CN111116856A - Single-component high-solid-content polyurethane resin and preparation method and application thereof - Google Patents
Single-component high-solid-content polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN111116856A CN111116856A CN201910248969.3A CN201910248969A CN111116856A CN 111116856 A CN111116856 A CN 111116856A CN 201910248969 A CN201910248969 A CN 201910248969A CN 111116856 A CN111116856 A CN 111116856A
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- polyol
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 76
- 150000003077 polyols Chemical class 0.000 claims abstract description 76
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 72
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 55
- 229920000570 polyether Polymers 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 27
- -1 cyclic lactone Chemical class 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000004970 Chain extender Substances 0.000 claims abstract description 5
- 239000007858 starting material Substances 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000002649 leather substitute Substances 0.000 claims description 27
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 18
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000003839 salts Chemical class 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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- TVSURRUHJZSEFC-UHFFFAOYSA-N 3-ethyl-5-methyloxolan-2-one Chemical compound CCC1CC(C)OC1=O TVSURRUHJZSEFC-UHFFFAOYSA-N 0.000 claims description 2
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 2
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- XTUSLLYSMVWGPS-UHFFFAOYSA-N carbonic acid;cyclohexene Chemical compound OC(O)=O.C1CCC=CC1 XTUSLLYSMVWGPS-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 210000004207 dermis Anatomy 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 24
- 239000011347 resin Substances 0.000 abstract description 24
- 239000010985 leather Substances 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 9
- 230000000704 physical effect Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 16
- 239000004744 fabric Substances 0.000 description 14
- 229920002635 polyurethane Polymers 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000007790 scraping Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a single-component high-solid-content polyurethane resin, a preparation method and application thereof, wherein the single-component high-solid-content polyurethane resin is prepared from the following components: isocyanate-terminated polyurethane prepolymer, curing agent and more than one of cyclic lactone or cyclic alkylene carbonate compound; the isocyanate-terminated polyurethane prepolymer is prepared by taking polymer polyol, a chain extender and isocyanate as starting materials; the polymer polyol is one or a mixture of polyether polyol and polyester polyol. The invention has high solid content resin, simple and convenient use, environmental protection and energy saving. The low-temperature storage stability is good, and the prepared leather has high peel strength and excellent physical properties.
Description
Technical Field
The invention relates to polyurethane resin and a preparation method and application thereof.
Background
The synthetic leather industry has developed to pursue product quality, appearance and price and pay more attention to the environmental protection performance of the product after years of development. Therefore, more and more industry is dedicated to the development of such environmentally friendly products, and the research on the waterborne polyurethane and the high solid content polyurethane resin is hot. However, the production line of the aqueous polyurethane resin has been changed due to poor physical properties and volatilization of water, and thus the application of the aqueous polyurethane resin has been limited.
The high solid content polyurethane has excellent physical property, high solid content and less solvent volatilization, and can be produced on the existing production line, so the application field is wider. Patent CN102964563A discloses a high solid content polyurethane resin, which still adopts the solvent of the traditional solvent type polyurethane resin, N, N-Dimethylformamide (DMF) and butanone are adopted, and the harm of DMF to the environment is great; the high solid content polyurethane composition disclosed in patent CN101613455B adopts a process technology of adding a blocking agent, the composition needs a higher temperature to realize deblocking, and volatilization of the blocking agent also causes harm to the environment, and the technology is a two-component system, and resin and a curing agent need to be mixed in a certain proportion, defoamed, filtered and the like before use, which is inconvenient to use.
None of the prior art addresses the problem of low temperature storage and transportation and use of high solids resins. In the field of synthetic leather, the requirement on the low-temperature stability of resin is high, and the constructability and the quality of a product are directly influenced, for example, the viscosity of polyurethane resin at low temperature is too high, the fluidity of the resin is poor, the scraping and coating construction of the synthetic leather is influenced, and the normal construction can be realized only by heating or diluting with a solvent; and if the resin contains crystalline particles, the scraping and coating of the synthetic leather is uneven, the flatness and the appearance of a finished product are directly influenced, the cutter is clamped under the condition, the production cannot be smoothly carried out, and the product quality and the production efficiency are influenced. High solids resins face significant challenges at lower temperatures, such as winter. In order to overcome the difficulty, the high solid resin can be insulated in the transportation and use processes, but the energy consumption and the cost are greatly increased, and the industrial feasibility is not high.
Therefore, there is a need for new environmentally friendly one-part high solids polyurethane resins that cure under certain conditions to polyurethane products, but are simple to use and maintain good flow and workability, especially at lower temperatures. The prior art high solid content polyurethane systems are stable above 25 ℃ and have good fluidity, however, at low temperatures, such as in winter, the temperature decrease can cause crystallization, the fluidity is poor due to high viscosity (such as viscosity exceeding 10 ten thousand CPs), and the transportation and use are affected. For high-solids polyurethane systems, it is particularly advantageous: maintaining stability at less than about 15 ℃ for at least 90 days, more preferably storage stability at 5-15 ℃ for 30 days; more preferably at least 10 days at 0-5 ℃; the viscosity is kept at a low level. Thus, the glass can be normally used even at low temperature.
Thus, there is a need for new one-component high-solids systems that are curable at moderate temperatures into thermoset polyurethane products, while being stable and flowable at lower temperatures during storage and use.
Disclosure of Invention
The invention aims to provide a single-component high-solid-content polyurethane resin, a preparation method and application thereof, so as to solve the technical problems.
The single-component high-solid-content polyurethane resin is prepared from the following components:
isocyanate-terminated polyurethane prepolymer, curing agent and more than one of cyclic lactone or cyclic alkylene carbonate compound;
the isocyanate-terminated polyurethane prepolymer is prepared by taking polymer polyol, a chain extender and isocyanate as initial raw materials, wherein the polymer polyol is one or a mixture of polyether polyol and polyester polyol;
when the polymer polyol is a mixture of polyether polyol and polyester polyol, the weight ratio is as follows: the ratio of the polyester polyol to the polyether polyol is 1: 0.6-9;
the isocyanate-terminated polyurethane prepolymer has NCO% content of 1.5-7.0%;
the polyether polyol preferably has a molecular weight of 250-6000, and the polyether polyol particularly preferably has a molecular weight of 400-2000;
the molecular weight of the polyester polyol is 1000-4000, and the molecular weight of the particularly preferable polyester polyol is 1800-3000;
preferably, the isocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate;
preferably, the polyether polyol is selected from more than one of polyether polyol GE210, polyether polyol GE220, polyether polyol GY440, polytetrahydrofuran ether PTMG1000 with the molecular weight of 1000 and the functionality of 2, or polytetrahydrofuran ether PTMG2000 with the molecular weight of 2000 and the functionality of 2;
more preferably;
the polyether polyol is a mixture of polyether polyol GE210 and polyether polyol GE220 or polytetrahydrofuran ether PTMG2000, and the weight parts of the polyether polyol are as follows:
polyether glycol GE210, polyether glycol GE220 or polytetrahydrofuran ether PTMG2000 is 0.5-5.3: 1;
or the following steps:
the polyether polyol is a mixture of polytetrahydrofuran ether PTMG1000 and polytetrahydrofuran ether PTMG2000, and the weight ratio is as follows: PTMG 1000: PTMG2000 is 5-5.5: 1;
wherein: polyether polyol GE210 differs from polyether polyol GE220 in that the molecular weight of polyether polyol GE210 is 1000 and the molecular weight of polyether polyol GE220 is 2000;
preferably, the polyester polyol is selected from more than one of polyester polyol PE1756 with molecular weight of 2000, polyester polyol PE98 with molecular weight of 3000, polyester polyol PE56 with molecular weight of 2000, polyester polyol PE3756 with molecular weight of 2000 and polyester polyol PE7018 with molecular weight of 1800;
more preferably, the polyester polyol is selected from more than one of polyester polyol PE1756 with molecular weight of 2000, polyester polyol PE98 with molecular weight of 3000, polyester polyol PE3756 with molecular weight of 2000 and polyester polyol PE7018 with molecular weight of 1800;
preferably, the mixture of polyester polyol and polyether polyol is a mixture of one of polyester polyol PE1756, polyester polyol PE56 and polyester polyol PE7018 and polyether polyol GE210, and the weight parts are as follows:
polyester polyol PE1756, polyester polyol PE56, or polyester polyol PE7018 to polyether polyol GE210 is 1: 0.6-9;
or the following steps:
the mixture of the polyester polyol and the polyether polyol is a mixture of polyester polyol PE3756, polyether polyol GE210 and polyether polyol GY440, and the weight parts ratio is as follows: polyester polyol PE3756 polyether polyol GE210 and polyether polyol GY440 of 35: 104;
or the following steps:
the mixture of the polyester polyol and the polyether polyol is a mixture of polyester polyol PE3756 and polytetrahydrofuran ether PTMG1000, and the weight parts ratio is as follows: polyester polyol PE 3756: polytetrahydrofuran ether PTMG1000 is 5: 13;
or the following steps:
the mixture of the polyester polyol and the polyether polyol is a mixture of polyester polyol PE56 and polytetrahydrofuran ether PTMG2000, and the weight parts ratio is as follows: polyester polyol PE56, polytetrahydrofuran ether PTMG2000 is 4: 5;
the chain extender is preferably neopentyl glycol, trimethylolpropane or diethanol amine;
the curing agent is a metal salt complex of methylenedianiline, wherein the metal comprises an alkali metal salt, an alkaline earth metal salt, a transition metal salt or a main group metal salt, preferably the alkali metal salt and the alkaline earth metal salt, and particularly preferably the alkali metal salt is sodium chloride. Metal salt complexes of methylenedianiline are commercially available as products from the company Chemtura Corporation.
Preferably, the cyclic lactone compound is selected from at least one of gamma-butyrolactone, gamma-valerolactone, epsilon-caprolactone, α gamma-dimethyl butyrolactone, β gamma-dimethyl butyrolactone, gamma-dimethyl butyrolactone or α -ethyl-gamma-methyl butyrolactone;
the cyclic alkylene carbonate compound is selected from more than one of ethylene carbonate, propylene carbonate, 1, 2-butylene carbonate, 2, 3-butylene carbonate, 1, 2-cyclohexene carbonate or styrene carbonate; wherein the above compounds or their mixtures having a boiling point of 80-250 ℃ and a melting point of above 0 ℃ are preferred;
preferably, the single-component high-solid-content polyurethane resin is prepared from the following components in parts by weight:
the polymer polyol is polyether polyol;
or: the paint is prepared from the following components in parts by weight:
the polymer polyol is polyester polyol;
or: the paint is prepared from the following components in parts by weight:
the polymer polyol A is polyether polyol
The polymer polyol B is polyester polyol.
Further preferably, the composition is prepared from the following components in parts by weight:
the polymer polyol is polyether polyol;
or: the paint is prepared from the following components in parts by weight:
the polymer polyol is polyester polyol
Or: the paint is prepared from the following components in parts by weight:
the polymer polyol A is polyether polyol
The polymer polyol B is polyester polyol.
The viscosity of the single-component high-solid-content polyurethane resin at 25 ℃ is 1600-10000 cps;
the preparation method of the single-component high-solid-content polyurethane resin comprises the following steps:
(1) stirring and mixing isocyanate and polymer polyol at room temperature, heating to 70-80 ℃, reacting for 3-4h, detecting the content of NCO% until the theoretical value is reached;
(2) reducing the reaction temperature to 55-60 ℃, adding the cyclic lactone or cyclic alkylene carbonate compound, and stirring for 0.5-1.0 h;
(3) reducing the temperature to 30-35 ℃, adding a curing agent, and stirring for 20-40 minutes to obtain the single-component high-solid-content polyurethane resin.
The single-component high-solid-content polyurethane resin can be used for preparing synthetic leather, genuine leather or PVC composite leather and is mainly used as middle layer resin; the facing material and the backing material can be water-based resin or solvent-based resin which is commercially available.
The application method comprises the following steps:
coating commercially available polyurethane fabric resin on release paper by a scraper bar, drying the release paper by an oven, coating the film-formed release paper with the single-component high-solid content polyurethane resin by the scraper bar, placing the film-formed release paper in the oven for curing, taking out the film-formed release paper, coating the film-formed release paper with commercially available primer resin by a scraper bar, sticking base cloth, drying the base cloth in the oven, taking out the base cloth and releasing the base cloth to obtain the leather. Different leather products can be obtained by adopting different base materials, for example, the microfiber synthetic leather can be obtained by basically adopting non-woven fabrics; the synthetic leather can be obtained by adopting the synthetic leather base cloth, and the genuine leather can be obtained by adopting the genuine leather bottom blank. VOC (total volatile matter) was measured by HJ/H400-2007 standard. And (3) standing the prepared synthetic leather at normal temperature for 72h, and measuring the peel strength of the synthetic leather according to QB/T2888-2007 standard, wherein the peel strength of the synthetic leather is more than 80N/3cm, namely the high-peel-strength leather.
Compared with the prior art, the invention has the beneficial effects that: 1. the single-component polyurethane high-solid resin is simple and convenient to use, and can be directly used without the processes of material preparation, defoaming, filtering and the like before use; 2. high solid content, no toxic substances released in the whole reaction and use process, environmental protection and energy saving. 3. The storage stability is good, especially the storage stability at low temperature is good, and the transportation by a heat preservation vehicle and the storage in a heat preservation room are not needed at lower temperature. 4. The leather prepared by the invention has high peel strength and excellent physical properties.
Detailed Description
Description of the raw materials used:
TDI: toluene diisocyanate
MDI: diphenylmethane diisocyanate
IPDI: isofluorone diisocyanates
PE-56: polyester polyol, molecular weight: 2000, Huafeng New materials Co., Ltd
PE-1756: polyester polyol, molecular weight: 2000, Huafeng New materials Co., Ltd
PE-3756: polyester polyol, molecular weight: 2000, Huafeng New materials Co., Ltd
PE-98: polyester polyol, molecular weight: 3000 Huafeng New materials Co Ltd
PE-7018: polyester polyol, molecular weight: 1800 Huafeng New materials Co Ltd
GE 210: polyether polyols, purchased from Shanghai Gaoqiao petrochemical company;
GE220 polyether polyol, purchased from Shanghai Gaoqiao petrochemical company;
GY 440: polyether polyols, available from Kunshan national chemical company;
PTMG 1000: polytetrahydrofuran ether, molecular weight: 1000, functionality: 2, available from BASF corporation;
PTMG 2000: polytetrahydrofuran ether, molecular weight: 2000, functionality: 2, available from BASF corporation;
curing agent: sodium chloride Complex of methylenedianiline, available from Chemtura Corporation under the designation
C3。
Example 1
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyols GE210 and GE220 into a reactor at room temperature, stirring and mixing, heating to 70 ℃, reacting for 4 hours at the temperature, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 5.8%);
(2) reducing the reaction temperature to 60 ℃, adding 1, 2-butylene carbonate, and stirring for 1.0 h;
(3) the temperature is reduced to 30 ℃, the curing agent is added, and the mixture is stirred for 40 minutes. Thus obtaining the single-component polyurethane resin with the solid content of 90 percent. The viscosity of the obtained one-component resin at 25 ℃ is 6490 cps.
Example 2
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyol GE210 and polytetrahydrofuran ether PTMG2000 into a reactor at room temperature, stirring and mixing, heating to 80 ℃, reacting for 3 hours at the temperature, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 5.65%);
(2) reducing the reaction temperature to 65 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 0.5 h;
(3) the temperature is reduced to 35 ℃, the end-capping type curing agent is added, and the mixture is stirred for 20 minutes. Thus obtaining the single-component polyurethane resin with the solid content of 80 percent by weight. The viscosity of the obtained one-component resin at 25 ℃ is 1610 cps.
Example 3
The formula is as follows: (parts by weight)
According to the preparation method of example 1, a one-component polyurethane resin having a solid content of 95% by weight and a viscosity of 5000cps at 25 ℃ was prepared.
Example 4
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyols PTMG1000 and PTMG2000 into a reactor at room temperature, stirring and mixing, slowly heating to 80 ℃, adding 100 parts of gamma-butyrolactone, reacting for 4 hours at the temperature, detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 4.7%);
(2) reducing the reaction temperature to 65 ℃, adding 136 parts of gamma-butyrolactone, and stirring for 0.5 h;
(3) reducing the temperature to 35 ℃, adding an end-capping type curing agent, and stirring for 30 minutes to prepare the single-component polyurethane resin with the solid content of 70 percent, wherein the viscosity is 9000cps at 25 ℃.
Example 5
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyol GE210 and PTMG2000 into a reactor at room temperature, stirring and mixing, slowly heating to 75 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding neopentyl glycol for reacting for 2 hours, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 1.5%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 1.0 h;
(3) the temperature is reduced to 35 ℃, the end-capping type curing agent is added, and the mixture is stirred for 30 minutes. The one-component polyurethane resin with the weight solid content of 80 percent is prepared, and the viscosity at 25 ℃ is 8100 cps.
Example 6
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyols GE210 and GE220 into a reactor at room temperature, stirring and mixing, slowly heating to 70 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding trimethylolpropane, reacting for 2 hours, detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 3.0%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 0.5 h;
(3) the temperature is reduced to 30 ℃, the end-capping type curing agent is added, and the mixture is stirred for 40 minutes. The prepared single-component polyurethane resin has the solid content of 80 percent by weight, and the viscosity of 2300cps at 25 ℃.
Example 7
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyols GE210 and GE220 into a reactor at room temperature, stirring and mixing, heating to 70 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding TMP, reacting for 2 hours, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 7.0%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 1.0 h; (3) the temperature is reduced to 30 ℃, the end-capping type curing agent is added, and the mixture is stirred for 40 minutes. The single-component polyurethane resin with the weight solid content of 80 percent is prepared, and the viscosity at 25 ℃ is 1800 cps. Comparison sample: selecting from commercially available Bayer Material science and technology Ltd
HS-85 LN100 parts and curing agent
8.5 parts of HS-C, before use, the two are mixed uniformly in proportion by a dispersion machine, defoamed by a vacuum defoaming machine to eliminate bubbles brought by a stirring process, and then filtered by a 160-mesh filter screen for use. At lower temperatures, e.g.
HS-85 LN viscosity of 13 ten thousand CPS @21 ℃, which is difficult to be mixed with HS-C uniformly, has too high viscosity in the using process and can not be normally used for scraping and coating synthetic leather (the normal construction viscosity of the synthetic leather needs to be below 2 ten thousand CPs), so the resin must be heated before construction to reduce the viscosity and the resin can be normally constructed under the heat preservation state.
Example 8
The one-component high-solid polyurethane resins obtained in examples 1 to 7 were respectively placed at a temperature of about 15 ℃ or lower to maintain stability for at least 90 days and at a temperature of 5 to 15 ℃ to maintain stability for 30 days; the viscosity is maintained below 2 million CPs when the storage stability is at 0-5 ℃ for at least 10 days. The construction can be carried out normally.
Taking 100 parts of the prepared single-component high-solid-content polyurethane resin, preparing a film on mirror surface release paper by using a 300-micrometer film maker, curing for 5min at 150 ℃, taking out the cured film, releasing the cured film from the release paper, standing at normal temperature for 72h, and testing the mechanical property according to the standard GB/T1040.3-2006, wherein the tensile strength is more than 30MPa, the fracture productivity is more than 500 percent, and the 100 percent elongation strength is 2-7 MPa. These physical properties fully satisfy the performance requirements of synthetic leather for resins.
Example 9
The preparation method of the synthetic leather comprises the following steps: the single-component high-solid-content resin is suitable for being used as middle layer resin of leather, and the shell fabric and the bottom material can be commercially available water-based resin, and the method comprises the following specific steps: adding a thickening agent such as AL-A of OMG company into commercially available fabric resin JF-PDY-851MY, adjusting the viscosity to be 3000-CPS, then scraping the emulsion onto release paper by using a 200-micron scraper bar, drying for 3min at 90 ℃, then drying for 3min at 110 ℃ and drying for 2min at 130 ℃, volatilizing the water in the waterborne polyurethane emulsion to form a film, then scraping the single-component high-solid-content polyurethane resin onto the film-formed release paper by using a 350-micron scraper bar, curing in a 150- ℃ drying oven, taking out, then taking the commercially available JF-PDY-511H as a base material, scraping 200 microns onto a cured film of the release paper, attaching base cloth, drying for 3min at 90 ℃, drying for 3min at 110 ℃ and drying for 2min at 130 ℃, and taking out the release cloth to obtain the synthetic leather. The VOC (total volatile matter) of the synthetic leather is measured to be lower than 10ppm by adopting the HJ/H400-2007 standard, the peel strength of the prepared synthetic leather is measured according to the QB/T2888-2007 standard after the synthetic leather is placed at normal temperature for 72 hours, and the peel strength is 110N/3cm (more than 80N/3cm is the high peel strength synthetic leather). The prepared synthetic leather is placed in a constant temperature and humidity box with 70 ℃ and 95% of R.H. for jungle test, and is taken out after 10 weeks, the surface of the leather is intact, and the peel strength is 100N/3 cm.
Example 10
The formula is as follows: (parts by weight)
(1) Adding TDI and polyester polyol PE-1756 into a reactor at room temperature, stirring and mixing, heating to 75 ℃, reacting for 3 hours at the temperature, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 3.8%);
(2) reducing the reaction temperature to 60 ℃, adding 1, 2-butylene carbonate, and stirring for 1.0 h;
(3) reducing the temperature to 30 ℃, adding a curing agent, and stirring for 40 minutes to obtain the single-component polyurethane resin with the weight solid content of 80 percent, wherein the viscosity of the single-component polyurethane resin at 25 ℃ is 6300 cps.
Example 11
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyol GE210 and polytetrahydrofuran ether PTMG2000 into a reactor at room temperature, stirring and mixing, heating to 80 ℃, reacting for 3 hours at the temperature, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 5.0%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 1.0 h;
(3) reducing the temperature to 35 ℃, adding an end-capping type curing agent, and stirring for 20 minutes to obtain the single-component polyurethane resin with the solid content of 90 percent by weight, wherein the viscosity of the single-component polyurethane resin is 6500cps at 25 ℃.
Example 12
The formula is as follows: (parts by weight)
According to the preparation method of example 10, a one-component polyurethane resin having a solid content of 95% by weight, which had a viscosity of 7500cps at 25 c, was prepared.
Example 13
The formula is as follows: (parts by weight)
(1) Adding TDI and polyester polyol PE-98 into a reactor at room temperature, stirring and mixing, slowly heating to 80 ℃, adding 300 parts of gamma-butyrolactone, reacting for 4 hours at the temperature, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 1.9%);
(2) reducing the reaction temperature to 65 ℃, adding 273 parts of gamma-butyrolactone, and stirring for 0.5 h; .
(3) Reducing the temperature to 35 ℃, adding an end-capping type curing agent, and stirring for 30 minutes to prepare the single-component polyurethane resin with the solid content of 70 percent by weight, wherein the viscosity of the single-component polyurethane resin at 25 ℃ is 8500 cps.
Example 14
The formula is as follows: (parts by weight)
(1) Adding TDI, polyether polyol GE210 and polyester polyol PE-3756 into a reactor at room temperature, stirring and mixing, slowly heating to 75 ℃, reacting for 4 hours at the temperature, cooling to 65 ℃, adding GY440, reacting for 2 hours, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 6.4%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 1.0 h;
(3) the temperature is reduced to 35 ℃, the end-capping type curing agent is added, and the mixture is stirred for 30 minutes to prepare the single-component polyurethane resin with the solid content of 80 percent by weight, wherein the viscosity of the single-component polyurethane resin is 5500cps at 25 ℃.
Example 15
The formula is as follows: (parts by weight)
(1) Adding TDI, polyester polyol PE-7018 and polyether polyol GE210 into a reactor at room temperature, stirring and mixing, slowly heating to 70 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding trimethylolpropane, reacting for 2 hours, detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 7.0%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate and gamma-butyrolactone, and stirring for 0.5 h;
(3) the temperature is reduced to 30 ℃, the end-capping type curing agent is added, and the mixture is stirred for 40 minutes to prepare the single-component polyurethane resin with the solid content of 85 percent, wherein the viscosity of the single-component polyurethane resin is 5500cps at 25 ℃.
Example 16
The formula is as follows: (parts by weight)
(1) Adding TDI, polyester polyol PE-3756 and polyether polyol PTMG1000 into a reactor at room temperature, stirring and mixing, heating to 70 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding trimethylolpropane, reacting for 2 hours, detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 5.6%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate, and stirring for 1.0 h;
(3) the temperature is reduced to 30 ℃, the end-capping type curing agent is added, and the mixture is stirred for 40 minutes to prepare the single-component polyurethane resin with the solid content of 80 percent by weight, and the viscosity of the single-component polyurethane resin at 25 ℃ is 9000 cps.
Example 17
The formula is as follows: (parts by weight)
(1) Adding TDI, polyester polyol PE-56 and polyether polyol PTMG2000 into a reactor at room temperature, stirring and mixing, heating to 70 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding 1, 4-butanediol, reacting for 2 hours, detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 4.5%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate, and stirring for 1.0 h;
(3) reducing the temperature to 30 ℃, adding an end-capping type curing agent, and stirring for 40 minutes to prepare the single-component polyurethane resin with the solid content of 70 percent by weight, wherein the viscosity of the single-component polyurethane resin is 7800cps at 25 ℃.
Example 18
The formula is as follows: (parts by weight)
(1) Adding TDI, polyester polyols PE-3756 and PE-7018 into a reactor at room temperature, stirring and mixing, heating to 70 ℃, reacting for 4 hours at the temperature, cooling to 60 ℃, adding diethanolamine, reacting for 2 hours, and detecting the content of NCO% until the theoretical value is reached (the content of NCO% is 3.9%);
(2) reducing the reaction temperature to 60 ℃, adding propylene carbonate, and stirring for 1.0 h;
(3) reducing the temperature to 30 ℃, adding an end-capping type curing agent, and stirring for 40 minutes to prepare the single-component polyurethane resin with the solid content of 70 percent by weight, wherein the viscosity of the single-component polyurethane resin at 25 ℃ is 8500 cps.
Comparison sample: selecting from commercially available Bayer Material science and technology Ltd
HS-85 LN100 parts and curing agent
8.5 parts of HS-C, before use, the two are mixed uniformly in proportion by a dispersion machine, defoamed by a vacuum defoaming machine to eliminate bubbles brought by a stirring process, and then filtered by a 160-mesh filter screen for use. At lower temperatures, e.g.
HS-85 LN viscosity of 13 ten thousand CPS @21 ℃, which is difficult to be mixed with HS-C uniformly, has too high viscosity in the using process and can not be normally used for scraping and coating synthetic leather (the normal construction viscosity of the synthetic leather needs to be below 2 ten thousand CPs), so the resin must be heated before construction to reduce the viscosity and the resin can be normally constructed under the heat preservation state.
Example 19
The one-component high-solid polyurethane resins obtained in examples 10 to 18 were stored at 5 to 15 ℃ for 30 days while maintaining stability at about 15 ℃ for at least 90 days; the storage stability is at least 10 days at 0-5 ℃, the viscosity is kept below 2 ten thousand CPs, and the construction can be normally carried out.
Taking 100 parts of the prepared single-component high-solid-content polyurethane resin, preparing a film on mirror surface release paper by using a 300-micrometer film maker, curing for 5min at 150 ℃, taking out the cured film, releasing the cured film from the release paper, standing at normal temperature for 72h, and testing the mechanical property according to the standard GB/T1040.3-2006, wherein the tensile strength is more than 20MPa, the fracture productivity is more than 500 percent, and the 100 percent elongation strength is 2-7 MPa. These physical properties fully satisfy the performance requirements of synthetic leather for resins.
Example 20
The preparation method of the synthetic leather comprises the following steps: the single-component high-solid-content resin is suitable for being used as middle layer resin of leather, and the shell fabric and the bottom material can be commercially available water-based resin, and the method comprises the following specific steps: adding a thickening agent such as AL-A of OMG company into commercially available fabric resin JF-PDY-851MY, adjusting the viscosity to be 3000-CPS, then scraping the emulsion onto release paper by using a 200-micron scraper bar, drying for 3min at 90 ℃, then drying for 3min at 110 ℃ and drying for 2min at 130 ℃, volatilizing the water in the waterborne polyurethane emulsion to form a film, then scraping the single-component high-solid-content polyurethane resin onto the film-formed release paper by using a 350-micron scraper bar, curing in a 150- ℃ drying oven, taking out, then taking the commercially available JF-PDY-511H as a base material, scraping 200 microns onto a cured film of the release paper, attaching base cloth, drying for 3min at 90 ℃, drying for 3min at 110 ℃ and drying for 2min at 130 ℃, and taking out the release cloth to obtain the synthetic leather. The VOC (total volatile matter) of the synthetic leather is measured to be lower than 10ppm by adopting the HJ/H400-2007 standard, the peel strength of the prepared synthetic leather is measured according to the QB/T2888-2007 standard after the synthetic leather is placed at normal temperature for 72 hours, and the peel strength is 110N/3cm (more than 80N/3cm is the high peel strength synthetic leather).
Claims (9)
1. The single-component high-solid-content polyurethane resin is characterized by being prepared from the following components:
the isocyanate-terminated polyurethane prepolymer contains 1.5-7.0% of NCO%, and at least one of a curing agent and a cyclic lactone or cyclic alkylene carbonate compound;
the isocyanate-terminated polyurethane prepolymer is prepared by taking polymer polyol, a chain extender and isocyanate as starting materials;
the polymer polyol is polyester polyol or a mixture of the polyester polyol and the polyether polyol;
the polyether polyol is selected from more than one of polyether polyol GE210, polyether polyol GE220, polyether polyol GY440, polytetrahydrofuran ether PTMG1000 with the molecular weight of 1000 and the functionality of 2 or polytetrahydrofuran ether PTMG2000 with the molecular weight of 2000 and the functionality of 2;
the polyester polyol is selected from more than one of polyester polyol PE175 with molecular weight of 2000, polyester polyol PE98 with molecular weight of 3000, polyester polyol PE56 with molecular weight of 2000, polyester polyol PE3756 with molecular weight of 2000 and polyester polyol PE7018 with molecular weight of 1800;
the mixture of the polyester polyol and the polyether polyol is a mixture of one of the polyester polyol PE1756 with the molecular weight of 2000, the polyester polyol PE56 with the molecular weight of 2000 or the polyester polyol PE7018 with the molecular weight of 1800 and the polyether polyol GE210, and the weight parts of the mixture are as follows:
polyester polyol PE1756 with molecular weight of 2000, polyester polyol PE56 with molecular weight of 2000 or polyester polyol PE7018 with molecular weight of 1800 to polyether polyol with molecular weight of 2000 being 1: 0.6-9; or the following steps:
the mixture of the polyester polyol and the polyether polyol is a mixture of polyester polyol PE3756 with molecular weight of 2000, polyether polyol GE210 and polyether polyol GY440, and the weight parts ratio is as follows: polyester polyol PE3756 polyether polyol GE210 and polyether polyol GY440 of 35: 104; or the following steps:
the mixture of the polyester polyol and the polyether polyol is a mixture of polyester polyol PE3756 with molecular weight of 2000 and polytetrahydrofuran ether PTMG1000, and the weight parts ratio is as follows: polyester polyol PE3756 with molecular weight of 2000: polytetrahydrofuran ether PTMG1000 ═ 5: 13; or the following steps:
the mixture of the polyester polyol and the polyether polyol is a mixture of polyester polyol PE56 with molecular weight of 2000 and polytetrahydrofuran ether PTMG2000, and the weight parts ratio is as follows: polyester polyol PE56 with molecular weight of 2000: polytetrahydrofuran ether PTMG2000 ═ 4: 5;
the curing agent is a metal salt complex of methylene dianiline, wherein the metal comprises alkali metal salt, alkaline earth metal salt, transition metal salt or main group metal salt.
2. The one-component high-solid polyurethane resin according to claim 1, wherein the isocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.
3. The one-component high-solid polyurethane resin according to claim 1, wherein the chain extender is selected from neopentyl glycol, trimethylolpropane or diethanolamine.
4. The one-component high-solid polyurethane resin according to claim 1, wherein the cyclic lactone compound is one or more selected from the group consisting of γ -butyrolactone, γ -valerolactone, e-caprolactone, α γ -dimethyl butyrolactone, β γ -dimethyl butyrolactone, γ γ -dimethyl butyrolactone, and α -ethyl- γ methyl butyrolactone;
the cyclic alkylene carbonate compound is selected from more than one of ethylene carbonate, propylene carbonate, 1, 2-butylene carbonate, 2, 3-butylene carbonate, 1, 2-cyclohexene carbonate or styrene carbonate.
5. The single-component high-solid polyurethane resin according to any one of claims 1 to 4, which is prepared from the following components in parts by weight:
the polymer polyol is polyester polyol;
or: the paint is prepared from the following components in parts by weight:
the polymer polyol A is polyether polyol;
the polymer polyol B is polyester polyol.
6. The single-component high-solid-content polyurethane resin according to claim 5, which is prepared from the following components in parts by weight:
the polymer polyol is polyester polyol
Or: the paint is prepared from the following components in parts by weight:
the polymer polyol A is polyether polyol
The polymer polyol B is polyester polyol.
7. The one-component high-solid polyurethane resin according to claim 6, wherein the viscosity is 1600-10000cps at 25 ℃.
8. The method for preparing a one-component high-solid polyurethane resin according to any one of claims 1 to 7, comprising the steps of:
(1) stirring and mixing isocyanate and polymer polyol at room temperature, heating to 70-80 ℃, reacting for 3-4h, detecting the content of NCO% until the theoretical value is reached;
(2) reducing the reaction temperature to 55-60 ℃, adding the cyclic lactone or cyclic alkylene carbonate compound, and stirring for 0.5-1.0 h;
(3) reducing the temperature to 30-35 ℃, adding a curing agent, and stirring for 20-40 minutes to obtain the single-component high-solid-content polyurethane resin.
9. Use of the one-component high-solid polyurethane resin according to any one of claims 1 to 7, for the preparation of synthetic leather or dermis.
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| CN106008900B (en) * | 2016-07-29 | 2018-11-27 | 河北工业大学 | A kind of polyurethane-polyesteramide compound and preparation method thereof |
| CN110028776A (en) * | 2019-04-23 | 2019-07-19 | 福建宝利特科技股份有限公司 | A kind of antifouling solvent-free artificial leather |
| CN110330628A (en) * | 2019-07-10 | 2019-10-15 | 福建元发树脂有限公司 | Non-solvent single-component polyurethane mirror surface resin |
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