CN117700682A - Novel polyurethane modified waterborne epoxy acrylate and preparation method thereof - Google Patents
Novel polyurethane modified waterborne epoxy acrylate and preparation method thereof Download PDFInfo
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- CN117700682A CN117700682A CN202311749523.1A CN202311749523A CN117700682A CN 117700682 A CN117700682 A CN 117700682A CN 202311749523 A CN202311749523 A CN 202311749523A CN 117700682 A CN117700682 A CN 117700682A
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000004814 polyurethane Substances 0.000 title claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000539 dimer Substances 0.000 claims abstract description 10
- GKNOFYAURJKRPM-UHFFFAOYSA-N hydroxymethyl 2-hydroxyacetate Chemical compound OCOC(=O)CO GKNOFYAURJKRPM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 22
- 239000012948 isocyanate Substances 0.000 claims description 21
- 150000002513 isocyanates Chemical group 0.000 claims description 21
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 15
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- -1 caprolactone modified hydroxyl acrylate Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical class OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 13
- 238000001723 curing Methods 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000012216 screening Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 14
- 238000005507 spraying Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- C08G18/67—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
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- 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
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 discloses a preparation method of novel polyurethane modified waterborne epoxy acrylate, which comprises the steps of reacting dimethylol carboxylic acid with diacid or anhydride to obtain diacid with a side group containing a large number of carboxyl groups, reacting acrylic monomers with different epoxy resins to obtain a product with terminal epoxy terminal double bonds, and reacting the product with diacid with the side group containing a large number of carboxyl groups to obtain an intermediate I; the dimer acid modified high-elasticity dihydric alcohol reacts with flexible diisocyanate to obtain an isocyanate-terminated product, and the isocyanate-terminated product is blocked at one end by modified hydroxyl acrylate to obtain an intermediate II; and (3) partially modifying the intermediate I by using the intermediate II to obtain an intermediate III, and finally carrying out phase inversion on the intermediate III by using a triethylamine aqueous solution. The invention obtains the optimal raw material composition, proportion and synthesis steps through a large number of experimental screening, and the prepared water-based photo-curing prepolymer has excellent storage stability, quick curing and good adhesive force, hardness and flexibility.
Description
Technical Field
The invention relates to an oligomer for photosensitive coating, in particular to a preparation method of novel polyurethane modified waterborne epoxy acrylate, and belongs to the technical field of high polymer materials.
Background
Ultraviolet curing is a material surface treatment technology which appears in the 60 s of the 20 th century, and is a technology that a photoinitiator (or a photosensitizer) is added into a system (generally called a photo-curing system) with a special formula, and the photoinitiator absorbs high-intensity ultraviolet light generated in ultraviolet photo-curing equipment to generate active free radicals or cations, so that polymerization, crosslinking, grafting and other reactions are initiated, and the reaction is converted from liquid to solid in a certain period of time. In recent years, the increasingly strict environmental protection requirements lead the research and development of the water-based system by domestic researchers at the present stage to be far more focused than any other time, and the use of the water-based system is dominant in part of application fields, especially in the spraying field which needs an organic solvent for viscosity reduction. Although the photo-curing system has the characteristic of '5E' (i.e. high efficiency, energy saving, environmental protection, economy and wide applicability), the photo-curing solvent-free spraying generally requires a large amount of photo-curing monomer to dilute the system, while the photo-curing monomer with low viscosity has poor film forming property, and the finally obtained paint film has higher cost or less excellent performance, so that the photo-curing solvent-free spraying system is improved to a situation which can be widely used. Although the water-based photo-curing also contains solvent water, the water is taken as an environment-friendly solvent, and does not influence the environment-friendly requirement of the system, so that the water-based photo-curing is a solvent-free scheme for developing a new way.
According to the invention, through the creative design scheme, the novel polyurethane modified waterborne epoxy acrylate is synthesized, so that the waterborne photo-curing prepolymer with excellent storage stability and quick curing speed is creatively obtained, and a paint film prepared from the prepolymer through solvent-free spraying has excellent adhesive force, moderate mechanical properties and excellent comprehensive properties.
Disclosure of Invention
The invention aims to: the invention aims to provide novel polyurethane modified waterborne epoxy acrylate, which is screened by a large number of experiments, wherein dimethylol carboxylic acid is firstly selected to react with diacid or anhydride to obtain diacid with a side group containing a large number of carboxyl groups, an acrylic monomer is used to react with different epoxy resins to obtain a terminal epoxy terminal double bond product, and then the product is reacted with diacid with the side group containing a large number of carboxyl groups to obtain an intermediate I; selecting dimer acid modified high-elasticity dihydric alcohol with proper molecular weight to react with flexible diisocyanate to obtain an isocyanate-terminated product, and then using modified hydroxyl acrylate to seal one end of the isocyanate-terminated product to obtain an intermediate II; and finally, partially modifying the intermediate I by using the intermediate II to obtain an intermediate III, and finally, carrying out phase inversion on the intermediate III by using a triethylamine aqueous solution to obtain the final novel polyurethane modified waterborne epoxy acrylate. According to the invention, the optimal raw material composition, the optimal proportion and the optimal technological synthesis steps are obtained through a large number of experimental screening, the prepared aqueous photo-curing prepolymer is excellent in storage stability and quick in curing, the prepolymer can be sprayed without an organic solvent, and a paint film prepared through spraying has excellent adhesive force, moderate mechanical properties and excellent comprehensive properties.
The technical scheme adopted by the invention for realizing the purposes is as follows:
the preparation method of the novel polyurethane modified waterborne epoxy acrylate is characterized by comprising the following steps of:
(1) Firstly, selecting 5-10 parts by mass of dimethylol carboxylic acid and 5-20 parts by mass of dibasic acid or anhydride to prepare dibasic acid with a side group containing a large amount of carboxyl groups under a certain reaction condition a; 0.5-2 parts by mass of acrylic monomer is selected to react with 2-10 parts by mass of different epoxy resins under a certain reaction condition b to obtain an epoxy end double bond product; and finally, continuously reacting the dibasic acid with a large amount of carboxyl groups on the side groups and the product with the end epoxy-terminated double bonds under a certain reaction condition c, and obtaining an intermediate I when the acid value of the system is stable and unchanged.
(2) 5-20 parts by mass of 1000 molecular weight dimer acid modified high-elasticity dihydric alcohol and 1-8 parts by mass of diisocyanate are selected to react under a certain reaction condition d to obtain an isocyanate-terminated product; then closing one end of a terminal isocyanate product by 0.5-5 parts by mass of caprolactone modified hydroxyl acrylate under a certain reaction condition e, and stopping the reaction when the isocyanate content of the system reaches a theoretical value to obtain an intermediate II;
(3) And (3) continuing the reaction of the intermediate I and the intermediate II under a certain reaction condition f, ending the reaction when the isocyanate content is less than 0.1% to obtain an intermediate III, and using 40-55 parts by mass of triethylamine aqueous solution to realize phase inversion of the intermediate III under high-speed dispersion, and simultaneously controlling the pH of a system to be slightly alkaline and solid to obtain a final product.
Preferably, the dimethylolcarboxylic acid used in the step (1) is one of dimethylolpropionic acid and dimethylolbutyric acid or any combination thereof;
the dibasic acid or anhydride used in the step (1) is one of all small molecule dibasic organic acids and all small molecule anhydrides or any combination thereof;
the certain reaction condition a used in the step (1) is that dimethylol carboxylic acid and dibasic acid or anhydride are put into a four-mouth flask at one time, 0.1 mass part of catalyst monobutyl tin oxide is added, the temperature is slowly increased to 150-250 ℃, water diversion reaction is carried out for 5-15 hours, and the reaction is finished after the acid value is stable;
the acrylic monomer used in the step (1) is one of acrylic acid and methacrylic acid or any combination thereof;
the epoxy resin used in the step (1) is one or any combination of bisphenol A type epoxy, bisphenol F type epoxy, difunctional linear glycidyl ether epoxy and phenolic epoxy;
the certain reaction condition b used in the step (1) is that an acrylic monomer and epoxy resin are put into a four-necked flask at one time, 0.1 mass part of catalyst triphenylphosphine is added, the temperature is slowly increased to 90-150 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished when the acid value is less than 2 mgKOH/g;
the certain reaction condition c used in the step (1) is that the dibasic acid with a large amount of carboxyl groups on the side groups and the product with the end-to-end double bond of the epoxy ring are put into a four-necked flask at one time, 0.1 mass part of catalyst triphenylphosphine is added, the temperature is slowly increased to 90-150 ℃ for 1-5 hours, and the reaction is finished after the acid value is stable;
the diisocyanate used in the step (2) is one of 1, 5-pentanediisocyanate, hexamethylene diisocyanate and lysine diisocyanate or any combination thereof;
the certain reaction condition d used in the step (2) is that 1000 molecular weight dimer acid modified high-elasticity dihydric alcohol and diisocyanate are put into a four-neck flask at one time, 0.1 mass part of catalyst organic bismuth is added, the temperature is slowly increased to 50-100 ℃ for reaction for 1-5 hours, and the reaction is finished after the isocyanate content is stable;
the caprolactone-modified hydroxyl acrylate used in the step (2) is one of caprolactone-modified hydroxyethyl acrylate, caprolactone-modified hydroxyethyl methacrylate, caprolactone-modified hydroxypropyl acrylate and caprolactone-modified hydroxypropyl methacrylate or any combination thereof;
the certain reaction condition e used in the step (2) is that caprolactone modified hydroxyl acrylate is added into the isocyanate-terminated product at one time, 0.1 mass part of catalyst organic bismuth and 0.5 mass part of polymerization inhibitor p-hydroxyanisole are added, the temperature is slowly increased to 50-100 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished after the isocyanate content is stable;
the certain reaction condition f used in the step (3) is that the synthesized intermediate I is added into the intermediate II at one time, 0.1 mass part of catalyst organic bismuth is added, the temperature is slowly increased to 70-100 ℃, the reaction is carried out for 1-5 hours, and the reaction is ended when the isocyanate content is less than 0.1%.
The key point of the invention is that the structure design is adopted, and the dimethylol carboxylic acid with a proper structure and the diacid or the anhydride are selected to synthesize the diacid structure with high acid value, and because the diacid with high acid value is introduced into the main chain of molecule when the epoxy acrylate is modified, the problem that the acid value adjustment is limited in the modification scheme of utilizing the anhydride on the hydroxyl at the side position of the epoxy acrylate in the prior art is avoided. Meanwhile, as the lateral hydroxyl on the epoxy acrylate is not used, the space for modifying the residual epoxy acrylate lateral hydroxyl by using polyurethane in the follow-up process is larger, and the performance of the final aqueous prepolymer obtained by modification is more excellent. In addition, the system takes water as a solvent, so that the system can realize environment-friendly solvent-free spraying, and has very wide application prospect in the application field requiring environment-friendly spraying.
The beneficial effects are that: according to the invention, through a large number of experimental screening, a large number of experimental screening is carried out, dimethylol carboxylic acid and diacid or anhydride are firstly selected to react to obtain diacid with side groups containing a large number of carboxyl groups, acrylic monomers are used to react with different epoxy resins to obtain a terminal epoxy terminal double bond product, and then the product is reacted with diacid with side groups containing a large number of carboxyl groups to obtain an intermediate I; selecting dimer acid modified high-elasticity dihydric alcohol with proper molecular weight to react with flexible diisocyanate to obtain an isocyanate-terminated product, and then using modified hydroxyl acrylate to seal one end of the isocyanate-terminated product to obtain an intermediate II; and finally, partially modifying the intermediate I by using the intermediate II to obtain an intermediate III, and finally, carrying out phase inversion on the intermediate III by using a triethylamine aqueous solution to obtain the final novel polyurethane modified waterborne epoxy acrylate. According to the invention, the optimal raw material composition, the optimal proportion and the optimal technological synthesis steps are obtained through a large number of experimental screening, the prepared aqueous photo-curing prepolymer is excellent in storage stability and quick in curing, the prepolymer can be sprayed without an organic solvent, a paint film prepared through spraying has excellent adhesive force and moderate mechanical properties, the comprehensive performance is excellent, and the defects in the prior art can be overcome.
Detailed Description
Example 1
A preparation method of novel polyurethane modified waterborne epoxy acrylate comprises the following steps:
sequentially adding 8.2 parts by mass of dimethylolpropionic acid and 6.3 parts by mass of oxalic acid into a four-necked flask, adding 0.1 part by mass of catalyst monobutyl tin oxide, slowly heating to 180 ℃, carrying out water diversion reaction for 10 hours, and ending the reaction when the acid value is stable; sequentially adding 1.2 parts by mass of acrylic acid and 4.3 parts by mass of butanediol diglycidyl ether into a four-necked flask, adding 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, slowly heating to 105 ℃, reacting for 3 hours, and finishing the reaction when the acid value is less than 2 mgKOH/g; and (3) putting the two reaction products into a four-neck flask at one time, adding 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.1 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, slowly heating to 110 ℃, reacting for 2 hours, and ending the reaction when the acid value is stable, thus obtaining an intermediate I.
15 parts by mass of 1000-molecular-weight dimer acid modified high-elasticity dihydric alcohol and 4.7 parts by mass of 1, 5-pentanediisocyanate are sequentially put into a four-neck flask, 0.1 part by mass of catalyst organic bismuth is added, the temperature is slowly increased to 75 ℃, the reaction is carried out for 2.5 hours, and the reaction is finished after the isocyanate content is stable; 3.6 parts by mass of caprolactone modified hydroxyl hexyl acrylate is added into the isocyanate-terminated product at one time, 0.1 part by mass of catalyst organic bismuth and 0.5 part by mass of polymerization inhibitor para-hydroxyanisole are added, the temperature is slowly increased to 80 ℃, the reaction is carried out for 2 hours, and the reaction is finished after the isocyanate content is stable, thus obtaining an intermediate II.
Adding the synthesized intermediate I into the intermediate II at one time, adding 0.1 part by mass of catalyst organic bismuth, slowly heating to 85 ℃, reacting for 2 hours, ending the reaction when the isocyanate content is less than 0.1%, adjusting the pH value of the system by using an aqueous solution of triethylamine, adjusting the pH value of the system to 7-8, supplementing water, and ensuring that the solid content of the system is 45%, thus obtaining the final product.
Example 2
A preparation method of novel polyurethane modified waterborne epoxy acrylate comprises the following steps:
sequentially adding 9.1 parts by mass of dimethylolbutyric acid and 15.6 parts by mass of tridecanedioic acid into a four-necked flask, adding 0.1 part by mass of catalyst monobutyl tin oxide, slowly heating to 210 ℃, and carrying out water diversion reaction for 12 hours, wherein the reaction is finished after the acid value is stabilized; sequentially adding 0.5 part by mass of methacrylic acid and 9.4 parts by mass of bisphenol A epoxy resin 604H into a four-necked flask, adding 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, slowly heating to 115 ℃, reacting for 2.5 hours, and finishing the reaction when the acid value is less than 2 mgKOH/g; and (3) putting the two reaction products into a four-neck flask at one time, adding 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.1 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, slowly heating to 118 ℃, reacting for 3 hours, and ending the reaction when the acid value is stable, thus obtaining an intermediate I.
Sequentially adding 5 parts by mass of 1000-molecular-weight dimer acid modified high-elasticity dihydric alcohol and 2.2 parts by mass of lysine diisocyanate into a four-neck flask, adding 0.1 part by mass of catalyst organic bismuth, slowly heating to 70 ℃, and reacting for 3.5 hours, wherein the reaction is finished after the isocyanate content is stable; 1.3 parts by mass of caprolactone modified hydroxypropyl methacrylate is added into the isocyanate-terminated product at one time, 0.1 part by mass of catalyst organic bismuth and 0.5 part by mass of polymerization inhibitor p-hydroxyanisole are added, the temperature is slowly increased to 80 ℃, the reaction is carried out for 2 hours, and the reaction is finished after the isocyanate content is stable, thus obtaining an intermediate II.
Adding the synthesized intermediate I into the intermediate II at one time, adding 0.1 part by mass of catalyst organic bismuth, slowly heating to 85 ℃, reacting for 3 hours, ending the reaction when the isocyanate content is less than 0.1%, adjusting the pH value of the system by using an aqueous solution of triethylamine, adjusting the pH value of the system to 7-8, supplementing water, and ensuring that the solid content of the system is 45%, thus obtaining the final product.
Example 3
A preparation method of novel polyurethane modified waterborne epoxy acrylate comprises the following steps:
sequentially adding 8.4 parts by mass of dimethylolpropionic acid and 6.1 parts by mass of succinic anhydride into a four-necked flask, adding 0.1 part by mass of catalyst monobutyl tin oxide, slowly heating to 170 ℃, and carrying out water diversion reaction for 10 hours, wherein the reaction is finished after the acid value is stabilized; sequentially adding 1.3 parts by mass of methacrylic acid and 5.3 parts by mass of bisphenol F epoxy resin 170 into a four-necked flask, adding 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, slowly heating to 110 ℃, reacting for 3 hours, and finishing the reaction when the acid value is less than 2 mgKOH/g; and (3) putting the two reaction products into a four-neck flask at one time, adding 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.1 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, slowly heating to 115 ℃, reacting for 3 hours, and ending the reaction when the acid value is stable, thus obtaining an intermediate I.
Sequentially adding 14 parts by mass of 1000-molecular-weight dimer acid modified high-elasticity dihydric alcohol and 4.7 parts by mass of hexamethylene diisocyanate into a four-neck flask, adding 0.1 part by mass of catalyst organic bismuth, slowly heating to 75 ℃, reacting for 3 hours, and finishing the reaction after the isocyanate content is stable; 3.5 parts by mass of caprolactone modified hydroxyethyl methacrylate is added into the isocyanate-terminated product at one time, 0.1 part by mass of catalyst organic bismuth and 0.5 part by mass of polymerization inhibitor p-hydroxyanisole are added, the temperature is slowly increased to 80 ℃, the reaction is carried out for 2.5 hours, and when the isocyanate content is stable, the reaction is finished, thus obtaining an intermediate II.
Adding the synthesized intermediate I into the intermediate II at one time, adding 0.1 part by mass of catalyst organic bismuth, slowly heating to 85 ℃, reacting for 2.5 hours, ending the reaction when the isocyanate content is less than 0.1%, adjusting the pH value of the system by using an aqueous solution of triethylamine, adjusting the pH value of the system to 7-8, supplementing water, and ensuring that the solid content of the system is 45%, thus obtaining the final product.
Example 4 Performance test
The novel polyurethane modified waterborne epoxy acrylates obtained in examples 1, 2 and 3 above were prepared into paint films (thickness 15 μm) by conventional spraying and the like, and the performance was measured, and the specific experimental results are shown in the following table 1.
TABLE 1 Performance test results
Note that: the storage stability in the table is characterized by the number of times the freeze thawing test has been completed, the thermal stability is measured in a forced air oven at 80℃with the test standard being that the system does not gel and phase separate with the naked eye, the curing speed is 300mW/cm directly on a UV curing machine 2 The light intensity of the ceramic tile is measured by a single curing, the adhesive force is measured on a standard test aluminum plate, and the yellowing resistance is measured on a white ceramic tile by a color difference meter (no obvious yellowing difference occurs in parallel comparison under natural illumination conditions), and the hardness, flexibility, gloss and adhesive force tests refer to GB/T13448-2006 standard.
The experimental result shows that the novel polyurethane modified waterborne epoxy acrylate prepared in the embodiment 1 of the invention has the characteristic of excellent comprehensive performance, and achieves outstanding technical effects.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the novel polyurethane modified waterborne epoxy acrylate is characterized by comprising the following steps of:
(1) Firstly, selecting 5-10 parts by mass of dimethylol carboxylic acid and 5-20 parts by mass of dibasic acid or anhydride to prepare dibasic acid with a side group containing a large amount of carboxyl groups under a certain reaction condition a; 0.5-2 parts by mass of acrylic monomer is selected to react with 2-10 parts by mass of different epoxy resins under a certain reaction condition b to obtain an epoxy end double bond product; finally, continuously reacting the dibasic acid with a large amount of carboxyl groups on the side groups and the epoxy end double bond end product under a certain reaction condition c, and obtaining an intermediate I when the acid value of the system is stable and unchanged;
(2) 5-20 parts by mass of 1000 molecular weight dimer acid modified high-elasticity dihydric alcohol and 1-8 parts by mass of diisocyanate are selected to react under a certain reaction condition d to obtain an isocyanate-terminated product; then closing one end of a terminal isocyanate product by 0.5-5 parts by mass of caprolactone modified hydroxyl acrylate under a certain reaction condition e, and stopping the reaction when the isocyanate content of the system reaches a theoretical value to obtain an intermediate II;
(3) And (3) continuing the reaction of the intermediate I and the intermediate II under a certain reaction condition f, ending the reaction when the isocyanate content is less than 0.1% to obtain an intermediate III, and using 40-55 parts by mass of triethylamine aqueous solution to realize phase inversion of the intermediate III under high-speed dispersion, and controlling the pH neutral and weak alkaline and solid content of the system to obtain a final product.
2. The method for preparing a novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the dimethylol carboxylic acid used in the step (1) is one of dimethylol propionic acid and dimethylol butyric acid or any combination thereof;
the dibasic acid or anhydride used in the step (1) is one of all small molecular dibasic fatty acids, all small molecular fatty anhydrides or any combination thereof.
3. The preparation method of the novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the certain reaction condition a used in the step (1) is that dimethylol carboxylic acid and dibasic acid or anhydride are put into a four-neck flask at one time, 0.1 mass part of catalyst monobutyl tin oxide is added, the temperature is slowly increased to 150-250 ℃, the water diversion reaction is carried out for 5-15 hours, and the reaction is finished after the acid value is stabilized.
4. The method for preparing the novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the acrylic monomer used in the step (1) is one of acrylic acid and methacrylic acid or any combination thereof; the epoxy resin used in the step (1) is one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, difunctional linear glycidyl ether epoxy resin, phenolic epoxy resin or any combination thereof.
5. The method for preparing the novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the certain reaction condition b used in the step (1) is that an acrylic monomer and epoxy resin are put into a four-neck flask at one time, 0.1 mass part of catalyst triphenylphosphine and 0.5 mass part of polymerization inhibitor para-hydroxyanisole are added, the temperature is slowly increased to 90-150 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished after the acid value is less than 2 mgKOH/g.
6. The preparation method of the novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the certain reaction condition c used in the step (1) is that the dibasic acid with a large amount of carboxyl groups on the side groups and the product with an epoxy end double bond are put into a four-neck flask at one time, 0.1 part by mass of triphenylphosphine serving as a catalyst and 0.1 part by mass of p-hydroxyanisole serving as a polymerization inhibitor are added, the temperature is slowly increased to 90-150 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished after the acid value is stable.
7. The method for preparing a novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the diisocyanate used in the step (2) is one of 1, 5-pentanediisocyanate, hexamethylene diisocyanate, lysine diisocyanate or any combination thereof.
8. The preparation method of the novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the certain reaction condition d used in the step (2) is that 1000 molecular weight dimer acid modified high-elasticity dihydric alcohol and diisocyanate are put into a four-neck flask at one time, 0.1 mass part of catalyst organic bismuth is added, the temperature is slowly raised to 50-100 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished after the isocyanate content is stabilized.
9. The method for preparing a novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the caprolactone-modified hydroxyl acrylate used in the step (2) is one of caprolactone-modified hydroxyethyl acrylate, caprolactone-modified hydroxyethyl methacrylate, caprolactone-modified hydroxypropyl acrylate, caprolactone-modified hydroxypropyl methacrylate or any combination thereof;
the certain reaction condition e used in the step (2) is that caprolactone modified hydroxyl acrylate is added into the isocyanate-terminated product at one time, 0.1 mass part of catalyst organic bismuth and 0.5 mass part of polymerization inhibitor p-hydroxyanisole are added, the temperature is slowly increased to 50-100 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished after the isocyanate content is stable.
10. The method for preparing the novel polyurethane modified waterborne epoxy acrylate according to claim 1, wherein the certain reaction condition f used in the step (3) is that the synthesized intermediate I is added into the intermediate II at one time, 0.1 part by mass of catalyst organic bismuth is added, the temperature is slowly increased to 70-100 ℃, the reaction is carried out for 1-5 hours, and the reaction is finished when the isocyanate content is less than 0.1%.
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