CN101735415B - Method for preparing organosilicon/acrylate double modified aqueous polyurethane - Google Patents
Method for preparing organosilicon/acrylate double modified aqueous polyurethane Download PDFInfo
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- CN101735415B CN101735415B CN2009102565212A CN200910256521A CN101735415B CN 101735415 B CN101735415 B CN 101735415B CN 2009102565212 A CN2009102565212 A CN 2009102565212A CN 200910256521 A CN200910256521 A CN 200910256521A CN 101735415 B CN101735415 B CN 101735415B
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- organosilicon
- aqueous polyurethane
- modified aqueous
- acrylate
- polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- 238000002360 preparation method Methods 0.000 claims description 19
- -1 acrylic ester Chemical class 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 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 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 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 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 150000003673 urethanes Chemical class 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 239000004432 silane-modified polyurethane Substances 0.000 abstract 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000001143 conditioned effect Effects 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to a method for preparing organosilicon/acrylate double modified aqueous polyurethane, which comprises the following steps: carrying out a reaction on isocyanate, polyhydric alcohol and dimethylolpropionic acid to obtain polyurethane prepolymer I; dropwise adding dimethylolpropionic acid into the polyurethane prepolymer I, and dropwise adding hydroxyethyl methacrylate containing a polymerization inhibitor into the polyurethane prepolymer I, thereby obtaining polyurethane prepolymer II containing double bonds; dropwise adding organosilane into the polyurethane prepolymer II to obtain silane-modified polyurethane; adding triethylamine into the silane-modified polyurethane to carry out salification reaction, adding deionized water, and stirring to obtain organosilicon-modified aqueous polyurethane emulsion; and finally, adding methyl methacrylate and butyl acrylate into the organosilicon-modified aqueous polyurethane emulsion to carry out emulsion polymerization, thereby obtaining the organosilicon/acrylate double modified aqueous polyurethane. The method has the advantages of convenient operation and simple technique; and the prepared polyurethane chain segmentcontains silane and acrylate and has the advantages of favorable water resistance and mechanical properties.
Description
Technical field:
The present invention relates to a kind of preparation method of organosilicon/acrylate double modified aqueous polyurethane, belong to the preparing technical field of water-based and ammonia ester paint.
Background technology:
Aqueous polyurethane coating is meant that urethane is water-soluble or is scattered in the water and the coating that forms.Over past ten years, the pressure from public opinion of the environment of preserving our planet grows with each passing day, and people's environmental consciousness constantly strengthens, and some developed countries have formulated fire codes and solvent rules, and these factors have promoted the exploitation of water-base polyurethane material.Aqueous polyurethane is basic medium with water, have do not fire, smell is little, free from environmental pollution, energy-conservation, operation advantage such as easy to process, be subject to people's attention.
But aqueous polyurethane also exists the shortcoming of poor-performings such as water tolerance, solvent resistance, chemical-resistant and physical strength.Acrylic resin has physical strength height, ageing-resistant, characteristics such as resistance is yellow, water-tolerant.Organosilicon material is the high molecular synthetic material that contains element silicon in the molecular structure, main chain contains siloxane bond, and adopt the organo silane coupling agent of amine, amino and residual isocyano reaction, hydrolyzable siloxane groups generation hydrolytie polycondensation and make crosslinked, the chain extension of system makes it have good weathering resistance, ageing-resistant, hydrophobic nature etc.Polyurethane-acrylate-organo-siloxane ternary is combined the preparation water-borne coatings, and it combines the advantage of acrylate, urethane, three kinds of resin materials of organosilicon, and has met environmental protection requirement with water as dispersion medium.The three organically combines, and according to the requirement of different purposes, bring into play its synergistic advantage, can make soap or soap-free emulsion, as coating.
Summary of the invention:
The objective of the invention is to shortcoming, aim to provide a kind of preparation method of organosilicon/acrylate double modified aqueous polyurethane at present polyurethane coating existence.
In order to realize the foregoing invention purpose, the present invention operates according to following steps by the following technical solutions:
The first step, the preparation of base polyurethane prepolymer for use as: will be incorporated with in the reactor of agitator, thermometer and prolong through the polyvalent alcohol and the dimethylol propionic acid of processed, add polyisocyanates and proper catalyst dibutyl tin laurate, react 2-3h down at 70-80 ℃, and then adding dimethylol propionic acid, continue reaction 2-3h, obtain base polyurethane prepolymer for use as I; Again the hydroxyethyl methylacrylate that contains stopper is added drop-wise among the base polyurethane prepolymer for use as I and reacts, react 2-3h down, obtain double bond containing base polyurethane prepolymer for use as II at 60-70 ℃.The viscosity that adds proper amount of diluting acetone conditioned reaction system in the reaction process.
Second step, organic-silicon-modified Synthesis of Waterborne Polyurethane: double bond containing base polyurethane prepolymer for use as II is cooled to 60 ℃, slowly drip the organosilane that is dissolved with acetone then, the dropping time is controlled at 30min, dropwise the back at 60-70 ℃ of reaction 2-3h, obtain silane-modified urethane, add the viscosity of proper amount of diluting acetone conditioned reaction system in the reaction process; Reaction system is cooled to below 40 ℃, add triethylamine and be carried out to reactant salt, triethylamine and dimethylol propionic acid mol ratio are 1: 1, stir 30min, add deionized water again, behind vigorous stirring 0.5～1h, underpressure distillation goes out acetone and obtains organic-silicon-modified aqueous polyurethane, solid content 20～40%.
The 3rd step, the preparation of organosilicon/acrylate double modified aqueous polyurethane: in organic-silicon-modified aqueous polyurethane, add the deionized water (this is water) that is dissolved with emulsifier sodium lauryl sulfate and OP, water is incorporated with in the reactor of agitator, thermometer and prolong; The oil-soluble initiator Diisopropyl azodicarboxylate is dissolved in (this is oil phase) in the acrylic ester monomer, oil phase is added drop-wise to aqueous phase, stir 30min, after dripping, continue to stir 30min; Be rapidly heated under condition of nitrogen gas then about 80 ℃, the reaction latter temperature is raised to about 90 ℃, and reaction 5-6h obtains the two modify-water based polyurethanes of organosilicon/acrylate, solid content 20～40%.The quality of acrylics is 3: 1～1: 5 with solid masses ratio in the aqueous polyurethane.By regulating the two ratio and add-on, can obtain the different material of snappiness.
The described polyisocyanates of the first step of the present invention is preferably tolylene diisocyanate (being called for short TDI), isophorone diisocyanate (being called for short IPDI), hexamethylene diisocyanate (being called for short HDI), 4,4-diphenylmethanediisocyanate (being called for short MDI).
The described polyvalent alcohol of the first step of the present invention is preferably polyester polyol, polyoxypropyleneglycol, polyethers N210, and molecular weight is 800-4000.
NCO in the first step of the present invention operation in the polyisocyanates is 1.6: 1～2 with OH mol ratio in the dimethylol propionic acid that adds the polyvalent alcohol and the first time, add dimethylol propionic acid once more behind reaction 2～3h, dimethylol propionic acid dissolves in N-Methyl pyrrolidone and adds, its add-on ratio of twice is any, and the per-cent that total adding quality accounts for base polyurethane prepolymer for use as I quality is 3～5%; The per-cent that the add-on of hydroxyethyl methylacrylate accounts for base polyurethane prepolymer for use as I quality is 0～2%; To add stopper be Resorcinol in institute, its quality account for ten thousand of hydroxyethyl methacrylate ester quality/.
The present invention's described organosilane of second step is KH550 organo silane coupling agent or KH590 organo silane coupling agent, and the mass percent that the quality of organosilane accounts for double bond containing base polyurethane prepolymer for use as II is 1～7%.Organosilane drips after being dissolved in acetone, and rate of addition must be slow, prevents to react too fast, causes reaction system viscosity to increase fast, influences reaction effect.
The thinner acetone that adjustment system viscosity of the present invention adds will be through super-dry, processed.
In the 3rd step letex polymerization of the present invention, the consumption of emulsifier sodium lauryl sulfate and OP is respectively institute and adds 3%, 1% of acrylic ester monomer quality, and the two compound use is than single the effective of sodium lauryl sulphate of using; Added esters of acrylic acid is methyl methacrylate and butyl acrylate, the two mass ratio 1: 4～4: 1, and the two total quality is 3: 1～1: 5 with solid masses ratio in the aqueous polyurethane.Initiator adopts oil-soluble Diisopropyl azodicarboxylate, quality for add 0.2～0.8% of acrylic ester monomer quality, add-on how much influence speed of reaction.But be not The more the better, react too fast, obtain emulsion particle diameter and become big, influence its stability.Heat up under nitrogen protection, heat-up rate will reach about 80 ℃ fast.In same thermotonus, the emulsion particle diameter that obtains like this distributes more even as far as possible.The emulsion polymerization later stage is improved temperature, and transformation efficiency is improved.
Compared with prior art, the present invention has following advantage:
(1) the amine organosilane that adopts of the present invention can react with isocyano, also can be crosslinked, and make the water tolerance of water-base polyurethane material of gained improve greatly, lower surface energy of polyurethane material and good hand feeling are given in organosilyl existence simultaneously.
(2) the present invention is on organic-silicon-modified basis, again with acrylate modified, improved tensile strength, wear resistance, weathering resistance of material etc.It combines the advantage of acrylate, urethane, three kinds of resin materials of organosilicon.
(3) modified waterborne polyurethane can be mixed with the water arbitrary proportion, and it is transparent to mix back solution, emulsion median size 80nm, and stability of emulsion is fine, and shelf stable for periods reached more than half a year.
(4) the inventive method is easy to operate, technology is simple, be easy to promotion and application.
Embodiment:
Below by specific embodiment the inventive method is described further.
Embodiment 1:
The first step, preparation base polyurethane prepolymer for use as technology: with the dimethylol propionic acid of the polyester polyol (M=1000) of 0.05mol and 0.02mol at 120 ℃ of decompressions 30min that draws water, cool to the tolylene diisocyanate and the appropriate amount of catalysts dibutyl tin laurate that add 0.112mol after 80 ℃, reaction 2.5h, add the dimethylol propionic acid 0.015mol that is dissolved in the N-Methyl pyrrolidone once more, continue reaction 2.5h, obtain base polyurethane prepolymer for use as I; The hydroxyethyl methylacrylate 0.01mol that will contain hydroquinone of polymerization retarder is added drop-wise among the base polyurethane prepolymer for use as I and reacts, and keeps 60～70 ℃ of reactions of temperature 2h, obtains double bond containing base polyurethane prepolymer for use as II.Add through the thinner acetone of processed in the whole process and regulate viscosity.The quality of hydroquinone of polymerization retarder account for ten thousand of hydroxyethyl methacrylate ester quality/.
Second step, the technology for preparing organic-silicon-modified aqueous polyurethane: double bond containing base polyurethane prepolymer for use as II is cooled to 60 ℃, the KH550 organo silane coupling agent of 0.025mol is dissolved in slowly is added drop-wise in the acetone among the base polyurethane prepolymer for use as II, the dropping time is controlled at 30min.Temperature keeps 60-70 ℃ of reaction 2h.The viscosity that adds proper amount of diluting acetone conditioned reaction system in the reaction process.Be cooled to below 40 ℃, the triethylamine that adds 0.035mol is carried out to reactant salt, adds deionized water 400g high-speed stirring 30min behind the stirring 30min, and last underpressure distillation goes out solvent acetone, obtains organic-silicon-modified aqueous polyurethane.
In the 3rd step, the OP emulsifiers dissolve that prepare sodium lauryl sulphate of organosilicon/acrylate double modified aqueous polyurethane: 3g and 1g joins (as water) in the organic-silicon-modified aqueous polyurethane after dissolving is complete in the deionized water of 150g; The initiator Diisopropyl azodicarboxylate of 0.3g is dissolved in the Butyl Acrylate Monomer of the methyl methacrylate of 60g and 40g (this is oil phase), oil phase is added drop-wise to aqueous phase, stir simultaneously, drip time 30min, after dripping, continue to stir 30min.Be rapidly heated under condition of nitrogen gas 80 ℃ then, the reaction latter temperature is raised to 90 ℃, and reaction 6h obtains organosilicon/acrylate double modified aqueous polyurethane.
Embodiment 2:
The first step, preparation base polyurethane prepolymer for use as technology: with the dimethylol propionic acid of the polyoxypropyleneglycol (M=2000) of 0.05mol and 0.01mol at 120 ℃ of decompressions 30min that draws water, cool to the tolylene diisocyanate and the appropriate amount of catalysts dibutyl tin laurate that add 0.12mol after 80 ℃, reaction 2.5h, add the dimethylol propionic acid 0.024mol that is dissolved in the N-Methyl pyrrolidone once more, continue reaction 2.5h, obtain base polyurethane prepolymer for use as I; The hydroxyethyl methylacrylate 0.005mol that will contain hydroquinone of polymerization retarder is added drop-wise among the base polyurethane prepolymer for use as I and reacts, and keeps 60～70 ℃ of reactions of temperature 2h, obtains double bond containing base polyurethane prepolymer for use as II.Add through the thinner acetone of processed in the whole process and regulate viscosity.The quality of hydroquinone of polymerization retarder account for ten thousand of hydroxyethyl methacrylate ester quality/.
Second step, the technology for preparing organic-silicon-modified aqueous polyurethane: double bond containing base polyurethane prepolymer for use as II is cooled to 60 ℃, the KH550 organo silane coupling agent of 0.035mol is dissolved in slowly is added drop-wise in the acetone among the base polyurethane prepolymer for use as II, the dropping time is controlled at 30min.Temperature keeps 60-70 ℃ of reaction 3h.The viscosity that adds proper amount of diluting acetone conditioned reaction system in the reaction process.Be cooled to below 40 ℃, the triethylamine that adds 0.035mol is carried out to reactant salt, adds deionized water 400g high-speed stirring 30min behind the stirring 30min, and last underpressure distillation goes out solvent acetone, obtains organic-silicon-modified aqueous polyurethane.
In the 3rd step, the OP emulsifiers dissolve that prepare sodium lauryl sulphate of organosilicon/acrylate double modified aqueous polyurethane: 1.8g and 0.6g joins (as water) in the organic-silicon-modified aqueous polyurethane after dissolving is complete in the deionized water of 100g; The initiator Diisopropyl azodicarboxylate of 0.3g is dissolved in the Butyl Acrylate Monomer of the methyl methacrylate of 30g and 30g (this is oil phase), oil phase is added drop-wise to aqueous phase, stir simultaneously, drip time 30min, after dripping, continue to stir 30min.Be rapidly heated under condition of nitrogen gas 80 ℃ then, the reaction latter temperature is raised to 90 ℃, and reaction 6h obtains organosilicon/acrylate double modified aqueous polyurethane.
Embodiment 3:
The first step, preparation base polyurethane prepolymer for use as technology: with the dimethylol propionic acid of the polyester diol (M=2000) of 0.05mol and 0.015mol at 120 ℃ of decompressions 30min that draws water, cool to the tolylene diisocyanate and the appropriate amount of catalysts dibutyl tin laurate that add 0.117mol after 80 ℃, reaction 2.5h, add the dimethylol propionic acid 0.02mol that is dissolved in the N-Methyl pyrrolidone once more, continue reaction 2.5h, obtain base polyurethane prepolymer for use as I; The hydroxyethyl methylacrylate 0.008mol that will contain hydroquinone of polymerization retarder is added drop-wise among the base polyurethane prepolymer for use as I and reacts, and keeps 60～70 ℃ of reactions of temperature 2.5h, obtains double bond containing base polyurethane prepolymer for use as II.Add through the thinner acetone of processed in the whole process and regulate viscosity.The quality of hydroquinone of polymerization retarder account for ten thousand of hydroxyethyl methacrylate ester quality/.
Second step, the technology for preparing organic-silicon-modified aqueous polyurethane: double bond containing base polyurethane prepolymer for use as II is cooled to 60 ℃, the KH550 organo silane coupling agent of 0.03mol is dissolved in slowly is added drop-wise in the acetone among the base polyurethane prepolymer for use as II, the dropping time is controlled at 30min.Temperature keeps 60-70 ℃ of reaction 3h.The viscosity that adds proper amount of diluting acetone conditioned reaction system in the reaction process.Be cooled to below 40 ℃, the triethylamine that adds 0.035mol is carried out to reactant salt, adds deionized water 400g high-speed stirring 30min behind the stirring 30min, and last underpressure distillation goes out solvent acetone, obtains organic-silicon-modified aqueous polyurethane.
In the 3rd step, the OP emulsifiers dissolve that prepare sodium lauryl sulphate of organosilicon/acrylate double modified aqueous polyurethane: 1.8g and 0.6g joins (as water) in the organic-silicon-modified aqueous polyurethane after dissolving is complete in the deionized water of 100g; The initiator Diisopropyl azodicarboxylate of 0.24g is dissolved in the Butyl Acrylate Monomer of the methyl methacrylate of 35g and 25g (this is oil phase), oil phase is added drop-wise to aqueous phase, stir simultaneously, drip time 30min, after dripping, continue to stir 30min.Be rapidly heated under condition of nitrogen gas 80 ℃ then, the reaction latter temperature is raised to 90 ℃, and reaction 5h obtains organosilicon/acrylate double modified aqueous polyurethane.
The technical indicator of the organosilicon/acrylate double modified aqueous polyurethane of the inventive method preparation:
| Solids content | 20～40％ |
| Apparent viscosity mPas | 0.01～0.03 |
| Saturated water absorption | ＜15％ |
| Breaking tenacity (MPa) | ＞5 |
| Elongation at break (%) | ＞500 |
| Emulsion particle diameter (nm) | 50-80 |
Claims (8)
1. the preparation method of an organosilicon/acrylate double modified aqueous polyurethane, it is characterized in that: operate according to following steps: the first step, preparation base polyurethane prepolymer for use as: will be incorporated with in the reactor of agitator, thermometer and prolong through the polyvalent alcohol and the dimethylol propionic acid of processed, add polyisocyanates and catalyzer dibutyl tin laurate, react 2-3h down at 70-80 ℃, and then the adding dimethylol propionic acid, continue reaction 2-3h, obtain base polyurethane prepolymer for use as I; Again the hydroxyethyl methylacrylate that contains stopper is added drop-wise among the base polyurethane prepolymer for use as I and reacts, react 2-3h down, obtain double bond containing base polyurethane prepolymer for use as II at 60-70 ℃; Second step, organic-silicon-modified Synthesis of Waterborne Polyurethane: double bond containing base polyurethane prepolymer for use as II is cooled to 60 ℃, slowly drips the organosilane that is dissolved with acetone then, drip time 30min, dropwise the back at 60-70 ℃ of reaction 2-3h, obtain silane-modified urethane; Reaction system is cooled to below 40 ℃, add triethylamine and be carried out to reactant salt, triethylamine and dimethylol propionic acid mol ratio are 1: 1, stir 30min, add deionized water again, behind vigorous stirring 0.5～1h, underpressure distillation goes out acetone and obtains organic-silicon-modified aqueous polyurethane, solid content 20～40%; In the 3rd step, in organic-silicon-modified aqueous polyurethane, the deionized water that adding is dissolved with emulsifier sodium lauryl sulfate and OP is incorporated with water in the reactor of agitator, thermometer and prolong as water; The oil-soluble initiator Diisopropyl azodicarboxylate is dissolved in the acrylic ester monomer as oil phase, oil phase is added drop-wise to aqueous phase, stir 30min, after dripping, continue to stir 30min; Be rapidly heated under condition of nitrogen gas then to 80 ℃, the reaction latter temperature rises to 90 ℃, reaction 5-6h, obtain the two modify-water based polyurethanes of organosilicon/acrylate, solid content 20～40%, wherein, acrylic ester monomer is 3: 1～1: 5 with solid masses ratio in the aqueous polyurethane.
2. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1, it is characterized in that: the described polyisocyanates of the first step is tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4, the 4-diphenylmethanediisocyanate.
3. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1, it is characterized in that: the described polyvalent alcohol of the first step is polyester polyol, polyoxypropyleneglycol, polyethers N210, and molecular weight is 800-4000.
4. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1, it is characterized in that: the OH mol ratio in the dimethylol propionic acid that NCO in the first step in the polyisocyanates and polyvalent alcohol and the first time add is 1.6: 1～2, add dimethylol propionic acid once more behind reaction 2～3h, dimethylol propionic acid dissolves in N-Methyl pyrrolidone and adds, the allocation proportion of its add-on of twice is any, and the per-cent that total adding quality accounts for base polyurethane prepolymer for use as I quality is 3～5%.
5. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1, it is characterized in that: second step, described organosilane was KH550 organo silane coupling agent or KH590 organo silane coupling agent, and the mass percent that the quality of organosilane accounts for double bond containing base polyurethane prepolymer for use as II is 1～7%.
6. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1 is characterized in that: in the 3rd step the consumption of emulsifier sodium lauryl sulfate and OP be respectively add 3%, 1% of acrylic ester monomer quality.
7. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1, it is characterized in that: the acrylic ester monomer described in the 3rd step is methyl methacrylate and butyl acrylate, the two mass ratio 1: 4～4: 1, the two total quality is 3: 1～1: 5 with solid masses ratio in the aqueous polyurethane.
8. the preparation method of a kind of organosilicon/acrylate double modified aqueous polyurethane according to claim 1 is characterized in that: the quality of described oil-soluble initiator Diisopropyl azodicarboxylate of the 3rd step is add 0.2～0.8% of acrylic ester monomer quality.
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