CN115010901A - Low-viscosity hydrolysis-resistant photocuring polyurethane resin and preparation method and application thereof - Google Patents
Low-viscosity hydrolysis-resistant photocuring polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN115010901A CN115010901A CN202210695476.6A CN202210695476A CN115010901A CN 115010901 A CN115010901 A CN 115010901A CN 202210695476 A CN202210695476 A CN 202210695476A CN 115010901 A CN115010901 A CN 115010901A
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- Prior art keywords
- polyurethane resin
- low
- acid
- viscosity
- resistant
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 56
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 38
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 38
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 41
- 229920000570 polyether Polymers 0.000 claims abstract description 41
- -1 ester polyol Chemical class 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002981 blocking agent Substances 0.000 claims description 5
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 2
- 229920000728 polyester Polymers 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003085 diluting agent Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-viscosity hydrolysis-resistant photocuring polyurethane resin and a preparation method and application thereof. According to the preparation method, particularly the reaction sequence of the raw materials, the polyester structure in the prepared polyether ester polyol can be directly linked with NCO groups in isocyanate at two sides to form a urethane chain end through reaction, and then the polyester chain end of another polyether ester molecule is linked, so that the hard segment length in the polyurethane resin is increased, the hydrolysis resistance of the polyurethane resin is improved, the bulk viscosity is low, the polyurethane resin is suitable for production and use, a solvent or an active diluent is not needed in the use process, and the polyurethane resin is more economic and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-viscosity hydrolysis-resistant photocuring polyurethane resin and a preparation method and application thereof.
Background
The light-cured resin is a photosensitive resin with relatively low molecular mass, has reactive groups such as unsaturated double bonds or epoxy groups, and can activate a photoinitiator to carry out curing reaction under the irradiation of ultraviolet light or visible light. It has the characteristics of high curing speed, less pollution, energy conservation, excellent performance of cured products and the like, so that it is widely used in the fields of coatings, printing, adhesives, optical fibers, compact discs, electronic elements or electronic devices and the like.
Common photocurable polyurethane resins are synthesized from polyester polyols or polyether polyols, but both have certain disadvantages. Specifically, though the light-cured polyurethane resin prepared by synthesizing polyether polyol has low bulk viscosity, the cured product has low strength and poor wear resistance, and the practical application is greatly limited; although the strength of the photocuring polyurethane resin prepared by synthesizing polyester polyol is high after curing, the photocuring polyurethane resin is basically solid at room temperature due to overlarge viscosity of the photocuring polyurethane resin, and can be normally used after being diluted by adding a solvent, an active diluent and the like, so that the energy consumption is greatly increased in the production and use processes, the production and coating efficiency is reduced, and the requirement on equipment is high; meanwhile, the polyester structure contains a large amount of ester groups, so that the hydrolysis resistance is poor, and the application performance is limited.
In order to solve the technical problems, polyether ester polyol is adopted as a raw material to synthesize polyurethane resin in the prior art, so that the hydrolysis resistance of the material can be improved within a certain range, but the viscosity of the material is still higher. Therefore, if the photo-curing polyurethane resin with the advantages of both is synthesized, the bulk viscosity of the photo-curing polyurethane resin is suitable for production and use, and the photo-curing polyurethane resin has higher strength and hydrolysis resistance, so that the application range of the photo-curing polyurethane resin can be greatly expanded, the production cost is saved, and the production efficiency is improved.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the polyurethane resin in the prior art is high in bulk viscosity, is not suitable for production and use (or needs to use a solvent and a reactive diluent), and the strength and hydrolysis resistance of the photocured polyurethane resin are required to be further improved, so that the low-viscosity hydrolysis-resistant photocured polyurethane resin and the preparation method and application thereof are provided.
Therefore, the invention provides the following technical scheme:
the invention provides a low-viscosity hydrolysis-resistant photocuring polyurethane resin, which comprises the following steps:
s1, polyether polyol is used as an initiator to react with dibasic acid or anhydride thereof and dihydric alcohol to obtain polyether polyol,
wherein the dihydric alcohol is a dihydric alcohol containing an alkyl branched chain;
s2, reacting the obtained polyether ester polyol with isocyanate and a blocking agent to obtain the low-viscosity hydrolysis-resistant photocuring polyurethane resin.
Optionally, the dihydric alcohol is at least one of 1, 3-butanediol and neopentyl glycol.
Optionally, the polyetherester polyol has a functionality of 2 and a number average molecular weight of 1000-.
Optionally, in step S1, the polyether polyol, the dibasic acid or the anhydride thereof, and the mass ratio of the dibasic alcohol is 100: (50-100): (50-100).
Optionally, step S1 is: reacting polyether polyol with dibasic acid or anhydride thereof in the presence of a catalyst at the temperature of 140-160 ℃ in a protective atmosphere, reacting until the acid value of the system is 150-275 mgKOH/g, adding the dibasic alcohol, raising the temperature to 180-220 ℃, reacting until the acid value of the system is less than 2mgKOH/g, and removing unreacted raw materials to obtain polyether ester polyol;
optionally, the catalyst is used in an amount of 0.1-2% by mass of the total reaction mass.
Optionally, in step S2, the mass ratio of the polyether ester polyol, the isocyanate, and the blocking agent is 100: (10-50): (10-30).
Optionally, step S2 is carried out in the presence of a catalyst, the amount of catalyst being 0.1-2% of the total reactant mass.
Typically, but not by way of limitation, the catalyst in step S1 may or may not be the same as the catalyst in step S2.
Optionally, the reaction temperature in step S2 is 60-100 ℃;
optionally, the reaction temperature is 70-90 ℃.
Optionally, the preparation method of the low-viscosity hydrolysis-resistant photo-curable polyurethane resin meets at least one of the following (1) to (8):
(1) the polyether polyol is polyoxypropylene polyol, and the functionality is 2;
(2) the number average molecular weight of the polyether polyol is 400-1000;
(3) the number average molecular weight of the polyether polyol is 400-800;
(4) the dibasic acid or the anhydride thereof is at least one of phthalic acid, terephthalic acid, isophthalic acid, 1, 6-adipic acid, 1, 4-succinic acid, maleic acid, fumaric acid and corresponding acid anhydride thereof;
(5) the isocyanic acid is one or a mixture of more of aliphatic isocyanate or aromatic isocyanate;
(6) the end capping agent is one or a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate;
(7) the catalyst is at least one of an organic tin catalyst, an organic bismuth catalyst or an organic titanium catalyst;
(8) the protective atmosphere is helium, nitrogen or argon.
The invention also provides the low-viscosity hydrolysis-resistant photocuring polyurethane resin prepared by the preparation method.
The invention also provides application of the low-viscosity hydrolysis-resistant photocuring polyurethane resin in the fields of photocuring coatings, photocuring adhesives and the like.
The technical scheme of the invention has the following advantages:
the invention provides a preparation method of a low-viscosity hydrolysis-resistant light-cured polyurethane resin, which comprises the following steps: s1, polyether polyol is used as an initiator to react with dibasic acid or anhydride thereof and dihydric alcohol to obtain polyether ester polyol, wherein the dihydric alcohol is dihydric alcohol containing alkyl branched chain; s2, reacting the obtained polyether ester polyol with isocyanate and a blocking agent to obtain the low-viscosity hydrolysis-resistant photocuring polyurethane resin. The invention can give consideration to both low viscosity and hydrolysis resistance by changing the synthesis process and the types of raw materials. Specifically, the specific dihydric alcohol containing the alkyl branched chain is selected, so that the hydrolysis of a polyester structural unit in the polyurethane resin can be effectively avoided, the viscosity of the product is low, and if the conventional dihydric alcohol without the branched chain is selected, such as ethylene glycol or 1, 4-butanediol, the obtained product is generally solid at normal temperature; by combining the preparation method of the invention, particularly the reaction sequence of the raw materials, the polyester structure in the prepared polyether ester polyol can be directly linked with NCO groups in isocyanate at two sides to form a urethane chain end through reaction, and then the polyester chain end of another polyether ester molecule is linked to increase the length of a hard segment in the polyurethane resin (the inventor finds that if the hard segment is concentrated and easily forms a micro-crystalline structure, the hydrolysis resistance of the polyurethane resin is improved to a certain extent), the hydrolysis resistance of the polyurethane resin is improved, and meanwhile, the bulk viscosity is lower, so that the polyurethane resin is suitable for production and use, and a solvent or an active diluent is not needed in the using process, so that the polyurethane resin is more economic and environment-friendly.
The preparation method of the low-viscosity hydrolysis-resistant light-cured polyurethane resin provided by the invention can ensure that the stability of a synthetic product can be ensured and the viscosity of the product can be kept in a reasonable range by limiting the functionality and the molecular weight of polyether polyol and polyether ester polyol.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a low-viscosity hydrolysis-resistant photo-curable polyurethane resin, and the preparation method comprises the following steps:
100g of PPG1000, 80g of 1, 6-adipic acid and 1.5g of dibutyltin dilaurate are added into a four-neck flask with a stirrer, nitrogen is introduced to bring out water generated by the reaction, the temperature is raised to 150 ℃, 55g of 1, 3-butanediol is added when the acid value of the system reaches 275mgKOH/g, the reaction temperature is gradually raised to 220 ℃ along with the rise of the polymerization degree, then vacuum dehydration is carried out for 1h, and when the acid value of the test system is less than 2mgKOH/g, unreacted raw materials are distilled out and discharged. The polyether ester polyol product was tested to have a hydroxyl value of 42.3mgKOH/g and a functionality of 2.
100g of the polyether ester polyol, 25g of isophorone diisocyanate, 20g of hydroxyethyl acrylate and 1g of dibutyltin dilaurate are reacted at 80 ℃ for 2h, the NCO value of a test system is less than 0.1%, and the polyurethane acrylate resin is discharged and tested to have the viscosity of 21000mPa.s (25 ℃).
Method for testing NCO value: refer to the determination of the isocyanate group content in the polyurethane prepolymer HG/T2409-1992 (the same applies below).
Example 2
The embodiment provides a low-viscosity hydrolysis-resistant photocuring polyurethane resin, which is prepared by the following steps:
adding 100g of PPG400, 60g of 1, 4-succinic acid and 1.4g of stannous octoate into a four-neck flask with stirring, introducing nitrogen to bring out water generated by reaction, heating to 150 ℃, adding 75g of neopentyl glycol when the acid value of a system reaches 187mgKOH/g, gradually raising the reaction temperature to 220 ℃ along with the rise of the polymerization degree, then carrying out vacuum dehydration for 1h, and distilling out unreacted raw materials when the acid value of the test system is less than 2mgKOH/g, and then discharging. The polyether ester polyol product has a hydroxyl value of 90.4mgKOH/g and a functionality of 2.
100g of the polyether ester polyol, 25g of isophorone diisocyanate, 25g of hydroxyethyl acrylate and 1g of dibutyltin dilaurate are reacted at 80 ℃ for 2h, the NCO value of a test system is less than 0.1%, and the polyurethane acrylate resin is discharged and tested to have the viscosity of 40000mPa.s (25 ℃).
Example 3
The embodiment provides a low-viscosity hydrolysis-resistant photocuring polyurethane resin, which is prepared by the following steps:
100g of PPG400, 90g of 1, 6-adipic acid and 1.3g of tetrabutyl titanate are added into a four-neck flask with a stirrer, nitrogen is introduced to bring out water generated by the reaction, the temperature is raised to 150 ℃, when the acid value of the system reaches 227mgKOH/g, 20g of 1, 3-butanediol and 48g of neopentyl glycol are added, the reaction temperature is gradually raised to 220 ℃ along with the rise of the polymerization degree, then vacuum dehydration is carried out for 1h, and when the acid value of the test system is less than 2mgKOH/g, unreacted raw materials are distilled out and discharged. The polyether ester polyol product was tested to have a hydroxyl value of 81.5mgKOH/g and a functionality of 2.
100g of the polyether ester polyol is reacted with 40g of isophorone diisocyanate, 25g of hydroxyethyl acrylate and 0.1g of dibutyltin dilaurate at the temperature of 80 ℃, the reaction time is 2h, the NCO value of a test system is less than 0.1 percent, and the viscosity of the polyurethane acrylate resin is 37000mPa.s (25 ℃) after the discharge is tested.
Comparative example 1
A preparation method of the polyurethane resin comprises the following steps:
100g of polyether polyol PPG1000 (hydroxyl value of 112mgKOH/g), 40g of isophorone diisocyanate, 20g of hydroxyethyl acrylate and 0.1g of dibutyltin dilaurate are reacted at 80 ℃ for 2h, and when the NCO value of a test system is less than 0.1%, discharging. The resin viscosity was tested to be 11500mPa.s (25 ℃).
Comparative example 2
A preparation method of the polyurethane resin comprises the following steps:
100g of PBA polyester polyol (a commercial product of 1, 4-butanediol adipate polyol with a hydroxyl value of 112mgKOH/g), 40g of isophorone diisocyanate, 20g of hydroxyethyl acrylate and 0.1g of dibutyltin dilaurate are reacted at 80 ℃, the reaction time is 2 hours, and when the NCO value of a test system is less than 0.1%, discharging. The resin was tested to be a solid at ambient temperature and to have a viscosity of 89000mPa.s at 60 ℃.
Comparative example 3
A preparation method of the polyurethane resin comprises the following steps: the difference compared to example 1 is the use of 1, 3-propanediol instead of 1, 3-butanediol. The test shows that the solid is pasty solid at normal temperature.
Performance testing
The photocurable resins prepared in the examples and the comparative examples are respectively mixed and stirred uniformly at 60 ℃ according to the formula shown in Table 1, then an automatic coating machine is adopted for coating, the thickness of the coating is controlled to be 1.0 +/-0.1 mm, and after photocuring is finished, the tensile strength and the elongation at break are tested according to GB/T1040; the pencil hardness is tested by referring to GB/T6739-: flexibility was tested with reference to GB/T1731-: the abrasion resistance is tested by referring to GB/T1768-2006: the adhesion is tested by reference to GB/T9286-1998, and the specific test results are shown in Table 2. The strength test after soaking in water is shown in table 3.
TABLE 1 formulation
TABLE 2 cured Performance test results
TABLE 3
Retention ═ test value after treatment ÷ value before treatment × 100%.
Because of the structure of polyester, ester bonds can be broken and decomposed when the ester groups meet water under the condition of acid and alkali, and then macroscopic change is the reduction of physical and chemical properties, polyether ester synthesized by polyether polyol with a branched chain structure has resistance to hydrolysis conditions because the polyester chain segment is connected to the polyether chain segment and is protected by the branched chain, and therefore, after testing, the reduction of physical and chemical properties of each embodiment is greatly reduced compared with that of polyester resin. The polyurethane resin synthesized by the polyether ester has obviously superior performance after curing, basically has no difference with the performance of the light-curable polyurethane resin synthesized by polyester, but has better hydrolysis resistance than the light-curable polyurethane resin with a polyester structure, and has much lower viscosity than the light-curable polyurethane resin, thereby being convenient to use and improving the use efficiency. Comparative example 3 is a pasty solid at room temperature, and has too high viscosity to be fluidized by heating, which causes difficulty in use and too high energy consumption, and secondly, has too high viscosity to be used by adding a diluent or a solvent. If the viscosity is not reduced, the leveling property is poor, the thickness of the coating film is uneven, and the performance and the appearance are affected. Under the formulation of table 1, the product of comparative example 3 could not be coated and the subsequent performance test could not be performed.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The preparation method of the low-viscosity hydrolysis-resistant photocuring polyurethane resin is characterized by comprising the following steps of:
s1, polyether polyol is used as an initiator to react with dibasic acid or anhydride thereof and dihydric alcohol to obtain polyether polyol,
wherein the dihydric alcohol is dihydric alcohol containing alkyl branched chain;
s2, reacting the obtained polyether ester polyol with isocyanate and a blocking agent to obtain the low-viscosity hydrolysis-resistant photocuring polyurethane resin.
2. The method for preparing the low-viscosity hydrolysis-resistant photo-curable polyurethane resin as claimed in claim 1, wherein the diol is at least one of 1, 3-butanediol and neopentyl glycol.
3. The method for preparing the low-viscosity hydrolysis-resistant photo-curable polyurethane resin as claimed in claim 1 or 2, wherein the polyetherester polyol has a functionality of 2 and a number average molecular weight of 1000-3000.
4. The method for preparing the low-viscosity hydrolysis-resistant light-cured polyurethane resin as claimed in claim 1, wherein the polyether polyol, the dibasic acid or the anhydride thereof and the diol in the step S1 are mixed in a mass ratio of 100: (50-100): (50-100).
5. The method for preparing the low-viscosity hydrolysis-resistant photo-curable polyurethane resin as claimed in claim 4, wherein the step S1 is: reacting polyether polyol with dibasic acid or anhydride thereof in the presence of a catalyst at the temperature of 140-160 ℃ in a protective atmosphere, reacting until the acid value of the system is 150-275 mgKOH/g, adding the dibasic alcohol, raising the temperature to 180-220 ℃, reacting until the acid value of the system is less than 2mgKOH/g, and removing unreacted raw materials to obtain polyether ester polyol;
optionally, the catalyst is used in an amount of 0.1 to 2% by mass of the total reaction mass.
6. The method for preparing the low-viscosity hydrolysis-resistant photo-curable polyurethane resin as claimed in claim 1, wherein in step S2, the mass ratio of the polyetherester polyol, the isocyanate and the blocking agent is 100: (10-50): (10-30);
optionally, step S2 is carried out in the presence of a catalyst, the amount of catalyst being 0.1-2% of the total reactant mass.
7. The method for preparing the low-viscosity hydrolysis-resistant photo-curable polyurethane resin as claimed in claim 6, wherein the reaction temperature in step S2 is 60-100 ℃;
optionally, the reaction temperature is 70-90 ℃.
8. The method for preparing a low viscosity hydrolysis resistant photo-curable polyurethane resin according to any one of claims 1 to 7, wherein at least one of the following (1) to (7) is satisfied:
(1) the polyether polyol is polyoxypropylene polyol, and the functionality is 2;
(2) the number average molecular weight of the polyether polyol is 400-1000;
(3) the dibasic acid or the anhydride thereof is at least one of phthalic acid, terephthalic acid, isophthalic acid, 1, 6-adipic acid, 1, 4-succinic acid, maleic acid, fumaric acid and corresponding anhydride thereof;
(4) the isocyanic acid is one or a mixture of more of aliphatic isocyanate or aromatic isocyanate;
(5) the end-capping reagent is one or a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate;
(6) the catalyst is at least one of an organic tin catalyst, an organic bismuth catalyst or an organic titanium catalyst;
(7) the protective atmosphere is helium, nitrogen or argon.
9. A low-viscosity hydrolysis-resistant photo-curable polyurethane resin prepared by the preparation method of any one of claims 1 to 8.
10. The use of the low viscosity hydrolysis resistant photo-curable polyurethane resin of claim 9 in the fields of photo-curable coatings and photo-curable adhesives.
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