forming adhesion property of emulsion are adjusted methylacrylic acid-beta-hydroxy ethyl ester.
Steps A 5: under 30～50 ℃,, be reflected at 15 minutes～accomplish in 30 minutes with triethylamine neutralization of ethylene base end-sealed type urethane;
Wherein, the addition of said triethylamine is so that the pH value of neutralization back system is a standard for 6-7.
Steps A 6: add a certain amount of zero(ppm) water in the ethenyl blocking type polyurethane that is neutralized, at room temperature high speed dispersion obtained ethenyl blocking type aqueous polyurethane in 30 minutes～60 minutes.
Wherein, the amount of the zero(ppm) water of interpolation is to calculate amount of water according to 40%～50% of the emulsion concentration of setting.Said emulsion concentration refers to the desired emulsion solid content of current production batch (abbreviation concentration).
Step B: utilize ethenyl blocking type aqueous polyurethane to synthesize the waterborne polyurethane-polyacrylate composite emulsion, its concrete grammar is:
Step B1: adopt the semi-continuous emulsion polymerizing method, ethenyl blocking type aqueous polyurethane is mixed with the load weighted acrylic ester monomer of calculating and stirs carry out preparatory emulsification and obtain preparatory emulsification;
Step B2: get 8%～10 % of the preparatory emulsification weight part that obtains among the step B1 and the initiator of 8%～10 % weight part and join in the reactor drum, logical N
2Protection was reacted 15 minutes～30 minutes down at 60 ℃～85 ℃, and said initiator is a Potassium Persulphate, and the total consumption of initiator is 1%～3% of a monomer weight; All monomers of participating in polyreaction comprise esters of acrylic acid, end hydroxy polyether, dimethylol propionic acid, vulcabond etc.
Step B3: added in the reactor drum reaction to remaining preparatory emulsification and Potassium Persulphate respectively 3 hours～5 hours, obtain milky stable composite emulsion, i.e. the waterborne polyurethane-polyacrylate compounded latex.
Wherein, the adding method of said preparatory emulsification and Potassium Persulphate is for becoming to drip in shape or the fine rule stream shape adding reactor drum.The final dispersion medium of said waterborne polyurethane-polyacrylate compounded latex is a deionized water, and dilutable water is regulated concentration (viscosity).
The structural formula of said ethenyl blocking type polyurethane is following:
In the formula, R
1For
Or
R
2Be cetomacrogol 1000 and W 166 1000 and PTMG 1000.
Said waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is a urethane, examines to be polyacrylic ester.
Below through 9 embodiment the present invention is done further explanation, but the present invention is not limited to these technical parameter of giving an example and processes.
, ethenyl blocking type aqueous polyurethane (VLWPU) preparation embodiment
Table 1 preparation ethenyl blocking type aqueous polyurethane is with raw material (weight part)
The preparation process is following:
Embodiment 1: the typical case of ethenyl blocking type aqueous polyurethane (VLWPU) synthesizes in a 250mL four-hole boiling flask that TM, mechanical stirrer and prolong (top is connected with drying tube) be housed and carries out.
At first at room temperature
PPG1000 (9.05 g),
DMPA(0.68 g) and 1,4-
BD(0.35 g) joins in the flask.Add subsequently
NMP(1.8 g) stirs until obtaining homogeneous system.Be warmed up to 60～90 ℃, in 30～60 min, dropwise add then
IPDI(4.65 g),
DBTDLThe mixed solution that (3～5) and acetone (5.0 g) are formed, sustained reaction 3～5 h, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).Again to wherein adding
HEMA(0.81 g) keeps being reflected at 60～80 ℃ and continuing down reaction 1.5～2.5 h, obtain the ethenyl blocking type polyurethane (
VLPU).Be cooled to subsequently under 30～50 ℃, use
TEA(0.56 g) neutralization
VLPU, be reflected in 15～30 min and accomplish.At last, slowly add zero(ppm) water (50 g) in the urethane that is neutralized, at room temperature to obtain carboxyl-content be 5% ethenyl blocking type aqueous polyurethane to high speed dispersion 30～60 min.
The above-mentioned formulation of foundation
VLWPUBe translucent blueing light emulsion, latex particle size is less and viscosity is little.Test through IR (KBr): ν=3330,2958,2847,2268,1727,1650,1110cm
-1
Embodiment 2: at room temperature
PPG1000 (10.07 g),
DMPA(0.45 g) and 1,4-
BD(0.33 g) joins in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment rise to 60～90 ℃ to temperature, in 30～60 min, dropwise add then
IPDI(4. 5 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.65 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.42 g) neutralization
VLPU, be reflected in 15～30 min and accomplish.At last, slowly add zero(ppm) water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 3% ethenyl blocking type aqueous polyurethane (
VLWPU).Embodiment 2 is prepared
VLWPUBe milky emulsion, latex particle size is big and deposition is unstable easily.
Embodiment 3: following of normal temperature
PPG1000 (9 g),
DMPA(0.55 g) and 1,4-
BD(0.28g) join in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment rise to 60～90 ℃ to temperature, in 30～60 min, dropwise add then
IPDI(4. 52 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.7 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.48 g) neutralization
VLPU, be reflected in 15～30 min and accomplish.At last, slowly add zero(ppm) water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 4% ethenyl blocking type aqueous polyurethane (
VLWPU).Obtain thus
VLWPUBe oyster white blueing light emulsion a little, latex particle size is bigger.
Embodiment 4: identical with the program of the several embodiment in front, at first at room temperature
PPG1000 (8 g),
DMPA(0.78 g) and 1,4-
BD(0.3g) join in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment rise to 60～90 ℃ to temperature, in 30～60 min, dropwise add then
IPDI(4. 52 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.8 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.6 g) neutralization
VLPU, be reflected in 15～30 min and accomplish.At last, slowly add zero(ppm) water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 6% ethenyl blocking type aqueous polyurethane (
VLWPU).Obtain thus
VLWPUBe translucent blueing light emulsion, latex particle size is less, but viscosity is big slightly.
Embodiment 5: synthesizer and operating process are the same,
At firstAt room temperature
PPG1000 (7.65 g),
DMPA(0.78 g) and 1,4-
BD(0.25g) join in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment rise to 60～90 ℃ to temperature, in 30～60 min, dropwise add then
IPDI(4. 52 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.77 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.68 g) neutralization
VLPU, be reflected in 15～30 min and accomplish.At last, slowly add zero(ppm) water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 7% ethenyl blocking type aqueous polyurethane (
VLWPU).By example 5 said formulation
VLWPUFor translucent and blue light phenomenon clearly, latex particle size is little, but system viscosity is bigger.
, the waterborne polyurethane-polyacrylate compounded latex preparation:
Table 2 preparation waterborne polyurethane-polyacrylate compounded latex is with raw material (weight part)
Concrete preparation process is following:
Embodiment 6: semicontinuous emulsifier-free emulsion polymerization method is adopted in the preparation of waterborne polyurethane-polyacrylate compounded latex; Be any one carboxyl-content of preparation among the embodiment 1～5 that 5% ethenyl blocking type aqueous polyurethane VLWPU (30g) mixes with vinylbenzene (5g) and Bing Xisuandingzhi (5g) at first, and under suitable stirring velocity, carry out preparatory emulsification.Join 10% preparatory emulsification and 10%KPS (amount of initiator be amount of monomer 1%) in the 250mL four-hole boiling flask earlier then, lead to N
2Protection, 60～80 ℃ are reacted 15～30min down.Be added dropwise to remaining preparatory emulsification and KPS with speed slowly respectively then and react 3～5h in the flask.Obtain the stable composite emulsion of oyster white blueing light at last.(TEM) observes its pattern with transmission electron microscope.Said waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is a urethane, examines to be polyacrylic ester.
Embodiment 7: primary process is with embodiment 6, is the carboxyl-content of preparation 5% earlier
VLWPU(30 g) mixes with vinylbenzene (3 g) and Bing Xisuandingzhi (7 g), and under suitable stirring velocity, carries out preparatory emulsification.Then earlier 10 %'s of the preparatory emulsification of 10 % and initiator total amount
KPSJoin in the 250 mL four-hole boiling flasks logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Be added dropwise to remaining preparatory emulsification and KPS with speed slowly respectively then and react 3～5 h in the flask.Obtain the composite emulsion of oyster white blueing light at last.
Embodiment 8: according to the program of embodiment 6, be carboxyl-content 5% earlier
VLWPU(30 g) and vinylbenzene (
Styrene, 7 g) and Bing Xisuandingzhi (3 g) mixing, carry out preparatory emulsification.Then earlier the preparatory emulsification of 10 % and 10 %
KPS(amount of initiator is 1 % of amount of monomer) joins in the 250 mL four-hole boiling flasks, logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Be added dropwise to remaining preparatory emulsification and KPS with speed slowly respectively then and react 3～5 h in the flask.Obtain milky composite emulsion at last.
Embodiment 9: adopt semicontinuous emulsifier-free emulsion polymerization legal system to be equipped with the waterborne polyurethane-polyacrylate compounded latex equally.Is carboxyl-content 5%
VLWPU(30 g) mixes with vinylbenzene (10 g) and carries out preparatory emulsification.Then earlier the preparatory emulsification of 10 % and 10 %
KPS(amount of initiator is 1 % of amount of monomer) joins in the 250 ml four-hole boiling flasks, logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Then remaining preparatory emulsification with
KPSBe added dropwise to speed slowly respectively and react 3～5 h in the flask.Obtain milky composite emulsion at last, emulsion is very unstable, is easy to sedimentation.
The waterborne polyurethane-polyacrylate compounded latex of above-mentioned steps B gained is filmed at room temperature dry 24 h, dry 24 h in 30～50 ℃ of thermostat containers then on tinplate.Testing standard is that hardness of film adopts GB/T 6739-1996; Film adhesive adopts GB 1720-79 (89) to measure; The snappiness of filming adopts GB/T 1731-93 to measure; The coating film gloss degree adopts GB 1743-79 (89) to measure; Water-resistance property of coating adopts GB/T 1733-93 to measure; The water-intake rate of filming is measured by HG 2-1612-85.Draw the following table data:
| The waterborne polyurethane-polyacrylate composite emulsion | Embodiment 6-8 sample actual measurement MV |
| Molecular weight | 310934 |
| Emulsion particle median size (μ m) | 13.5 |
| Second-order transition temperature (℃) | 41.23 |
| Initial heat decomposition temperature (℃) | 276.12 |
| Fracture tensile strength (MPa) | 10.05 |
| Pencil hardness | H |
| Sticking power | 100% |
| Snappiness | 2 |
| Glossiness | 97 |
| Water-intake rate | 34% |
| Water tolerance (48 h) | Slight corrosion |
The performance of table 3 waterborne polyurethane-polyacrylate compounded latex
Waterborne polyurethane-polyacrylate composite emulsion of the present invention is through ir spectra, and methods such as gel permeation chromatography and TEM characterize, and has confirmed composite emulsion structure, molecular weight, particle diameter and pattern.
The waterborne polyurethane-polyacrylate compounded latex that the present invention makes, the material choice scope is bigger, and cost is lower; Has the self-emulsifying function, the emulsion stable storing; Deionized water with or the inexpensive solvent that has no side effect such as ethanol in can disperse well, " green " environmental protection is easy to adjust concentration and viscosity when subsequent applications; Film forming properties is good, and tint retention is good, and is good to the color developing of pigment, and glossiness is high.
Should be understood that application of the present invention is not limited to above-mentioned giving an example, concerning those of ordinary skills, can improve or conversion that all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
Claims (10)
1. the preparation method of a waterborne polyurethane-polyacrylate compounded latex, it may further comprise the steps: steps A: synthesis of vinyl end-sealed type aqueous polyurethane;
Step B: utilize ethenyl blocking type aqueous polyurethane to synthesize the waterborne polyurethane-polyacrylate composite emulsion,
Wherein, said steps A specifically comprises:
Steps A 1: with end hydroxy polyether, dimethylol propionic acid and 1, the 4-butyleneglycol mixes and is dissolved in and forms mixing solutions in the organic solvent;
Steps A 2: under 40 ~ 65 ℃, catalyzer, diisocyanate cpd and acetone are splashed in the mixing solutions;
Steps A 3: be warmed up to 65 ℃～95 ℃ after dropwising, and under this temperature, reacted 3 hours～5 hours, make diisocyanate terminated type polyurethane;
Steps A 4: in diisocyanate terminated type polyurethane, add vinyl monomer, under 60～80 ℃, proceed to react 1.5 hours～2.5 hours, obtain the ethenyl blocking type polyurethane;
Steps A 5: under 30～50 ℃,, be reflected at 15 minutes～accomplish in 30 minutes with triethylamine neutralization of ethylene base end-sealed type urethane;
Steps A 6: add a certain amount of zero(ppm) water in the ethenyl blocking type polyurethane that is neutralized, at room temperature high speed dispersion obtained ethenyl blocking type aqueous polyurethane in 30 minutes～60 minutes.
2. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, said step B specifically comprises:
Step B1: adopt the semi-continuous emulsion polymerizing method, ethenyl blocking type aqueous polyurethane is mixed with the load weighted acrylic ester monomer of calculating and stirs carry out preparatory emulsification and obtain preparatory emulsification;
Step B2: get 8%～10 % of the preparatory emulsification weight part that obtains among the step B1 and the initiator of 8%～10 % weight part and join in the reactor drum, logical N
2Protection, 60 ℃～85 ℃ down reactions 15 minutes～30 minutes, said initiator is a Potassium Persulphate, the total consumption of initiator is 1%～3% of the monomer weight of all participation polyreactions;
Step B3: added in the reactor drum reaction to remaining preparatory emulsification and Potassium Persulphate respectively 3 hours～5 hours, obtain the waterborne polyurethane-polyacrylate compounded latex.
3. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, said end hydroxy polyether is cetomacrogol 1000, W 166 1000 or PTMG 1000.
4. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1; It is characterized in that; Said organic solvent is a polar solvent; Select acetone, N for use, N-diformamide or N-Methyl pyrrolidone, consumption of organic solvent for the weight that adds whole raw materials used before the organic solvent and 10%～15%.
5. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1; It is characterized in that; Said catalyzer is butyl(tetra)titanate, dibutyl tin laurate or titanium isopropylate, and catalyst consumption is 0.5%～1% of a vulcabond weight.
6. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, said diisocyanate cpd is tolylene diisocyanate or isophorone diisocyanate.
7. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, said vinyl monomer is vinylbenzene, TEB 3K, methylacrylic acid second fat, methyl acrylate or Bing Xisuandingzhi.
8. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, the addition of said triethylamine is so that the pH value of neutralization back system is a standard for 6-7.
9. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, the structural formula of said ethenyl blocking type polyurethane is following:
10. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, said waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is a urethane, examines to be polyacrylic ester.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786651A (en) * | 2012-08-23 | 2012-11-21 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN106749940A (en) * | 2016-12-03 | 2017-05-31 | 范进 | A kind of preparation method of high-toughness polypropylene yogurt glue |
| CN109096446A (en) * | 2018-07-18 | 2018-12-28 | 江苏景宏新材料科技有限公司 | Modification acrylate and preparation method thereof, printing ink and application thereof |
| CN110483698A (en) * | 2019-08-26 | 2019-11-22 | 广东工业大学 | A kind of aqueous polyurethane multiple emulsion and preparation method thereof |
| CN119119919A (en) * | 2024-08-26 | 2024-12-13 | 皇冠新材料科技股份有限公司 | Heat-adhesive pressure-sensitive adhesive composition and pressure-sensitive adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
| CN101875711A (en) * | 2010-07-22 | 2010-11-03 | 武汉工程大学 | Preparation method of hydroxyl type waterborne polyurethane-acrylate resin hybrid body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
| CN101875711A (en) * | 2010-07-22 | 2010-11-03 | 武汉工程大学 | Preparation method of hydroxyl type waterborne polyurethane-acrylate resin hybrid body |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786651A (en) * | 2012-08-23 | 2012-11-21 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN102786651B (en) * | 2012-08-23 | 2013-12-11 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN106749940A (en) * | 2016-12-03 | 2017-05-31 | 范进 | A kind of preparation method of high-toughness polypropylene yogurt glue |
| CN109096446A (en) * | 2018-07-18 | 2018-12-28 | 江苏景宏新材料科技有限公司 | Modification acrylate and preparation method thereof, printing ink and application thereof |
| CN109096446B (en) * | 2018-07-18 | 2021-05-28 | 江苏景宏新材料科技有限公司 | Modified acrylate and preparation method thereof, printing ink and application thereof |
| CN110483698A (en) * | 2019-08-26 | 2019-11-22 | 广东工业大学 | A kind of aqueous polyurethane multiple emulsion and preparation method thereof |
| CN119119919A (en) * | 2024-08-26 | 2024-12-13 | 皇冠新材料科技股份有限公司 | Heat-adhesive pressure-sensitive adhesive composition and pressure-sensitive adhesive |
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