CN102276502B - Method for preparing ultraviolet cured polyurethane acrylate oligomer - Google Patents
Method for preparing ultraviolet cured polyurethane acrylate oligomer Download PDFInfo
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- CN102276502B CN102276502B CN201110116858.0A CN201110116858A CN102276502B CN 102276502 B CN102276502 B CN 102276502B CN 201110116858 A CN201110116858 A CN 201110116858A CN 102276502 B CN102276502 B CN 102276502B
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- vulcabond
- acrylate oligomer
- hydroxy ester
- crylic acid
- acid hydroxy
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 239000004814 polyurethane Substances 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- -1 hydroxy ester Chemical class 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 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 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 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 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 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 4
- 239000000203 mixture Substances 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 230000007794 irritation Effects 0.000 abstract 1
- 229920000052 poly(p-xylylene) Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 235000019633 pungent taste Nutrition 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 2
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical class C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical class CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a method for preparing ultraviolet cured poly urethane acrylate oligomer. The method comprises the following steps of: preparing for materials according to the mol ratio of diisocyanate to acrylic hydroxyl ester of 1:(2.1-2.2); adding the diisocyanate containing a polymerization inhibitor and an antioxygen into acrylic hydroxyl ester containing the polymerization inhibitor at 45-65 DEG C; adding a catalyst after reacting for 2 h; reacting at 75-85 DEG C; and obtaining the reaction product of the polyurethane acrylate oligomer when the NCO value of the system is less than 0.2%. The polyurethane acrylate oligomer is solid at normal temperature and can be cured in an ultraviolet manner. The polyurethane acrylate oligomer can be dissolved in acrylic monomer and also can be dissolved after being heated to 60 DEG C. The process disclosed by the invention is simple and feasible. The ultraviolet cured poly urethane acrylate oligomer is conveyed and stored conveniently. Liquid resin irritation resulted from the process is reduced. The ultraviolet cured poly urethane acrylate oligomer has a great anti-irritation performance and is a safety and green polymer curable material.
Description
Technical field
The invention belongs to ultraviolet light polymerization oligopolymer preparation field, particularly under a kind of normal temperature, be the synthetic preparation method of UV curable polymer of solid state.
Background technology
Ultraviolet-curing paint is the coating of a kind of environment-friendly and green of 20 middle of century exploitations, and in China, the time that is less than 20 years is produced in research and development.Due to its environmental protection, energy-conservation, be efficiently that a kind of green building that China and even the whole world are tried hard to recommend is decorated protecting materials.Jin Banian China is all with 25 ﹪ speed increase development.UV-light is because of environmental protection, efficiently extremely property is applied to a lot of fields gradually.The ultraviolet photocureable material that expansion is applied in woodenware, metal, electronic industry has far-reaching social effect.
The oligopolymer of ultraviolet light polymerization is commonly called as the skeleton composition that resin is ultraviolet light polymerization, and the fundamental property after ultraviolet photocureable material solidifies comprises that hardness, snappiness, sticking power, optical property etc. are mainly to be determined by oligopolymer.Can there be several classes such as unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate for the conventional oligopolymer of ultraviolet light polymerization at present, because the performance of synthesis of polyurethane acrylate can be by the selection of group is carried out to modification, so most widely used on ultraviolet photocureable material of urethane acrylate at present.
Although the use finished product after ultraviolet light polymerization solidifies is very environmental protection, but before solidifying owing to being all a little low-molecular-weight acrylate, polarity is large, no matter be resin or monomer, skin is had to corrosion pungency, be not easy to produce and transportation, if therefore the oligopolymer of energy synthesis of solid relatively has superiority, be convenient to transportation and reduce pungency, can play a positive role to the security of industry.
Summary of the invention
For under existing ultraviolet light polymerization oligopolymer normal temperature being liquid state, there is pungency and be not partial to the shortcomings such as transportation, the invention provides a kind of preparation method of UV-cured polyurethane acrylate oligopolymer, the ultraviolet curing urethane oligopolymer of preparation is solid-state at normal temperatures, and pungency is little, be easy to transportation.
Technical scheme of the present invention is: a kind of preparation method of UV-cured polyurethane acrylate oligopolymer, the ratio that is 1:2.1-2.2 according to the mol ratio of vulcabond and crylic acid hydroxy ester is got the raw materials ready, vulcabond containing stopper and oxidation inhibitor is added in the crylic acid hydroxy ester containing stopper at 45-65 ℃, react and add catalyzer after 2 hours, 75-85 ℃ of reaction, when measurement system nco value is less than 0.2%, obtain reaction product urethane acrylate oligomer.
Described vulcabond is any one in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate.
Described toluene diisocyanate is toluene 2,4-vulcabond or toluene 2, one or both in 6-vulcabond arbitrarily than mixture.
Described crylic acid hydroxy ester is any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410.
Described stopper is MEHQ, and consumption is 0.5% of crylic acid hydroxy ester total mass.
Described catalyzer is that mass percent is the N-BUTYL ACETATE solution of 10% dibutyl tin laurate, and catalyst levels is the 0.02-0.05% of crylic acid hydroxy ester and vulcabond total mass.
Described oxidation inhibitor is 264 oxidation inhibitor (2,6 di tert butyl 4 methyl phenols), and consumption is the 0.5-1% of crylic acid hydroxy ester and vulcabond total mass.
Described UV-cured polyurethane acrylate oligopolymer can be dissolved in acrylate monomer and can ultraviolet light polymerization in the presence of light trigger.
beneficial effect:
UV-cured polyurethane acrylate oligopolymer prepared by the present invention is solid-state being less than at 35 ℃, is convenient to transportation, and skin irritation is lower than common liquid ultraviolet light polymerization oligopolymer.In temperature, be in a liquid state during higher than 60 ℃, also can be dissolved in the liquid monomer of acrylate the convenient, flexible ultraviolet photocureable material that is used in.
Embodiment
Preparation used in the present invention, so long as qualified industrial goods are not limited to producer, is all commercially available conventional products.
A kind of preparation method of UV-cured polyurethane acrylate oligopolymer, the mol ratio of tolylene diisocyanate and crylic acid hydroxy ester is that 1:2.1-2.2 feeds intake, vulcabond containing stopper and oxidation inhibitor is added in the crylic acid hydroxy ester containing stopper at 45-65 ℃, reaction at 75-85 ℃, the nco value of measurement system is less than 0.2%, obtains reaction product urethane acrylate oligomer.
Described vulcabond refers to any one in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI).Tolylene diisocyanate can be toluene 2,4-vulcabond or toluene 2, any one in 6-vulcabond or arbitrarily than mixture.
Described crylic acid hydroxy ester mainly refers to the crylic acid hydroxy ester of the following alcohol of four carbon, as any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410.In reaction, can only select a kind of hydroxy ester, if the inside be mixed with other hydroxy ester quality necessarily can not surpass 5-10%.
Described stopper refers to that MEHQ is as stopper.Consumption is 0.5% of crylic acid hydroxy ester total mass,
In described preparation method, the terminal of finally controlling is the content with isocyanic ester (NCO), is less than 0.2% for well.
Described catalyzer is dibutyl tin laurate, and consumption is the 0.02-0.05% of crylic acid hydroxy ester and vulcabond total mass.During use, the N-BUTYL ACETATE solution that is mixed with mass percent and is 10% dibutyl tin laurate is used.
264 type oxidation inhibitor for described oxidation inhibitor, consumption is the 0.5-1% of crylic acid hydroxy ester and vulcabond total mass.
The oligopolymer that described preparation method is made, can ultraviolet light polymerization, and at normal temperature, referring to be less than at 35 ℃ is solid resin.But can be dissolved in acrylate monomer, be heated to 60 ° of C and also can finely be dissolved into the solid resin of liquid.
embodiment 1
By 174 grams of TDI and the there-necked flask that adds 500 milliliters, at 45-65 ℃, with dropping funnel, add containing 286 grams of the hydroxyethyl methylacrylates of 1.43 grams of MEHQ and 2 gram of 246 oxidation inhibitor, add the reaction of 75-85 ℃ of rear control temperature and add 0.92 gram of catalyzer after 2 hours, when nco value drops to discharging while being less than 0.2%..
Synthetic product is in a liquid state at 60 ℃, water-white transparence, records NCO<0.077%, and viscosity is 3800mpa.s/60 ℃, starts to crystallize to that 35 ℃ solidify completely and are solid while being cooled to 40 ℃.
embodiment 2
By 174 grams of TDI and the there-necked flask that adds 500 milliliters, at 45-65 ℃, by addition funnel, add containing 250 grams of the Hydroxyethyl acrylates of 1.25 grams of MEHQ and 2 gram of 246 oxidation inhibitor, add the reaction of 75-85 ℃ of rear control temperature and add 0.85 gram of catalyzer after 2 hours, when nco value drops to discharging while being less than 0.2%..
Synthetic product becomes water-white transparent at 60 ℃, records NCO<0.11%, and viscosity is 3500mpa.s/60 ℃, and cooling 38 ℃ start to crystallize into solid.
embodiment 3
By 174 grams of TDI and the there-necked flask that adds 500 milliliters, at 45-65 ℃, by addition funnel, add containing 280 grams of the hydroxyethyl methylacrylates of 1.43 grams of MEHQ and 2 gram of 246 oxidation inhibitor, add the reaction of 75-85 ℃ of rear control temperature and add 0.90 gram of catalyzer after 2 hours, when nco value drops to discharging while being less than 0.2%..
Synthetic product becomes water-white transparent at 60 ℃, records NCO<0.17%, and viscosity is 3750mpa.s/60 ℃, and cooling 40 ℃ start to crystallize into solid.
embodiment 4
By 174 grams of TDI and the there-necked flask that adds 500 milliliters, at 45-65 ℃, by addition funnel, add containing 280 grams of the Propylene glycol monoacrylates of 1.43 grams of MEHQ and 2 gram of 246 oxidation inhibitor, add the reaction of 75-85 ℃ of rear control temperature and add 0.90 gram of catalyzer after 2 hours, when nco value drops to discharging while being less than 0.2%..
Synthetic product becomes water-white transparent at 60 ℃, records NCO<0.17%, and viscosity is 4050mpa.s/60 ℃, and cooling 40 ℃ start to crystallize into solid.
embodiment 5
By 174 grams of IPDI and the there-necked flask that adds 500 milliliters, at 45-65 ℃, by addition funnel, add containing 200 grams of the Hydroxyethyl acrylates of 1.2 grams of MEHQ and 1.6 gram of 246 oxidation inhibitor, add the reaction of 75-85 ℃ of rear control temperature and add 1.8 grams of catalyzer after 2 hours, when nco value drops to discharging while being less than 0.2%..
Synthetic product becomes water-white transparent at 60 ℃, records NCO<0.05%, and viscosity is 2800mpa.s/60 ℃, and cooling 50 ℃ start to crystallize into solid.
embodiment 6
By 174 grams of IPDI and the there-necked flask that adds 500 milliliters, at 45-65 ℃, by addition funnel, add containing 220 grams of the Propylene glycol monoacrylates of 1.2 grams of MEHQ and 1.8 gram of 246 oxidation inhibitor, add the reaction of 75-85 ℃ of rear control temperature and add 1.9 grams of catalyzer after 2 hours, when nco value drops to discharging while being less than 0.2%..
Synthetic product becomes water-white transparent at 60 ℃, records NCO<0.03%, and viscosity is 3200mpa.s/60 ℃, and cooling 45 ℃ start to crystallize into solid.
embodiment 7
By 50 grams of fusings at 65 ℃ of the synthetic product of example 1, join 35 grams of HDDA(1,6 hexanediyl esters) and 20 grams of TPGDA(tripropylene glycol diacrylates), with high speed dispersor, under 1200r/min, disperse 20 20 minutes, then add under the low speed 5 grams of light trigger 1173(2-hydroxy-2-methyl-1-phenyl-1-acetone).Disperse 10 minutes.With knifing spreader on sheet glass, make 100um thick at 250mj/cm
2uV-light energy under solidify, cured film can reach hardness 2H.
embodiment 8
By 50 grams of fusings at 65 ℃ of the synthetic product of example 6, join 35 grams of HDDA(1,6 hexanediyl esters) and 20 grams of TPGDA(tripropylene glycol diacrylates), with high speed dispersor, under 1200r/min, disperse 20 20 minutes, then add under the low speed 5 grams of light trigger 1173(2-hydroxy-2-methyl-1-phenyl-1-acetone).Disperse 10 minutes.With knifing spreader on sheet glass, make 100um thick at 250mj/cm
2uV-light energy under solidify, cured film can reach hardness 1H.
Claims (2)
1. the preparation method of a UV-cured polyurethane acrylate oligopolymer; it is characterized in that: the ratio that is 1:2.1-2.2 according to the mol ratio of vulcabond and crylic acid hydroxy ester is got the raw materials ready; vulcabond containing stopper and oxidation inhibitor is added in the crylic acid hydroxy ester containing stopper at 45-65 ℃; react and add catalyzer after two hours; 75-85 ℃ of reaction; when measurement system nco value is less than 0.2%, obtain reaction product urethane acrylate oligomer; Described vulcabond is any one in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate; Described crylic acid hydroxy ester is any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate; Described stopper is MEHQ, and consumption is 0.5% of crylic acid hydroxy ester total mass; Described catalyzer is that mass percent is the N-BUTYL ACETATE solution of 10% dibutyl tin laurate, and catalyst levels is the 0.02-0.05% of crylic acid hydroxy ester and vulcabond total mass; Described oxidation inhibitor is 2,6 di tert butyl 4 methyl phenol, and consumption is the 0.5-1% of crylic acid hydroxy ester and vulcabond total mass.
2. the preparation method of the UV-cured polyurethane acrylate oligopolymer described in requirement according to claim 1, it is characterized in that: described tolylene diisocyanate is toluene 2,4-vulcabond or toluene 2, one or both in 6-vulcabond arbitrarily than mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110116858.0A CN102276502B (en) | 2011-05-06 | 2011-05-06 | Method for preparing ultraviolet cured polyurethane acrylate oligomer |
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| CN201110116858.0A CN102276502B (en) | 2011-05-06 | 2011-05-06 | Method for preparing ultraviolet cured polyurethane acrylate oligomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103224458A (en) * | 2013-04-16 | 2013-07-31 | 沈阳化工大学 | Preparation method of HMA-HDI-HMA diacrylate macromonomer |
| CN103694443B (en) * | 2013-12-12 | 2016-03-02 | 苏州博纳化学科技有限公司 | A kind of synthetic method of polynary cross-linking monomer |
| CN104311724B (en) * | 2014-10-11 | 2017-04-26 | 湖南中汉高分子材料科技有限公司 | Preparation method of volatile polyacrylate elastic resin |
| CN105199077B (en) * | 2015-10-23 | 2017-12-08 | 青岛展辰新材料有限公司 | A kind of high-ranking official it is wear-resisting can cold light source cured polyurethane acrylate preparation method |
| SE1730230A1 (en) | 2017-08-31 | 2019-02-19 | Perstorp Ab | Novel oligomer or polymer and composition comprising the same |
| CN107915829B (en) * | 2017-11-21 | 2020-09-25 | 瑞通高分子科技(浙江)有限公司 | Self-initiated ultraviolet curing oligomer and preparation method thereof |
| CN111909588A (en) * | 2020-08-18 | 2020-11-10 | 直尚化工(上海)有限公司 | Polymethyl methacrylate coating and application thereof |
| CN114940742B (en) * | 2022-07-12 | 2023-11-24 | 湖南艾硅特新材料有限公司 | Acrylic polyurethane and synthetic method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2905205A1 (en) * | 1979-02-12 | 1980-08-14 | Huels Chemische Werke Ag | METHOD FOR PRODUCING STORAGE-STABLE URETHANE ACRYLIC |
| US5294692A (en) * | 1993-06-30 | 1994-03-15 | National Starch And Chemical Investment Holding Corporation | Associative monomers and polymers |
| US6028212A (en) * | 1997-12-16 | 2000-02-22 | Morton International, Inc. | Solid vinyl ether terminated urethane curing agent |
| CN101157640B (en) * | 2007-09-20 | 2010-05-26 | 湖南大学 | Acrylic polyurethane having star-structure six functional groups and synthesizing method thereof |
| DE102009008569A1 (en) * | 2009-02-12 | 2010-08-19 | Bayer Materialscience Ag | Process for the preparation of particularly reactive and low-viscosity allophanates with actinically curable groups and their use for the production of particularly scratch-resistant coatings |
| CN101948409A (en) * | 2010-08-04 | 2011-01-19 | 辽宁恒星精细化工有限公司 | Hydroxyethyl methacrylate-modified isophorone diisocyanate and preparation method thereof |
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