CN113278125A - Photo-curing polyurethane and application thereof - Google Patents
Photo-curing polyurethane and application thereof Download PDFInfo
- Publication number
- CN113278125A CN113278125A CN202110593721.8A CN202110593721A CN113278125A CN 113278125 A CN113278125 A CN 113278125A CN 202110593721 A CN202110593721 A CN 202110593721A CN 113278125 A CN113278125 A CN 113278125A
- Authority
- CN
- China
- Prior art keywords
- diol
- polyurethane
- dihydric alcohol
- double bond
- photocuring
- 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.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 61
- 239000004814 polyurethane Substances 0.000 title claims abstract description 61
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000010146 3D printing Methods 0.000 claims abstract description 24
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 150000002009 diols Chemical class 0.000 claims description 82
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 239000004711 α-olefin Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920005749 polyurethane resin Polymers 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 10
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 6
- 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 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- 229940035437 1,3-propanediol Drugs 0.000 claims description 4
- 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
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- PFUKECZPRROVOD-UHFFFAOYSA-N 1,3,5-triisocyanato-2-methylbenzene Chemical compound CC1=C(N=C=O)C=C(N=C=O)C=C1N=C=O PFUKECZPRROVOD-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019766 L-Lysine Nutrition 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920006295 polythiol Polymers 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 20
- 238000001035 drying Methods 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The embodiment of the application discloses photocuring polyurethane and application thereof, wherein the photocuring polyurethane has a structure shown in a formula (1), wherein R is a residue of isocyanate, and a plurality of Rs are the same or different; x is the residue of dihydric alcohol, a plurality of X are the same or different, and X comprises at least one residue of dihydric alcohol containing an ethylenically unsaturated double bond or dihydric alcohol containing an unsaturated triple bond, and the molecular weight of the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond is 0-1500 and does not comprise 0; a is a capping group comprising at least one ethylenically unsaturated double bond; n is an integer of 1 to 3. An unsaturated double bond structure is introduced into polyurethane to improve the curing rate of resin, so that the surface drying performance of the resin is effectively improved, the obtained photocuring polyurethane has excellent flexibility, curing rate and surface drying performance, and the photocuring polyurethane can be used in the technical field of photocuring 3D printing or the technical field of adhesives.
Description
Technical Field
The embodiment of the application relates to the technical field of photocuring, in particular to photocuring polyurethane and application thereof.
Background
As a photosensitive resin (UV) resin, there is a photosensitive resin having both a fast curing rate and a slow curing rate, and a cured product of a photosensitive resin having a fast curing rate generally has a relatively high hardness. Therefore, in practical applications, it is necessary to balance the properties with a photosensitive resin having good flexibility.
Polyurethane is used as a photosensitive oligomer which is applied more, and can endow photosensitive resin with good toughness, adhesiveness and chemical stability. At present, the photosensitive polyurethane resin with good flexibility mainly comprises difunctional polyurethane, and the synthetic route is generally polyether/polyester diol + isocyanate (IPDI) + hydroxyethyl acrylate/hydroxyethyl methacrylate. The synthetic line is slow in curing speed, and the surface layer of the cured polyurethane resin is poor in drying performance, so that further application of the polyurethane is influenced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a photocuring polyurethane and application thereof.
According to one aspect of the present invention, there is provided a photocurable polyurethane comprising the general formula shown in formula (1):
r is the residue of an isocyanate, and a plurality of R are the same or different;
x is the residue of dihydric alcohol, a plurality of X are the same or different, and X comprises at least one residue of dihydric alcohol containing an ethylenically unsaturated double bond or dihydric alcohol containing an unsaturated triple bond, and the molecular weight of the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond is 0-1500 and does not comprise 0;
a is a capping group comprising at least one ethylenically unsaturated double bond;
n is an integer of 1 to 3.
Preferably, the number average molecular weight of the photo-curable polyurethane is 3000-6000.
Preferably, the ethylenically unsaturated double bond-containing diol or unsaturated triple bond-containing diol has a molecular weight of 0 to 500 and does not include 0.
Preferably, as R, it is the residue of an isocyanate represented by R (NCO) m, said m being a natural number greater than 1, preferably m is 2 or 3, more preferably m is 2.
Preferably, the isocyanate comprises methylene diphenyl diisocyanate, toluene diisocyanate, p-phenyl diisocyanate, 4, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate HDI), isophorone diisocyanate, triphenylmethane-4, 4,4 triisocyanate, toluene-2, 4, 6-triyl triisocyanate, 1,3, 5-triazine-2, 4, 6-triisocyanate, ethyl ester L-lysine triisocyanate or a mixture thereof or a copolymer thereof.
Preferably, the ethylenically unsaturated double bond-containing diol may be a terminal hydroxyl group-modified diene- α -olefin copolymer.
Preferably, the unsaturated triple bond-containing diol is 1, 4-butynediol.
Preferably, the hydroxyl-terminated modified diene- α -olefin copolymer has a general formula shown in formula (2):
wherein n is1And n2Is a natural number greater than or equal to 1, and the number average molecular weight of the copolymer is 0-1500 and does not include 0.
Preferably, the dihydric alcohol further comprises ethylene glycol, propylene glycol, 1, 3-propanediol or 1, 4-butanediol;
preferably, the dihydric alcohol further comprises high-molecular polyol, and the high-molecular polyol is high-molecular polyol with the number average molecular weight of 300-5000;
preferably, the high molecular weight polyol includes polyether diol, polyester diol, polylactone diol, polyesteramide diol, polyacrylic diol, polythioester diol, polythioether diol, polyhydrocarbon diol, polycarbonate diol, polysiloxane diol, polyurethane diol, or a mixture thereof or a copolymer thereof, etc., for example, any one of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly-3-methyl-tetramethylene ether glycol, THF/EO copolymerized diol, or THF/3-M-THF copolymerized diol.
Preferably, the molar ratio of the dihydric alcohol containing the ethylenically unsaturated double bond or the unsaturated triple bond to other types of dihydric alcohols is 0.3-1: 1, the other types of dihydric alcohols comprise small molecular diols and/or high molecular polyols, and the small molecular diols comprise ethylene glycol, propylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
Preferably, a has a structure as shown in formula (3):
wherein, R is3Is hydrogen or methyl, said R4Is an alkyl group of C1 to C10, preferably-CH2-CH2-.
According to one aspect of the present invention, there is provided a photocurable adhesive composition containing the photocurable polyurethane as described above.
According to an aspect of the present invention, there is provided a photocurable polyurethane resin composition for 3D printing containing the photocurable polyurethane as described above.
According to an aspect of the present invention, there is provided a use of the photocurable polyurethane as described above in photocurable 3D printing.
According to an aspect of the present invention, there is provided a method of photocuring 3D printing using the urethane resin composition for photocuring 3D printing as described above.
According to an aspect of the present invention, there is provided a 3D printing molded body obtained by photocuring 3D printing molding of the urethane resin composition for photocuring 3D printing as described above.
Has the advantages that: the photocuring rate of the photocuring polyurethane is obviously promoted, the surface drying performance of the photocuring polyurethane is effectively improved, and the obtained photocuring polyurethane has excellent flexibility, curing rate and surface drying performance.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are for purposes of illustration and not limitation.
In order to solve the defects of the prior art, the invention provides a photocuring polyurethane, a photocuring adhesive composition containing the photocuring polyurethane, a polyurethane resin composition for photocuring 3D printing, a photocuring 3D printing method and a 3D printing forming body. On the premise of good flexibility, the photocuring polyurethane resin improves the curing rate, has excellent surface drying performance, and has flexibility, curing rate and surface drying performance.
The inventors have surprisingly found that: an unsaturated double bond structure is introduced into polyurethane to improve the curing rate of resin, and finally the structure is found to obviously promote the photocuring rate of the photocuring polyurethane, so that the surface drying performance of the photocuring polyurethane is effectively improved, and the obtained photocuring polyurethane has excellent flexibility, curing rate and surface drying performance, and the invention is completed. That is, the present invention provides a method for improving the surface drying property of a photocurable polyurethane by introducing a diol having an ethylenically unsaturated double bond.
According to an aspect of the present invention, there is provided a photocurable polyurethane comprising the general formula shown in formula (1):
r is the residue of an isocyanate, and a plurality of R are the same or different;
x is the residue of dihydric alcohol, a plurality of X are the same or different, and X comprises at least one dihydric alcohol containing an ethylenically unsaturated double bond or dihydric alcohol residue containing an unsaturated triple bond, and the molecular weight of the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond is 0-1500, and 0 is not included;
a is a capping group comprising at least one ethylenically unsaturated double bond;
n is an integer of 1 to 3.
The photocurable polyurethane of the present invention is a substance that is cured by irradiation with light, and refers to a polymer that is crosslinked and polymerized into a polymer network structure. In the present specification, the UV light is mainly described, but the present invention is not limited to the UV light, and can be applied to other light.
In the present invention, for UV curing, a photocurable functional group is bonded to the polyurethane, said photocurable functional group comprising first a terminating group a, a comprising at least one ethylenically unsaturated double bond. Meanwhile, at least one of the dihydric alcohol containing the olefinic unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond exists, the double bond and the triple bond can participate in the reaction of free radicals, the service life of the free radicals is prolonged to a certain extent, and the curing rate is improved on the whole, so that the curing rate of the polyurethane can be further improved by adopting the scheme of the invention, so that the polyurethane has excellent flexibility, curing rate and surface drying performance.
In the invention, the molecular weight of the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond is 0-1500 and does not include 0, the required dihydric alcohol is difficult to realize due to too low molecular weight, the content of the original end capping agent is too low and the curing rate is too slow due to too high molecular weight, and even if the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond has the effect of resisting oxygen and inhibiting polymerization, ideal photocuring polyurethane with good curing is difficult to obtain.
In a preferred embodiment of the present invention, the number average molecular weight of the photocurable polyurethane is 3000 to 6000.
In a preferred embodiment of the present invention, the ethylenically unsaturated double bond-containing diol or unsaturated triple bond-containing diol has a molecular weight of 0 to 500 and does not include 0. The use of a relatively low molecular weight ensures better cure while maintaining the original glycol characteristics (i.e., physical properties such as elongation).
R is the residue of an isocyanate represented by R (NCO) m, which is a natural number greater than 1, preferably m is 2 or 3, and more preferably m is 2. When m is 2, R is the residue of diisocyanate represented by OCNRNCO.
Common examples of isocyanates include, but are not limited to, methylene diphenyl diisocyanate (MDI), Toluene Diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 4, 4' -dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate HDI), isophorone diisocyanate (IPDI), triphenylmethane-4, 4,4 triisocyanate, toluene-2, 4, 6-triyl triisocyanate, 1,3, 5-triazine-2, 4, 6-triisocyanate, ethyl ester L-lysine triisocyanate, or mixtures or copolymers thereof, and the like.
In the present invention, X is a residue of a diol represented by OHXOH. Both OH groups of HOXOH are alcoholic hydroxyl groups, and X's may be the same or different, but they must include at least one residue of an ethylenically unsaturated double bond-containing diol or an unsaturated triple bond-containing diol, that is, the diol includes at least one ethylenically unsaturated double bond-containing diol or unsaturated triple bond-containing diol, and the ethylenically unsaturated double bond-containing diol or unsaturated triple bond-containing diol has a molecular weight of 0 to 1500 and does not include 0. The ethylenically unsaturated double bond or unsaturated triple bond serves as a photo-curing functional group, which can increase the curing rate of the polyurethane.
In a preferred embodiment of the present invention, the ethylenically unsaturated double bond-containing diol may be a terminal hydroxyl group-modified diene- α -olefin copolymer.
In a preferred embodiment of the present invention, the unsaturated triple bond-containing diol may be 1, 4-butynediol.
The structural formula of 1, 4-butynediol is:
Alpha-Olefins (Alpha Olefins) refer to mono-Olefins with double bonds at the end of the molecular chain, and a typical but non-limiting formula is R1-CH＝CHR2As a typical but non-limiting example, R1May be selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C10-C40 condensed aryl, R2Can be selected from any one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl and substituted or unsubstituted C10-C40 condensed aryl. Typically but not by way of limitation, alpha-olefins such as styrene.
Dienes, typically but not limited to of the formula CnH(2n-2) Typical but non-limiting dienes are 1, 3-butadiene or 1, 3-pentadiene. Further, H in the diene may be substituted with a substituent such as an alkyl group of C1 to C4, for example, a methyl group, an ethyl group or the like.
Typical but non-limiting hydroxyl-terminated modified diene-alpha-olefin copolymers have the general formula shown in formula (2):
wherein n is1And n2Is a natural number greater than or equal to 1, and the number average molecular weight of the copolymer is 0-1500 and does not include 0.
A typical but non-limiting method for preparing the hydroxyl-terminated modified diene-alpha-olefin copolymer is as follows:
the preparation method of the terminal hydroxyl modified diene-alpha-olefin copolymer (1, 3-butadiene or 1, 3-pentadiene) comprises the following steps:
245 parts of 1, 3-butadiene (or 1, 3-pentadiene), 70 parts of styrene monomer, 250 parts of isopropanol, 2 parts of water and 100 parts of 35% hydrogen peroxide are added into an autoclave, and the mixture is heated to 140 ℃ and then reacted for 90 minutes. The butadiene-styrene copolymer modified by hydroxyl groups is obtained after cooling, and the number average molecular weight is about 1000.
In the present invention, the dihydric alcohol may be only an ethylenically unsaturated double bond-containing dihydric alcohol or an unsaturated triple bond-containing dihydric alcohol. In a preferred embodiment of the invention, the X-element is the residue of a diol, preferably comprising, in addition to at least one ethylenically unsaturated double bond-containing diol, other types of diols. That is, in the general formula of formula (1) of the present invention, X is a residue of a diol, and the diol preferably contains two different types of diols, one is an ethylenically unsaturated double bond-containing diol having a molecular weight of 0 to 1500 excluding 0, and the other is another type of diol, wherein the other type of diol may be, typically but not limited to, a low molecular weight polyol having a molecular weight of less than 200 such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, and may also be a high molecular weight polyol. The polymer polyol is preferably a polymer polyol having a number average molecular weight of 300 to 5000.
Typical, but non-limiting, polymeric polyols include polyether diols, polyester diols, polylactone diols, polyesteramide diols, polyacrylic diols, polythioester diols, polythioether diols, polyalkylene diols, polycarbonate diols, polysiloxane diols, polyurethane diols, or mixtures or copolymers thereof, and the like, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly-3-methyl-tetramethylene ether glycol, THF/EO copolyol (tetrahydrofuran/ethylene oxide), THF/3-M-THF copolyol (tetrahydrofuran/methyltetrahydrofuran), and the like.
In a preferred embodiment of the present invention, the molar ratio of the diol containing the ethylenically unsaturated double bond or the unsaturated triple bond to other types of diols (low molecular weight polyol having a molecular weight of less than 200, such as ethylene glycol, propylene glycol, 1, 3-propanediol or 1, 4-butanediol and/or high molecular weight polyol) is 0.3 to 1: 1. The overall improvement in the curing rate is achieved within a certain overall molecular weight range, and if the molecular weight is too high or too low (number average molecular weight of the photocurable polyurethane is 3000-6000), the effect of containing ethylenically unsaturated double bonds is not significant. In addition, the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond plays a role in assisting the curing speed of the photo-curable polyurethane resin obtained by other types of dihydric alcohol originally to be improved, and if the proportion is high, the performance of the photo-curable polyurethane resin deviates far from the original resin performance.
A is a blocking group, which is in fact the residue of a blocking agent, comprising at least one ethylenically unsaturated double bond, as a photocuring functional group.
In a preferred embodiment of the present invention, a has a group represented by formula (3):
the R is3Is hydrogen or methyl, said R4Is an alkyl group of C1 to C10, preferably-CH2-CH2-.
The preparation method of the photo-curable polyurethane of formula (1) of the present invention is not particularly limited, and the preparation method is typically but not limited to the following:
adding 900 g of other types of dihydric alcohol (polytetramethylene ether glycol, molecular weight is 1000) and 100 g of dihydric alcohol containing olefinic unsaturated double bond (hydroxyl-terminated modified diene-alpha-olefin copolymer) into a bottle with a thermometer and a stirrer, dehydrating under vacuum at 110 ℃ for 2 hours, cooling to below 70 ℃, adding 444.0 g of isophorone diisocyanate, stirring uniformly, adding 1 g of catalyst dibutyltin dilaurate, and keeping the temperature at
Degree 3 hours. Finally, 300 g of blocking agent (hydroxyethyl acrylate) and 1 g of dibutyltin dilaurate serving as a catalyst were added to block the reaction mixture, and the temperature was maintained
And (3) discharging for 3 hours to obtain the photocuring polyurethane. The hydroxyl-terminated modified diene- α -olefin copolymer is a hydroxyl-terminated modified butadiene-styrene copolymer obtained by the above-described method.
It should be understood by those skilled in the art that the preparation method is only an illustrative example, and those skilled in the art can obtain other polyurethane structures of the present invention by modifying the preparation method, such as replacing the diol with other types of diols (e.g. polyether diol, polyester diol, etc.), replacing the diol containing the ethylenically unsaturated double bond with other diols containing the ethylenically unsaturated double bond, and replacing isophorone diisocyanate with other isocyanates, so as to obtain the photocuring polyurethane with other structures. In this preparation method, the kind of the blocking agent can be selected by those skilled in the art at their discretion.
According to another aspect of the present invention, there is provided a photocurable adhesive composition containing the photocurable polyurethane as described above.
According to another aspect of the present invention, there is provided a photocurable polyurethane resin composition for 3D printing containing the photocurable polyurethane as described above.
According to another aspect of the present invention, there is provided a use of the photocurable polyurethane as described above in photocurable 3D printing.
According to another aspect of the present invention, there is provided a method of photocuring 3D printing using the urethane resin composition for photocuring 3D printing as described above.
According to another aspect of the present invention, there is provided a 3D printing molded body obtained by photocuring 3D printing molding of the urethane resin composition for photocuring 3D printing as described above.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Preparation of photo-curable polyurethanes
Synthesis example 1
Adding 900 g of dihydric alcohol (polytetramethylene ether glycol, molecular weight is 1000) and 100 g of dihydric alcohol containing olefinic unsaturated double bond (hydroxyl-terminated modified diene-alpha-olefin copolymer BS1000) into a stirrer bottle provided with a thermometer, dehydrating in vacuum at 110 ℃ for 2 hours, cooling to below 70 ℃, adding 444.0 g of isophorone diisocyanate, stirring uniformly, adding 1 g of dibutyltin dilaurate serving as a catalyst, and keeping the temperature at
Degree 3 hours. Finally, 300 g of blocking agent (hydroxyethyl acrylate) and 1 g of dibutyltin dilaurate serving as a catalyst were added to block the reaction mixture, and the temperature was maintained
And (3) discharging for 3 hours to obtain the photocuring polyurethane.
Wherein the hydroxyl-terminated modified diene-alpha-olefin copolymer is prepared by the following method:
245 parts of 1, 3-butadiene (or 1, 3-pentadiene), 70 parts of styrene monomer, 250 parts of isopropanol, 2 parts of water and 100 parts of 35% hydrogen peroxide are added into an autoclave, and the mixture is heated to 140 ℃ and then reacted for 90 minutes. Cooling and post-processing to obtain the terminal hydroxyl modified butadiene-styrene copolymer BS 1000. The number average molecular weight is about 1000.
Synthesis examples 2 to 4 are shown in Table 1
TABLE 1
Of these, NL1005B polycarbonate (Mitsubishi, MI TSUBI SH I ENEBIOL NL1005B) had a number average molecular weight of 1000.
2. Photocurable composition
The above-mentioned synthesis examples of the present invention, which were prepared by mixing the polyurethane of synthesis example 1 with a diol having no ethylenically unsaturated double bond or unsaturated triple bond added thereto, were verified for their effects on the properties of the cured product by the following formulation tests.
Synthesis example 1 polyurethane: 50 parts, hydroxyethyl acrylate: 20 parts of isobornyl methacrylate: 20 parts of silicon gas: 5 parts, photoinitiator 184: 2.5 parts of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus 2.5 parts.
Test experiments: tack-free testing
An LED light source with the wavelength of 365nm is selected and illuminates for 30-2 s. After 10min the surface was observed to cure.
The polyurethane of synthesis example 1 was replaced with the polyurethane of synthesis/comparative examples 1 to 4, and a tack-free test was performed to observe the curing.
| Sample (I) | Tack free cure time |
| Synthesis example 1 | 8s |
| Comparative example 1 | 10s |
| Synthesis example 2 | 6s |
| Comparative example 2 | 10s |
| Synthesis example 3 | 12s |
| Comparative example 3 | 16s |
| Synthesis example 4 | Slightly sticky for 14s |
| Comparative example 4 | Slightly sticky for 22s |
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present application and the technical principles employed. It will be understood by those skilled in the art that the present application is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the application. Therefore, although the present application has been described in more detail with reference to the above embodiments, the present application is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present application, and the scope of the present application is determined by the scope of the appended claims.
Claims (10)
1. A photocurable polyurethane comprising the general formula shown in formula (1):
r is the residue of an isocyanate, and a plurality of R are the same or different;
x is the residue of dihydric alcohol, a plurality of X are the same or different, and X comprises at least one residue of dihydric alcohol containing an ethylenically unsaturated double bond or dihydric alcohol containing an unsaturated triple bond, and the molecular weight of the dihydric alcohol containing the ethylenically unsaturated double bond or the dihydric alcohol containing the unsaturated triple bond is 0-1500 and does not comprise 0;
a is a capping group comprising at least one ethylenically unsaturated double bond;
n is an integer of 1 to 3.
2. The photocurable polyurethane of claim 1, wherein the photocurable polyurethane has a number average molecular weight of 3000 to 6000;
preferably, the ethylenically unsaturated double bond-containing diol or unsaturated triple bond-containing diol has a molecular weight of 0 to 500 and does not include 0;
preferably, as R, it is the residue of an isocyanate represented by R (NCO) m, said m being a natural number greater than 1, preferably m is 2 or 3, more preferably m is 2;
preferably, the isocyanate comprises methylene diphenyl diisocyanate, toluene diisocyanate, p-phenyl diisocyanate, 4, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate HDI, isophorone diisocyanate, triphenylmethane-4, 4,4 triisocyanate, toluene-2, 4, 6-triyl triisocyanate, 1,3, 5-triazine-2, 4, 6-triisocyanate, ethyl ester L-lysine triisocyanate or a mixture thereof or a copolymer thereof.
3. The photocurable polyurethane according to claim 1 or 2, wherein the diol having an ethylenically unsaturated double bond is a terminal hydroxyl group-modified diene- α -olefin copolymer;
preferably, the unsaturated triple bond-containing diol is 1, 4-butynediol;
preferably, the hydroxyl-terminated modified diene- α -olefin copolymer has a general formula shown in formula (2):
wherein n is1And n2Is a natural number greater than or equal to 1, and the number average molecular weight of the copolymer is 0-1500 and does not include 0.
4. The photocurable polyurethane of claim 1 or 2 wherein the diol further comprises ethylene glycol, propylene glycol, 1, 3-propanediol, or 1, 4-butanediol;
preferably, the dihydric alcohol further comprises high-molecular polyol, and the high-molecular polyol is high-molecular polyol with the number average molecular weight of 300-5000;
preferably, the high molecular polyol includes polyether diol, polyester diol, polylactone diol, polyesteramide diol, polyacrylic diol, polythioester diol, polythioether diol, polyhydrocarbon diol, polycarbonate diol, polysiloxane diol, polyurethane diol, or a mixture thereof or a copolymer thereof, etc., for example, any one of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly-3-methyl-tetramethylene ether glycol, THF/EO copolymerized diol, or THF/3-M-THF copolymerized diol;
preferably, the molar ratio of the dihydric alcohol containing the ethylenically unsaturated double bond or the unsaturated triple bond to other types of dihydric alcohols is 0.3-1: 1, the other types of dihydric alcohols comprise small molecular diols and/or high molecular polyols, and the small molecular diols comprise ethylene glycol, propylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
5. The photocurable polyurethane of claim 1 or 2, wherein a has the structure according to formula (3):
wherein, R is3Is hydrogen or methyl, said R4Is an alkyl group of C1 to C10, preferably-CH2-CH2-.
6. A photocurable adhesive composition comprising the photocurable polyurethane according to any one of claims 1-5.
7. A photocurable polyurethane resin composition for 3D printing comprising the photocurable polyurethane according to any one of claims 1-5.
8. Use of a photocurable polyurethane according to any of claims 1-5 for photocuring 3D printing.
9. A method of photocuring 3D printing using the photocuring 3D printing polyurethane resin composition of claim 7.
10. A3D printing molded body obtained by photocuring 3D printing molding of the photocuring 3D printing polyurethane resin composition according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110593721.8A CN113278125A (en) | 2021-05-28 | 2021-05-28 | Photo-curing polyurethane and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110593721.8A CN113278125A (en) | 2021-05-28 | 2021-05-28 | Photo-curing polyurethane and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113278125A true CN113278125A (en) | 2021-08-20 |
Family
ID=77282444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110593721.8A Pending CN113278125A (en) | 2021-05-28 | 2021-05-28 | Photo-curing polyurethane and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113278125A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316203A (en) * | 2021-12-21 | 2022-04-12 | 郑州轻工业大学 | Polyurethane acrylate photocuring resin material, preparation method thereof and preparation method of polyurethane acrylate prepolymer |
| CN117106403A (en) * | 2023-07-17 | 2023-11-24 | 韦尔通科技股份有限公司 | Flexible solvent-free double-component PU (polyurethane) structural adhesive and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910215A (en) * | 2004-01-14 | 2007-02-07 | 氰特表面技术有限公司 | Adhesives |
| CN101372530A (en) * | 2008-08-08 | 2009-02-25 | 中国工程物理研究院化工材料研究所 | Aqueous photo-curing polyurethane resin and preparation thereof |
| CN102585155A (en) * | 2012-01-20 | 2012-07-18 | 王跃川 | PUA (polyurethane) reactive resin and preparation method thereof |
| CN103135348A (en) * | 2011-11-29 | 2013-06-05 | 富士胶片株式会社 | Resin composition for laser engraving, flexographic printing plate precursor for laser engraving and process for producing same, and flexographic printing plate and process for making same |
| CN104892890A (en) * | 2014-09-30 | 2015-09-09 | 深圳市浩力新材料技术有限公司 | Ultra-flexible polyurethane acrylate resin and liquid-state optical adhesive composition thereof |
| CN105294986A (en) * | 2015-10-29 | 2016-02-03 | 广州擎天材料科技有限公司 | Solid-state hypocrystalline unsaturated polyurethane prepolymer and preparation method thereof |
| CN107502273A (en) * | 2017-08-31 | 2017-12-22 | 瑞安市隆联新材料有限公司 | A kind of preparation of solvent-free double solidification polyurethane binder |
| CN109957083A (en) * | 2017-12-25 | 2019-07-02 | 江苏百赛飞生物科技有限公司 | A kind of manufacturing method of unsaturated polyol and photocurable polyurethane and they prepared therefrom |
| CN111040102A (en) * | 2019-12-02 | 2020-04-21 | 中国科学院福建物质结构研究所 | Photosensitive resin and preparation method and application thereof |
-
2021
- 2021-05-28 CN CN202110593721.8A patent/CN113278125A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910215A (en) * | 2004-01-14 | 2007-02-07 | 氰特表面技术有限公司 | Adhesives |
| CN101372530A (en) * | 2008-08-08 | 2009-02-25 | 中国工程物理研究院化工材料研究所 | Aqueous photo-curing polyurethane resin and preparation thereof |
| CN103135348A (en) * | 2011-11-29 | 2013-06-05 | 富士胶片株式会社 | Resin composition for laser engraving, flexographic printing plate precursor for laser engraving and process for producing same, and flexographic printing plate and process for making same |
| CN102585155A (en) * | 2012-01-20 | 2012-07-18 | 王跃川 | PUA (polyurethane) reactive resin and preparation method thereof |
| CN104892890A (en) * | 2014-09-30 | 2015-09-09 | 深圳市浩力新材料技术有限公司 | Ultra-flexible polyurethane acrylate resin and liquid-state optical adhesive composition thereof |
| CN105294986A (en) * | 2015-10-29 | 2016-02-03 | 广州擎天材料科技有限公司 | Solid-state hypocrystalline unsaturated polyurethane prepolymer and preparation method thereof |
| CN107502273A (en) * | 2017-08-31 | 2017-12-22 | 瑞安市隆联新材料有限公司 | A kind of preparation of solvent-free double solidification polyurethane binder |
| CN109957083A (en) * | 2017-12-25 | 2019-07-02 | 江苏百赛飞生物科技有限公司 | A kind of manufacturing method of unsaturated polyol and photocurable polyurethane and they prepared therefrom |
| CN111040102A (en) * | 2019-12-02 | 2020-04-21 | 中国科学院福建物质结构研究所 | Photosensitive resin and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316203A (en) * | 2021-12-21 | 2022-04-12 | 郑州轻工业大学 | Polyurethane acrylate photocuring resin material, preparation method thereof and preparation method of polyurethane acrylate prepolymer |
| CN117106403A (en) * | 2023-07-17 | 2023-11-24 | 韦尔通科技股份有限公司 | Flexible solvent-free double-component PU (polyurethane) structural adhesive and preparation method thereof |
| CN117106403B (en) * | 2023-07-17 | 2024-06-04 | 韦尔通科技股份有限公司 | Flexible solvent-free double-component PU (polyurethane) structural adhesive and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6365674B1 (en) | Thermoplastic polyurethane resin | |
| US7262260B2 (en) | Segmented urea and siloxane copolymers and their preparation methods | |
| CN104884492B (en) | Thermoplastic polyurethane with the crystallization end of the chain | |
| CN106459344B (en) | Curable urethane (meth) acrylate polymer compositions and methods | |
| TW201725221A (en) | Polymer, composition for making polyurethane, and method of preparing polyurethane, elastomeric product and polyfarnesene | |
| US20050288476A1 (en) | Thermoplastic copolymers through stoichiometric reactions between diisocyanates and oligomeric diols and diamines | |
| KR102441743B1 (en) | Method for producing carboxyl group-containing aqueous resin composition, molded article, and polycarbodiimide compound | |
| KR20050055704A (en) | Polyurethane and polyurethane-urea elastomers from polytrimethylene ether glycol | |
| CA2009456A1 (en) | Bulk polyurethane ionomers | |
| US20080139687A1 (en) | Vinyl Ether/Acrylate Block Resins, Compositions and Methods of Making Same | |
| WO2006083343A1 (en) | Vinyl ether/acrylate block resins, compositions and methods of making same | |
| CN113278125A (en) | Photo-curing polyurethane and application thereof | |
| CN101321796A (en) | Low haze thermoplastic polyurethane using co-chain extenders | |
| CN107903372A (en) | A kind of UV photocurings flexibility ultra-branched polyurethane acrylate resin and preparation method and application | |
| KR100325895B1 (en) | Extrudeable Thermoplastic Elastic Urea Extended Polyurethane | |
| EP1090940A2 (en) | Soft, transparent and processable thermoplastic polyurethane | |
| JP2525181B2 (en) | Silicone-modified polyurethane and method for producing the same | |
| CN113755126B (en) | Adhesive and preparation method and application thereof | |
| TW202112869A (en) | Thermoplastic polyurethane and process for making a thermoplastic polyurethane and components thereof | |
| US20080027201A1 (en) | Segmented urea and siloxane copolymers and their preparation methods | |
| JP2004189878A (en) | Curable composition | |
| TW202204463A (en) | Active energy ray-curable polyurethane resin, curable resin composition, and production method for active energy ray-curable polyurethane resin | |
| JP4102505B2 (en) | Urethane resin composition | |
| JP3096559B2 (en) | Moisture-curable urethane composition | |
| JPS62225516A (en) | Silicone-modified polyurethane and silicone compound for modification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210820 |
|
| RJ01 | Rejection of invention patent application after publication |