CN104119543B - A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate - Google Patents
A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate Download PDFInfo
- Publication number
- CN104119543B CN104119543B CN201410337993.1A CN201410337993A CN104119543B CN 104119543 B CN104119543 B CN 104119543B CN 201410337993 A CN201410337993 A CN 201410337993A CN 104119543 B CN104119543 B CN 104119543B
- Authority
- CN
- China
- Prior art keywords
- preparation
- ester compound
- catalyst
- reaction
- isocyanate ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 title claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 239000012948 isocyanate Substances 0.000 claims abstract description 33
- 239000004970 Chain extender Substances 0.000 claims abstract description 29
- -1 isocyanate ester compound Chemical class 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229920000151 polyglycol Polymers 0.000 claims abstract description 16
- 239000010695 polyglycol Substances 0.000 claims abstract description 16
- 150000001298 alcohols Chemical class 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 238000013019 agitation Methods 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- 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 15
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 230000008034 disappearance Effects 0.000 claims description 11
- 150000003335 secondary amines Chemical class 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000012952 cationic photoinitiator Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 238000003860 storage Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000010792 warming Methods 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000002245 particle Substances 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 241000047703 Nonion Species 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
Abstract
A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate, concrete preparation process is as follows: (1) is at 40 50 DEG C, to react 13 hours under the effect of poly glycol monomethyl ether and isocyanate ester compound catalyst, then add with isocyanate ester compound with the polyhydroxy base class secondary amine of mole at 50 60 DEG C；(2) by dihydroxylic alcohols and isocyanate ester compound with catalyst 40 50 DEG C of reactions, add the chain extender that step (1) obtains, after 50 70 DEG C of reactions 13 hours, add and dihydroxylic alcohols with the photosensitive monomer acrylate of mole 60 70 DEG C of reactions；(3) step (2) is obtained prepolymer and adds deionized water under stirring and light trigger carries out emulsifying 12 hours.This method building-up process is simple, and condition is controlled, and the emulsion obtained has good storage stability, and solid content is higher, can be used for functional paint, and fabric finish etc..
Description
Technical field
The present invention relates to technical field of polymer materials, especially relate to two kinds of methods preparing ultraviolet light solidfication water polyurethane acrylate.
Background technology
The advantage that ultraviolet light solidfication water polyurethane combines photocuring technology and water paint, have efficiently, energy-saving and environmental protection, economy, the advantage of wide adaptability, it is applied in terms of the coating of woodenware, metal and plastic basis material, thus obtains the extensive concern of domestic and international researcher.What research in recent years was more is the aqueous polyurethane of anionic and cationic, because it contains ionic group, good hydrophilic property, there is easily emulsification, the advantage that emulsion storage stability is good, but the ultraviolet light solidfication water polyurethane of ionic is the most sensitive to electrolyte etc., is therefore subject to certain restrictions in the occasion being applied to electrolyte.Non-ion aqueous polyurethane does not have an ionic group, thus to acid, alkali, salt stability all preferable, and unparalleled electron structure, the most insensitive to electrolyte.
The method generally preparing non-ion aqueous polyurethane has two kinds, and one is that high speed shear obtains emulsion in the presence of external emulsifying agent, and another is hydrophilic radical or the hydrophilic segment of nonionic to be introduced in molecular structure.Using the emulsion that external emulsifying agent obtains, its technical process is difficult to control, and the polyaminoester emulsion storage stability obtained is poor, thus the method that the hydrophilic segment without ionic group is incorporated in polymer architecture generally used now so that it is there is hydrophilic interaction.
The many reports of patent is the preparation method about ionic photocuring waterborne polyurethane resin the most both at home and abroad.As the patent of number of patent application 200610038981.4 used dihydromethyl propionic acid introduce carboxyl, and introduce double bond, there is after neutralization hydrophily, obtain anionic photocuring aqueous polyurethane coating.This kind of method mainly increases the content of double bond by adding reactive diluent, in the patent of number of patent application 200810045778.9, point out that the patent of application number 200610038981.4 uses reactive diluent to increase the way of double bond content, cause adhesive force poor, and workmen's health is caused damage by the excitant of reactive diluent.
The patent of number of patent application 201110178207.6 use in-situ method prepare photocuring Waterborne Polyurethane Prepolymer, butyl acrylate (BA) and tripropylene glycol double methacrylate (TPGDA) is selected to regulate soft or hard section ratio as reactive diluent, the emulsion prepared is homogeneous, stable, has preferable mechanical property.But light-cured polyurethane double bond content prepared by the method is not the highest, causes hardening time longer, and gel content is the highest.
United States Patent (USP) US3920598 utilizes zerewitinoff
Method by organic compound and the side chain with active hydrogen atom with repetitive (CH2CH2O) di-isocyanate reaction, obtains the non-ionic water polyurethane that can be dispersed in water.Polyethylene glycol is introduced in molecular structure, play the mainly methylol groups of hydrophilic interaction, have document report ethoxy repeating units to be positioned at side chain better than the hydrophily being positioned at main chain.With trimethylolpropane polyethoxy ether as hydrophilic chain extender in patent CN101638472A, hydrophilic radical polyethoxy is incorporated on side-chain structure, prepares the non-ion aqueous polyurethane emulsion with side-chain structure.Patent CN102432992A is pointed out, through repeatedly testing, the shelf-life of the non-ion aqueous polyurethane that use trimethylolpropane polyethoxy ether obtains is the shortest, and process of depositing easily is degraded rotten.
Summary of the invention
The problems referred to above existed for prior art, the applicant provides the preparation method of two kinds of nonionic ultraviolet light solidfication water polyurethane acrylate emulsions.This method building-up process is simple, and condition is controlled, and the emulsion obtained has good storage stability, and solid content is higher, can be used for functional paint, and fabric finish etc..
Technical scheme is as follows:
The preparation method of the first nonionic ultraviolet light solidfication water polyurethane acrylate, concrete preparation process is as follows:
(1) at 40-50 DEG C, poly glycol monomethyl ether and isocyanate ester compound are reacted 1-3 hour under the effect of catalyst with the ratio of mol ratio 1:1, wherein catalyst is the 0.02-0.03% of poly glycol monomethyl ether and isocyanate ester compound gross mass, then add with isocyanate ester compound with the polyhydroxy base class secondary amine of mole at 50-60 DEG C, continue reaction to the infrared transform spectrometer of Fourier and record the disappearance of NCO characteristic absorption peak, stop reaction, i.e. obtain the side chain chain extender with hydrophilic long-chain polymer；
(2) by dihydroxylic alcohols and isocyanate ester compound with the ratio of mol ratio 1:2 with catalyst 40-50 DEG C of reaction, wherein catalyst is the 0.02-0.03% of dihydroxylic alcohols and isocyanate ester compound gross mass, after measuring, by toluene-di-n-butylamine back titration method, the 2.6-2.8% that NCO group content reaches the most all addition reactant gross masses, add the chain extender that step (1) obtains, after 50-70 DEG C of reaction 1-3 hour, add and stop reaction with the photosensitive monomer acrylate of mole in 60-70 DEG C of reaction to the characteristic absorption peak disappearance recording NCO with FTIS with dihydroxylic alcohols, obtain nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer；
(3) step (2) is obtained prepolymer and under the mechanical agitation that temperature is 30 DEG C, adds deionized water and light trigger carries out emulsification 1-2 hour, obtain the emulsion that solid content is 10-40%.One or more in polyester diol and polyether Glycols of described dihydroxylic alcohols.
The preparation method of the second nonionic ultraviolet light solidfication water polyurethane acrylate emulsion, concrete preparation process is as follows:
(1) at 40-50 DEG C, poly glycol monomethyl ether and isocyanate ester compound are reacted 1-3 hour under the effect of catalyst with the ratio of mol ratio 1:1, wherein catalyst is the 0.01-0.05% of poly glycol monomethyl ether and isocyanate ester compound gross mass, then add with isocyanate ester compound with the polyhydroxy base class secondary amine of mole at 50-60 DEG C, continue reaction to the infrared transform spectrometer of Fourier and record the disappearance of NCO characteristic absorption peak, stop reaction, i.e. obtain the side chain chain extender with hydrophilic long-chain polymer；
(2) by PCDL and isocyanate ester compound with the ratio of mol ratio 1:2 with catalyst 40-50 DEG C of reaction, wherein catalyst is the 0.01-0.05% of PCDL and isocyanate ester compound gross mass, after measuring, by toluene-di-n-butylamine back titration method, the 2.6%-2.8% that NCO group mass content reaches the most all addition reactant gross masses, add the chain extender that step (1) obtains, after 50-70 DEG C of reaction 1-3 hour, add and stop reaction with the photosensitive monomer acrylate of mole in 60-70 DEG C of reaction to the characteristic absorption peak disappearance recording NCO with FTIS with PCDL, obtain nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer；
(3) step (2) is obtained prepolymer and under the mechanical agitation that temperature is 30 DEG C, adds deionized water and light trigger carries out emulsification 1-2 hour, obtain the emulsion that solid content is 10-40%.Described PCDL is selected from one or more in Merlon i.e. PCD, and T5650J, T5651, T5652 series PCDL of being produced of Asahi Kasei Corporation.
The molecular weight of described poly glycol monomethyl ether is 500-2000；
One or more in IPDI, toluene di-isocyanate(TDI), MDI, hexamethylene diisocyanate, meta-xylene diisocyanate or 4,4 '-dicyclohexyl methyl hydride diisocyanate of described isocyanate ester compound；
One or more in the secondary amine with two and two or more hydroxy functional group of described polyhydroxy base class secondary amine, preferably one or more in diethanol amine, diisopropanolamine (DIPA), methyl diethanolamine；
One or more in hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate of described photosensitive monomer acrylate；
Step (1) and one or more in tertiary amine catalyst, organic tin catalyst of (2) described catalyst；
Described light trigger includes radical photoinitiator, cationic photoinitiator, alpha-alcohol ketone photoinitiator or α-aminoketone photoinitiator, consumption is the 1-5% of step (2) gained prepolymer gross mass, concrete, light trigger includes one or more in 1173,184,2959,907,369；
Wherein, reactant gross mass in the 2.6-2.8% of all addition reactant gross masses " NCO group content reach " in the step (2) of two kinds of methods, refer to the dihydroxylic alcohols in the poly glycol monomethyl ether in step (1), isocyanate ester compound, catalyst, polyhydroxy base class secondary amine, and step (2), isocyanate ester compound, the gross mass of catalyst.
The present invention uses three-step reaction, is accessed on urethane acrylate side chain by hydrophilic long-chain polymer, and then obtains novel nonionic ultraviolet light solidfication water polyurethane acrylate emulsion.Detailed process is: first passes through poly glycol monomethyl ether and reacts with isocyanates and polyhydroxy secondary amine, prepares the side chain glycol chain extender with hydrophilic long-chain；The intermediate obtaining two ends with unreacted isocyanate group is reacted subsequently with dihydroxylic alcohols and isocyanates；Last chain extender and the photosensitive monomer acrylate that the addition first step obtains in above-mentioned intermediate continues reaction, finally give nonionic ultraviolet light solidfication water polyurethane acrylate performed polymer, by emulsified in mechanical agitation according to a certain ratio to this performed polymer and deionized water, prepare nonionic ultraviolet light solidfication water polyurethane acrylate emulsion.
Specific to detailed raw material and step, the preparation thinking of the present invention is such that first passing through poly glycol monomethyl ether and prepares the side chain hydrophilic chain extender with polyethoxy group with IPDI and diethanol amine reaction, by two-step method reaction, the above-mentioned chain extender prepared is incorporated in urethane acrylate segmented structure, prepare nonionic UV-cured polyurethane acrylate prepolymer, and then obtain photocuring aqueous polyurethane acrylate emulsion.
Useful the having the technical effect that of the present invention
The nonionic ultraviolet light solidfication water polyurethane acrylate that the present invention prepares, it is not necessary to additional emulsifying agent can be dispersed in water；By preparing the side chain method with hydrophilic long-chain polymer chain extender, the emulsion storage stability prepared is preferable；The advantage of photocuring technology being combined with non-ionic water polyurethane acid and alkali-resistance, salt tolerant, the performance of electrolyte-resistant, expand the range of application of non-ionic water polyurethane, the coating obtained has the excellent properties such as high, water-fast, the acid and alkali-resistance of intensity；The final products emulsion particle diameter obtained, within 50-200nm, has good storage stability, and solid content is high, and curing rate is fast, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is embodiment 1 ~ 3 nonionic ultraviolet light solidfication water polyurethane acrylate infrared spectrum；
Fig. 2 is embodiment 1 ~ 3 nonionic ultraviolet light solidfication water polyurethane acrylate emulsion particle diameter distribution map；
Fig. 3 is embodiment 5 nonionic ultraviolet light solidfication water polyurethane acrylate infrared spectrum；
Fig. 4 is embodiment 5 nonionic ultraviolet light solidfication water polyurethane acrylate emulsion particle diameter distribution map.
Detailed description of the invention
Embodiment 1
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic long-chain polymer
Take 11.12 grams of (0.05mol) IPDIs and add in there-necked flask, and take 50 grams of poly glycol monomethyl ether (molecular weight: 1000,0.05mol), add the catalyst dibutyltin dilaurylate of 0.018 gram, dropping is started at 45 DEG C, react 2 hours, until recording NCO group content by toluene-di-n-butylamine method to reach theoretical value 3.44%, add diethanol amine 5.26 grams (0.05mol), it is warming up to 50 DEG C, continue reaction 2 hours, stop to recording the disappearance of NCO characteristic absorption peak with the infrared transform spectrometer of Fourier；
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
It is 1000 by number-average molecular weight, hydroxyl value is the PTMG dihydroxylic alcohols (PTMG) 100 grams (0.1mol) of 110mgKOH/g, IPDI (IPDI) 44.4 grams (0.2mol) joins in reaction vessel, reacts 3 hours under 40 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO content reaches 8.90%, adds chain extender 66.3 grams prepared by (1), is warming up to 55 DEG C and reacts 2 hours；After NCO content reaches 2.61%, adding the photosensitive monomer hydroxyethyl methacrylate (HEMA) 13 grams (0.1mol) with unsaturated double-bond and be warming up to 60 DEG C of reactions 3 hours, disappearing to the characteristic absorption peak recording NCO with FTIS to stop reaction；
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
The prepolymer 10 grams obtained by (2) is put in there-necked flask, 0.417 gram of light trigger 184 is added at 30 DEG C, mechanical agitation 30 minutes, after add under high velocity agitation deionized water 24.3 grams emulsify 1.5 hours, obtain the nonionic ultraviolet light solidfication water polyurethane emulsion of transparent blue light.The emulsion obtained is deviate from solvent in 30 minutes 35 DEG C of decompression distillations, obtains the nonionic ultraviolet light solidfication water polyurethane emulsion that solid content is 30%.
Embodiment 2
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic long-chain polymer
As shown in embodiment 1 step (1)；
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
It is 1000 by number-average molecular weight, hydroxyl value is the polyoxypropyleneglycol (PPG) 100 grams (0.1mol) of 110mgKOH/g, IPDI (IPDI) 44.4 grams (0.2mol) joins in reaction vessel, reacts 3 hours under 40 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO content reaches 8.90%, adds chain extender 66.3 grams prepared by (1), is warming up to 55 DEG C and reacts 2.5 hours；After NCO content reaches 2.71%, adding the photosensitive monomer hydroxyethyl methacrylate (HEMA) 13 grams (0.1mol) with unsaturated double-bond and be warming up to 65 DEG C of reactions 2 hours, disappearing to the characteristic absorption peak recording NCO with FTIS to stop reaction；
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
As shown in embodiment 1 step (3).
Embodiment 3
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic radical
As shown in embodiment 1 step (1)；
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
It is 1000 by number-average molecular weight, hydroxyl value is the polycaprolactone glycol (PCL) 100 grams (0.1mol) of 109-119mgKOH/g, IPDI (IPDI) 44.4 grams (0.2mol) joins in reaction vessel, reacts 1 hour under 50 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO content reaches 8.90%, adds chain extender 66.3 grams prepared by (1), is warming up to 60 DEG C and reacts 2 hours；After NCO content reaches 2.63%, adding the photosensitive monomer hydroxyethyl methacrylate (HEMA) 13 grams (0.1mol) with unsaturated double-bond and be warming up to 70 DEG C of reactions 1.5 hours, disappearing to the characteristic absorption peak recording NCO with FTIS to stop reaction；
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
As shown in embodiment 1 step (3).
Embodiment 4
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic radical
As shown in embodiment 1 step (1)；
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
It is 1000 by number-average molecular weight, hydroxyl value is the polycaprolactone glycol (PCL) 100 grams (0.1mol) of 109-119mgKOH/g, IPDI (IPDI) 44.4 grams (0.2mol) joins in reaction vessel, reacts 3 hours under 45 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO content reaches 8.90%, adds chain extender 66.3 grams prepared by (1), is warming up to 55 DEG C and reacts 3 hours；After NCO content reaches 2.68%, addition hydroxyl value is 160mgKOH/g, photosensitive monomer pentaerythritol triacrylate (PETA) 34.9 grams (0.1mol) with unsaturated double-bond is warming up to 60 DEG C of reactions 1.5 hours, and disappearing to the characteristic absorption peak recording NCO with FTIS to stop reaction；
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
As shown in embodiment 1 step (3).
Fig. 1 is the infrared spectrum of embodiment 1-3, is positioned at 2270cm in figure-1Place's NCO group characteristic peak all disappears, and indicates carrying out completely of reaction；
Fig. 2 is the emulsion particle diameter figure of embodiment 1-3, and along with the difference of addition dihydroxylic alcohols kind in figure, emulsion particle diameter differs, in the range of being positioned at 70-160 nm.Wherein WPU is aqueous polyurethane.
Embodiment 5
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic long-chain polymer
Take 11.12 grams of (0.05mol) IPDIs and add in there-necked flask, and take 50 grams of poly glycol monomethyl ether (molecular weight: 1000,0.05mol), add the catalyst dibutyltin dilaurylate of 0.018 gram, dropping is started at 45 DEG C, react 3 hours, until recording NCO group content by toluene-di-n-butylamine method to reach theoretical value 3.44%, add diethanol amine 5.26 grams (0.05mol), it is warming up to 50 DEG C, continue reaction 2 hours, stop to recording the disappearance of NCO characteristic absorption peak with the infrared transform spectrometer of Fourier.
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
It is 1000 by number-average molecular weight, hydroxyl value is the PCDL (PCD) 50 grams (0.1mol) of 100-120mgKOH/g, IPDI (IPDI) 44.4 grams (0.2mol) joins in reaction vessel, reacts 2.5 hours under 45 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO functional group content reaches 8.90%, adds chain extender 66.3 grams prepared by (1), is warming up to 50 DEG C and reacts 3 hours；After NCO functional group content reaches 2.61%, adding and be warming up to 60 DEG C with the photosensitive monomer hydroxyethyl methacrylate (HEMA) 13 grams (0.1mol) of unsaturated double-bond and react 2 hours, Fig. 3 uses FTIS to record to be positioned at 2250 cm-1The characteristic absorption peak of place NCO, along with reaction is carried out, NCO characteristic peak is progressively smaller until disappearance, illustrates that reaction carries out completely, can stop reaction.
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
The prepolymer 10 grams obtained by (2) is put in there-necked flask, 0.417 gram of light trigger 184 is added at 30 DEG C, mechanical agitation 30 minutes, after add under high velocity agitation deionized water 24.3 grams emulsify 1.5 hours, obtain the nonionic ultraviolet light solidfication water polyurethane emulsion of transparent blue light.The emulsion obtained is deviate from solvent in 30 minutes 35 DEG C of decompression distillations, obtains the nonionic ultraviolet light solidfication water polyurethane emulsion that solid content is 30%.
Embodiment 6
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic radical
As shown in embodiment 5 step (1).
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
It is 1000 by number-average molecular weight, hydroxyl value is the PCDL (T5651) 50 grams (0.1mol) of 100-120mgKOH/g, toluene di-isocyanate(TDI) (TDI) 34.8 grams (0.2mol) joins in reaction vessel, reacts 3 hours under 50 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO content reaches 9.91%, adds chain extender 66.3 grams prepared by (1), is warming up to 50 DEG C and reacts 2 hours；After NCO content reaches 2.78%, adding the photosensitive monomer hydroxyethyl methacrylate (HEMA) 13 grams (0.1mol) with unsaturated double-bond and be warming up to 65 DEG C of reactions 3 hours, disappearing to the characteristic absorption peak recording NCO with FTIS to stop reaction.
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
As shown in embodiment 5 step (3).
Embodiment 7
(1) side chain is with the synthesis of the chain extender with two hydroxyls of hydrophilic radical
As shown in embodiment 5 step (1).
(2) synthesis of nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer
Being 2000 by number-average molecular weight, PCDL (T5652) 200 grams (0.1mol), IPDI (IPDI) 44.4 grams (0.2mol) joins in reaction vessel, reacts 3 hours under 40 DEG C of mechanical agitation；Toluene-di-n-butylamine method records after NCO content reaches 8.90%, adds chain extender 66.3 grams prepared by (1), is warming up to 55 DEG C and reacts 1.5 hours；After NCO content reaches 2.61%, addition hydroxyl value is 160mgKOH/g, photosensitive monomer pentaerythritol triacrylate (PETA) 34.9 grams (0.1mol) with unsaturated double-bond is warming up to 70 DEG C of reactions 1 hour, and disappearing to the characteristic absorption peak recording NCO with FTIS to stop reaction.
(3) synthesis of nonionic ultraviolet light solidfication water polyurethane emulsion
As shown in embodiment 5 step (3).Fig. 4 gives the grain size distribution of embodiment 5 and 7 gained aqueous polyurethane emulsion.It can be seen that the HEMA end-blocking emulsion particle diameter using the photosensitive monomer PETA that degree of functionality is big to block gained emulsion particle diameter less than degree of functionality is big.
Above-described embodiment is used for illustrating the present invention rather than limiting the invention, in the protection domain of spirit and claims of the present invention, and any modifications and changes that the present invention is made, both fall within protection scope of the present invention.
Claims (13)
1. a preparation method for nonionic ultraviolet light solidfication water polyurethane acrylate, concrete preparation process is as follows:
(1) at 40-50 DEG C, poly glycol monomethyl ether and isocyanate ester compound are reacted 1-3 hour under the effect of catalyst with the ratio of mol ratio 1:1, wherein catalyst is the 0.02-0.03% of poly glycol monomethyl ether and isocyanate ester compound gross mass, then add with isocyanate ester compound with the polyhydroxy base class secondary amine of mole at 50-60 DEG C, continue reaction to the infrared transform spectrometer of Fourier and record the disappearance of NCO characteristic absorption peak, stop reaction, i.e. obtain the side chain chain extender with hydrophilic long-chain polymer；
Characterized by further comprising:
(2) by dihydroxylic alcohols and isocyanate ester compound with the ratio of mol ratio 1:2 with catalyst 40-50 DEG C of reaction, wherein catalyst is the 0.02-0.03% of dihydroxylic alcohols and isocyanate ester compound gross mass, after measuring, by toluene-di-n-butylamine back titration method, the 2.6-2.8% that NCO group content reaches the most all addition reactant gross masses, add the chain extender that step (1) obtains, after 50-70 DEG C of reaction 1-3 hour, add and stop reaction with the photosensitive monomer acrylate of mole in 60-70 DEG C of reaction to the characteristic absorption peak disappearance recording NCO with FTIS with dihydroxylic alcohols, obtain nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer；
(3) step (2) is obtained prepolymer and under the mechanical agitation that temperature is 30 DEG C, adds deionized water and light trigger carries out emulsification 1-2 hour, obtain the emulsion that solid content is 10-40%.
2. a preparation method for nonionic ultraviolet light solidfication water polyurethane acrylate emulsion, concrete preparation process is as follows:
(1) at 40-50 DEG C, poly glycol monomethyl ether and isocyanate ester compound are reacted 1-3 hour under the effect of catalyst with the ratio of mol ratio 1:1, wherein catalyst is the 0.01-0.05% of poly glycol monomethyl ether and isocyanate ester compound gross mass, then add with isocyanate ester compound with the polyhydroxy base class secondary amine of mole at 50-60 DEG C, continue reaction to the infrared transform spectrometer of Fourier and record the disappearance of NCO characteristic absorption peak, stop reaction, i.e. obtain the side chain chain extender with hydrophilic long-chain polymer；
Characterized by further comprising:
(2) by PCDL and isocyanate ester compound with the ratio of mol ratio 1:2 with catalyst 40-50 DEG C of reaction, wherein catalyst is the 0.01-0.05% of PCDL and isocyanate ester compound gross mass, after measuring, by toluene-di-n-butylamine back titration method, the 2.6%-2.8% that NCO group mass content reaches the most all addition reactant gross masses, add the chain extender that step (1) obtains, after 50-70 DEG C of reaction 1-3 hour, add and stop reaction with the photosensitive monomer acrylate of mole in 60-70 DEG C of reaction to the characteristic absorption peak disappearance recording NCO with FTIS with PCDL, obtain nonionic ultraviolet light solidfication water polyurethane acrylate prepolymer；
(3) step (2) is obtained prepolymer and under the mechanical agitation that temperature is 30 DEG C, adds deionized water and light trigger carries out emulsification 1-2 hour, obtain the emulsion that solid content is 10-40%.
Preparation method the most according to claim 1, it is characterised in that one or more in polyester diol and polyether Glycols of described dihydroxylic alcohols.
Preparation method the most according to claim 2, it is characterised in that described PCDL is selected from one or more in Merlon i.e. PCD, and T5650J, T5651, T5652 series PCDL of being produced of Asahi Kasei Corporation.
Preparation method the most according to claim 1 and 2, it is characterised in that the molecular weight of described poly glycol monomethyl ether is 500-2000.
Preparation method the most according to claim 1 and 2, it is characterized in that one or more in IPDI, toluene di-isocyanate(TDI), MDI, hexamethylene diisocyanate, meta-xylene diisocyanate or HMDI of described isocyanate ester compound.
Preparation method the most according to claim 1 and 2, it is characterised in that one or more in the secondary amine with two and two or more hydroxy functional group of described polyhydroxy base class secondary amine.
8. according to the preparation method described in claim 1 or 2 or 7, it is characterised in that one or more in diethanol amine, diisopropanolamine (DIPA), methyl diethanolamine of described polyhydroxy base class secondary amine.
Preparation method the most according to claim 1 and 2, it is characterised in that one or more in hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate of described photosensitive monomer acrylate.
Preparation method the most according to claim 1 and 2, it is characterised in that step (1) and one or more in tertiary amine catalyst, organic tin catalyst of (2) described catalyst.
11. preparation methods according to claim 1 and 2, it is characterised in that described light trigger includes one or more in radical photoinitiator, cationic photoinitiator, consumption is the 1-5% of step (2) gained prepolymer gross mass.
12. preparation method according to claim 1 and 2, it is characterised in that described light trigger includes one or more in alpha-alcohol ketone photoinitiator or α-aminoketone photoinitiator.
13. preparation methods according to claim 1 and 2, it is characterised in that described light trigger includes one or more in 1173,184,2959,907,369.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337993.1A CN104119543B (en) | 2014-07-16 | 2014-07-16 | A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337993.1A CN104119543B (en) | 2014-07-16 | 2014-07-16 | A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104119543A CN104119543A (en) | 2014-10-29 |
| CN104119543B true CN104119543B (en) | 2016-09-07 |
Family
ID=51765197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410337993.1A Active CN104119543B (en) | 2014-07-16 | 2014-07-16 | A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119543B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038568B (en) * | 2015-06-05 | 2018-01-16 | 江苏理工学院 | The wooden ancient building acid-resisting paint of Heavy Industrial environment, preparation method and application method |
| CN106634525A (en) * | 2016-10-19 | 2017-05-10 | 东莞市霖辉金属表面处理材料有限公司 | Polyurethane-acrylate cathodic electrophoretic coating material, preparation method therefor and application of polyurethane-acrylate cathodic electrophoretic coating material |
| CN107418410B (en) * | 2017-08-24 | 2021-02-12 | Ppg涂料(天津)有限公司 | Low VOC aqueous UV-curable single layer coating composition, method of coating and substrates coated therewith |
| CN111019082B (en) * | 2019-12-16 | 2021-07-27 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
| CN111072910A (en) * | 2019-12-31 | 2020-04-28 | 湖南松井新材料股份有限公司 | Nonionic polyurethane acrylate and preparation method and application thereof |
| CN111234168B (en) * | 2020-03-05 | 2021-09-10 | 合肥安利聚氨酯新材料有限公司 | Nonionic neutralizer and preparation method thereof, waterborne polyurethane and preparation method and application thereof |
| CN115433340B (en) * | 2022-09-26 | 2023-12-22 | 山东安然纳米实业发展有限公司 | Preparation method of photo-curing functional slurry, preparation method of functional fiber and functional fiber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724574B (en) * | 2013-12-06 | 2016-01-20 | 四川达威科技股份有限公司 | A kind of preparation method of leather finish non-ion aqueous polyurethane-poly acrylate composite emulsion |
-
2014
- 2014-07-16 CN CN201410337993.1A patent/CN104119543B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104119543A (en) | 2014-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119543B (en) | A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate | |
| CN102219886B (en) | Preparation method of aqueous polyurethane emulsion with high solid content | |
| CN101638464B (en) | Method for preparing polyurethane-polyacrylic ester microemulsion | |
| Nanda et al. | The influence of the ionic concentration, concentration of the polymer, degree of neutralization and chain extension on aqueous polyurethane dispersions prepared by the acetone process | |
| CN107254251B (en) | A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function | |
| CN105367743B (en) | A kind of synthetic method of aqueous polyurethane emulsion | |
| CN106866929A (en) | A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application | |
| CN107266654A (en) | A kind of ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin and preparation method thereof | |
| CN101235130B (en) | Cation water polyurethane emulsion and preparation method thereof | |
| CN104086742B (en) | A kind of preparation method of glass baseplate acid and alkali-resistance ultraviolet light solidified glue film resin | |
| CN107903373B (en) | UV-cured water-based hyperbranched polyurethane acrylate and preparation method thereof | |
| CN103833956A (en) | High molecular weight urethane acrylate resin and preparation method thereof | |
| CN101372530A (en) | Aqueous photo-curing polyurethane resin and preparation thereof | |
| CN101235195A (en) | Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof | |
| CN106905504B (en) | Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof | |
| JP6778254B2 (en) | Polyurethane (meth) acrylate oligomer and curable composition containing the oligomer | |
| CN102863605A (en) | Water-borne polyurethane synthetic leather size and preparation method and application thereof | |
| CN108017761A (en) | A kind of polyaminoester emulsion of acrylic monomer modification, its preparation method and application thereof | |
| CN102786655A (en) | Branched waterborne polyurethane with hydrophobic group and preparation method thereof | |
| CN104193941A (en) | Hyperbranched non-ionic waterborne polyurethane leather finishing agent and preparation method thereof | |
| CN115521437A (en) | Preparation method of water-soluble ultraviolet-curing hyperbranched polyurethane acrylic resin | |
| CN108264644B (en) | Water-based polyurethane acrylate emulsion with re-emulsifiability and preparation method thereof | |
| CN106753161A (en) | Compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof | |
| CN114149565B (en) | Preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate | |
| CN104031227A (en) | Aqueous polyurethane preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240131 Address after: 101200 room 205-211526, No. 40, Fuqian West Street, Pinggu town, Pinggu District, Beijing (cluster registration) Patentee after: BEIJING YONGBO TECHNOLOGY CO.,LTD. Guo jiahuodiqu after: Zhong Guo Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University Guo jiahuodiqu before: Zhong Guo |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240307 Address after: 262736 Beiyangtou Village, Taitou Town, Shouguang City, Weifang City, Shandong Province Patentee after: Weifang Wanfang waterproof Engineering Co.,Ltd. Guo jiahuodiqu after: Zhong Guo Address before: 101200 room 205-211526, No. 40, Fuqian West Street, Pinggu town, Pinggu District, Beijing (cluster registration) Patentee before: BEIJING YONGBO TECHNOLOGY CO.,LTD. Guo jiahuodiqu before: Zhong Guo |
|
| TR01 | Transfer of patent right |