CN115417968B - Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof - Google Patents
Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof Download PDFInfo
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- CN115417968B CN115417968B CN202211233964.1A CN202211233964A CN115417968B CN 115417968 B CN115417968 B CN 115417968B CN 202211233964 A CN202211233964 A CN 202211233964A CN 115417968 B CN115417968 B CN 115417968B
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- Prior art keywords
- isocyanuric acid
- reaction
- core
- acrylate
- diisocyanate
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000004814 polyurethane Substances 0.000 title claims abstract description 24
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920005862 polyol Polymers 0.000 claims abstract description 29
- 150000003077 polyols Chemical class 0.000 claims abstract description 29
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 19
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 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 8
- 239000000463 material Substances 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-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
- 238000004321 preservation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 3
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 6
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical group C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IPDYIFGHKYLTOM-UHFFFAOYSA-N 2-(2-prop-2-enoyloxypropoxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(C)OCC(C)OC(=O)C=C IPDYIFGHKYLTOM-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004383 yellowing Methods 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
- C08G18/3853—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring containing cyanurate and/or isocyanurate groups
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The invention discloses hyperbranched polyurethane acrylic ester with isocyanuric acid as a core and a preparation method thereof; the hyperbranched polyurethane acrylic ester is prepared by the reaction of the following substances: an isocyanuric acid-based polyol, at least one diisocyanate, and at least one hydroxy acrylate. Wherein the polyol taking the isocyanuric acid as the core is prepared by taking triglycidyl isocyanurate and diethanolamine as raw materials through reaction. The polyurethane acrylic ester oligomer not only inherits the high hardness, high wear resistance and high temperature resistance of the isocyanuric acid structure, but also improves the flexibility, water resistance and corrosion resistance, and has lower viscosity and lower production cost.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to hyperbranched polyurethane acrylate taking isocyanuric acid as a core and a preparation method thereof.
Background
In recent years, along with the requirements of green, environmental protection, low pollution and the like, the photocuring technology with the characteristics of high efficiency, wide adaptability, economy, energy conservation and environmental protection is increasingly favored by people, and the yields of corresponding photocuring oligomers and monomers are rapidly increased year by year. With the development of technology, the market continually puts higher demands on the light-cured oligomer in terms of hardness, gloss, adhesion, flame retardance and the like.
Isocyanuric acid, also called cyanuric acid, has a structure shown in a chemical formula (A), and has triazine rings with high hardness, chemical stability and thermal stability. The triglycidyl isocyanurate, also called as tri (2, 3-epoxypropyl) isocyanurate, is obtained by grafting epoxy on the secondary amine group, and the structure of the triglycidyl isocyanurate is shown as a chemical formula (B) for short; structurally, it can be seen that TGIC has three active epoxy groups and a triazine ring with better hardness, chemical stability and thermal stability, so that TGIC is mainly used as a curing agent in powder coating at present, and has better weather resistance, thermal stability, yellowing resistance and excellent mechanical properties. Connecting hydroxyethyl to the secondary amine group of the isocyanuric acid to obtain tris (2-hydroxyethyl) isocyanuric acid (THEIC), wherein the structure is shown as a chemical formula (C); the THEIC has good heat stability and insulativity and is used for producing heat-resistant enameled wires, and lacquers and polyester plastics with excellent mechanical properties.
Because of these superior properties of TGIC and THEIC and from a structural point of view it has a stable core and three active groups uniformly distributed around the core, making it possible to prepare multi-functional photocurable monomers or oligomers via relatively simple reactions, there have been many studies desiring to convert them into photocurable monomers or oligomers.
Chinese patent CN104557753 reports a photo-curable monomer prepared by esterification reaction of tris (2-hydroxyethyl) isocyanurate and acrylic acid, which not only has better chromaticity, purity and yield, but also can significantly improve hardness, heat resistance and weather resistance of the coating when applied to UV coating, and has a fast curing speed and a high crosslinking density, thus being a multifunctional acrylate monomer with good performance.
Chinese patent CN102260221 is also a photo-curing monomer prepared by esterification reaction of tris (2-hydroxyethyl) isocyanurate and acrylic acid or methacrylic acid with different molar ratios, and the photo-curing monomer of difunctional and trifunctional isocyanurate acrylate or isocyanurate methacrylate can be obtained by controlling the molar ratio. After the monomer is singly cured, the pencil hardness can reach 6H, the water resistance and the solvent resistance are good, the color change, the bubbling or the falling off are avoided after the monomer is soaked in water and an organic solvent for 24 hours, the water absorption is less than 1%, and the oil absorption is about 2%.
The paper "synthesis and application of tri (epoxypropyl) isocyanurate acrylate" uses triglycidyl isocyanurate and acrylic acid to obtain tri (epoxypropyl) isocyanurate acrylate under the catalysis of amine organic base, and uses the tri (epoxypropyl) isocyanurate acrylate as main resin to prepare UV coating with quick curing speed and high glossiness, so that it is a photosensitive resin with excellent performance.
At present, most of the technologies use raw materials containing triazine ring structures to synthesize photocuring monomers and oligomers with simpler structures through one-step reaction, and the potential of the raw materials in preparing the photocuring materials with hyperbranched structures with better performance is not exerted. For example, the prior art for synthesizing oligomers from triglycidyl isocyanurate starting material in a single step has the following problems:
1. triglycidyl isocyanurate is a solid with higher hardness and melting point, and the oligomer obtained by simple modification has better hardness but poor flexibility after solidification;
2. the viscosity of the simple modified oligomer product is great, which can be inconvenient to use.
3. The triglycidyl isocyanurate is reacted in one step to obtain an oligomer product, the consumption of the triglycidyl isocyanurate is high, and the production cost of the oligomer product is high due to the high price of the triglycidyl isocyanurate.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide hyperbranched polyurethane acrylate taking isocyanuric acid as a core and a preparation method thereof; the polyurethane acrylic ester oligomer not only inherits the high hardness, high wear resistance and high temperature resistance of the isocyanuric acid structure, but also improves the flexibility, water resistance and corrosion resistance, and has lower viscosity and lower production cost.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the hyperbranched polyurethane acrylic ester with the isocyanuric acid as the core is prepared by the reaction of the following substances:
(a) An isocyanuric acid-based polyol;
(b) At least one diisocyanate; and (3) with
(c) At least one hydroxy acrylate.
Wherein, the polyatomic alcohol taking the isocyanuric acid as the core is prepared by taking triglycidyl isocyanurate and diethanolamine as raw materials through reaction.
Preferably, the isocyanuric acid-based hyperbranched urethane acrylate has an exemplary structure represented by formula (I):
wherein R is 1 R represents diisocyanates of different structures 2 Represents hydroxy acrylates of different structures.
Further, the isocyanuric acid-based polyol has 9 hydroxyl groups.
Preferably, the diisocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
Preferably, the hydroxy acrylate is selected from the group consisting of hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, trimethylol propane diacrylate or pentaerythritol triacrylate.
The invention further provides a preparation method of hyperbranched polyurethane acrylic ester taking isocyanuric acid as a core, which comprises the following steps:
sequentially adding diisocyanate, a catalyst and a polymerization inhibitor into a reactor, heating to a certain temperature, slowly dripping polyol with isocyanuric acid as a core, performing chain extension reaction, heating to a certain temperature after the reaction is finished, dripping hydroxyl acrylate, performing end-capping reaction, and cooling, cooling and discharging after the reaction is complete to obtain the hyperbranched polyurethane acrylate with isocyanuric acid as a core. Wherein, according to the mole ratio, the polyol: a diisocyanate: hydroxyl acrylate = 1: (6-9): (6-9), and the molar ratio of diisocyanate to hydroxyl acrylate is 1:1.
wherein, the preparation method of the polyol taking the isocyanuric acid as the core comprises the following steps:
heating and melting triglycidyl isocyanurate shown in the chemical formula (II), dropwise adding diethanolamine shown in the chemical formula (III) into triglycidyl isocyanurate under the stirring condition, carrying out heat preservation reaction for a certain time after the dropwise adding is finished, and cooling and discharging to obtain polyol shown in the chemical formula (IV) and taking isocyanuric acid as a core; wherein, the mol ratio of triglycidyl isocyanurate to diethanolamine is 1:3; the reaction route is as follows:
further, the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, o-methyl hydroquinone, phenothiazine and di-tert-butyl hydroquinone; the dosage of the polymerization inhibitor is 0.05 to 0.1 percent of the total mass of the reaction materials.
Further, the catalyst is at least one of triethanolamine, triethylenediamine, dibutyl tin laurate, stannous octoate and lead naphthenate; the dosage of the catalyst is 0.05 to 0.1 percent of the total mass of the reaction materials.
Further, in the preparation method of the polyol taking the isocyanuric acid as the core, the temperature of the heat preservation reaction is 80-90 ℃ and the reaction time is 1-2 h.
Further, in the preparation method of the hyperbranched polyurethane acrylate, the reaction temperature in the chain extension reaction stage is 40-50 ℃ and the reaction time is 0.5-1 h; the reaction temperature of the end capping reaction stage is 70-90 ℃ and the reaction time is 0.5-2 h.
In the preparation method of the hyperbranched polyurethane acrylate oligomer, the molar ratio of diisocyanate to polyol can be adjusted according to the requirement, so that the hydroxyl groups of the polyol are adjusted to participate in the reaction amount, and the viscosity of the oligomer and the adhesive force to different base materials can be adjusted by retaining part of hydroxyl groups.
The beneficial effects of the invention are as follows:
based on the high reactivity of epoxy groups of triglycidyl isocyanurate and amino groups of diethanolamine and the principle that two hydroxyl groups on diethanolamine molecules react to generate one hydroxyl group, the triglycidyl isocyanurate and the diethanolamine can obtain hyperbranched polyol with 9 hydroxyl groups and excellent performance after one-step simple reaction, and then the hyperbranched polyol is utilized to react with diisocyanate and hydroxyl acrylate with different structures sequentially to synthesize various multifunctional polyurethane acrylate oligomers with hyperbranched structures.
The invention has the following advantages:
1. the introduction of nitrogen atoms and hydroxyl polar groups can effectively improve the flexibility and the substrate adhesion of the oligomer cured film;
2. the existence of the hyperbranched structure can obviously reduce the viscosity of the oligomer, and is more beneficial to the use and construction of the oligomer;
3. the existence of the hyperbranched structure can improve the crosslinking density of the oligomer curing film, thereby improving the water resistance and corrosion resistance;
4. the invention reduces the consumption of triglycidyl isocyanurate and the production cost of the oligomer product.
In conclusion, the hyperbranched polyurethane acrylic ester taking the isocyanuric acid as the core not only inherits the high hardness, high wear resistance and high temperature resistance of the isocyanuric acid structure, but also improves the flexibility, water resistance and corrosion resistance, and has lower viscosity and production cost.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides hyperbranched polyurethane acrylic ester taking isocyanuric acid as a core, which is prepared by the reaction of the following substances:
(a) An isocyanuric acid-based polyol;
(b) At least one diisocyanate; and (3) with
(c) At least one hydroxy acrylate.
Wherein, the polyatomic alcohol taking the isocyanuric acid as the core is prepared by taking triglycidyl isocyanurate and diethanolamine as raw materials through reaction; the isocyanuric acid-based polyol has 9 hydroxyl groups.
The hyperbranched polyurethane acrylate taking the isocyanuric acid as the core has an example structure shown in a chemical formula (I):
wherein R is 1 R represents diisocyanates of different structures 2 Represents hydroxy acrylates of different structures.
Wherein the diisocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
Wherein the hydroxy acrylate is selected from hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, trimethylol propane diacrylate or pentaerythritol triacrylate.
The invention further provides a preparation method of hyperbranched polyurethane acrylic ester taking isocyanuric acid as a core, which comprises the following steps:
in the first step, an isocyanuric acid-based polyol is prepared: heating triglycidyl isocyanurate shown in the chemical formula (II) to 80-90 ℃ for melting, dropwise adding diethanolamine shown in the chemical formula (III) into triglycidyl isocyanurate under the stirring condition, carrying out heat preservation reaction for 1-2 h at 80-90 ℃ after the dropwise adding is finished, and cooling and discharging to obtain polyol taking isocyanuric acid as a core shown in the chemical formula (IV); the reaction route is as follows:
in the first reaction step, the mol ratio of triglycidyl isocyanurate to diethanolamine is 1:3.
Sequentially adding diisocyanate, a catalyst and a polymerization inhibitor into a reactor, heating to a certain temperature, slowly dripping polyalcohol taking isocyanuric acid as a core, and performing chain extension reaction at the reaction temperature of 40-50 ℃ for 0.5-1 h; after the reaction is finished, heating to 70-90 ℃, dropwise adding hydroxyl acrylate, and carrying out end-capping reaction for 0.5-2 h; after the reaction is completed, cooling and discharging are carried out to obtain the hyperbranched polyurethane acrylate taking the isocyanuric acid as a core.
In the second reaction step, the polyol is in a molar ratio: a diisocyanate: hydroxyl acrylate = 1: (6-9): (6-9), and the molar ratio of diisocyanate to hydroxyl acrylate is 1:1.
in the preparation method of the hyperbranched polyurethane acrylate, the diisocyanate is selected from one or more than two of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
The hydroxy acrylate is selected from one or more of hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, trimethylolpropane diacrylate and pentaerythritol triacrylate.
Wherein the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, o-methyl hydroquinone, phenothiazine and di-tert-butyl hydroquinone; the dosage of the polymerization inhibitor is 0.05 to 0.1 percent of the total mass of the reaction materials in the second step.
Wherein the catalyst is at least one of triethanolamine, triethylenediamine, dibutyl tin laurate, stannous octoate and lead naphthenate; the dosage of the catalyst is 0.05 to 0.1 percent of the total mass of the reaction materials in the second step.
In the preparation method of the hyperbranched polyurethane acrylate, a diluent can be optionally added. The diluent is one or more than two of tri-propylene glycol diacrylate, di-propylene glycol diacrylate, hexanediol diacrylate and trimethylolpropane triacrylate. The addition amount of the diluent is less than 30 percent.
The present invention will be described in further detail with reference to the following examples.
Example 1
Firstly, 297g of triglycidyl isocyanurate is added into a 1L three-neck flask, the three-neck flask is heated to 80-90 ℃ to melt, then a stirring paddle is started, 315g of diethanolamine is slowly added dropwise through a separating funnel, the mixture is reacted for 1h at 85 ℃ after the dropwise addition is finished, a viscous transparent liquid product is obtained, and the product is cooled and discharged, so that the polyol taking the isocyanuric acid as a core is obtained.
Secondly, 222g of isophorone diisocyanate, 0.5g of hydroquinone and 0.5g of stannous octoate are added into a 1L three-neck flask, the mixture is mechanically stirred and heated to 45 ℃, 68g of the polyol synthesized in the first step is dropwise added by using a constant pressure dropping funnel for 0.5h, and the reaction is continued for 1h after the dropwise addition is completed; then heating to 80 ℃ and adding 100g of hexanediol diacrylate serving as a diluent, dropwise adding 116g of hydroxyethyl acrylate by using a constant pressure dropping funnel for 0.5h, and continuing to react for 1h after the dropwise adding is finished, cooling and discharging.
Example 2
The first reaction was the same as that of example 1.
And the second step of reaction: 156g of isophorone diisocyanate, 0.25g of hydroquinone and 0.25g of stannous octoate are added into a 1L three-neck flask, the mixture is heated to 45 ℃ by mechanical stirring, 68g of the polyol synthesized in the first step is added dropwise by using a constant pressure dropping funnel for 0.5h, and the reaction is continued for 1h after the dropwise addition is completed; then heating to 80 ℃, adding 81g of hydroxyethyl acrylate dropwise by using a constant pressure dropping funnel for 0.5h, and continuing to react for 1h after the dropwise addition is finished, cooling and discharging.
Example 3
The first reaction was the same as that of example 1.
And the second step of reaction: 174g of toluene-2, 4-diisocyanate, 0.3g of p-hydroxyanisole and 0.3g of dibutyl tin laurate are added into a 1L three-neck flask, the mixture is heated to 45 ℃ by mechanical stirring, 68g of the polyol synthesized in the first step is dropwise added by using a constant pressure dropping funnel, the dropwise adding time is 0.5h, and the reaction is continued for 1h after the dropwise adding is completed; then heating to 80 ℃ and adding 100g of hexanediol diacrylate serving as a diluent, dropwise adding 116g of hydroxyethyl acrylate by using a constant pressure dropping funnel for 0.5h, and continuing to react for 1h after the dropwise adding is finished, cooling and discharging.
Example 4
The first reaction was the same as that of example 1.
And the second step of reaction: 168g of toluene-2, 4-diisocyanate, 0.5g of p-hydroxyanisole and 0.5g of dibutyl tin laurate are added into a 1L three-neck flask, the mixture is heated to 45 ℃ by mechanical stirring, 68g of the polyol synthesized in the first step is dropwise added by using a constant pressure dropping funnel, the dropwise adding time is 0.5h, and the reaction is continued for 1h after the dropwise adding is completed; then heating to 80 ℃, adding 298g of pentaerythritol triacrylate dropwise by using a constant pressure dropping funnel for 0.5h, and continuing to react for 1h after the dripping is finished, cooling and discharging.
Example 5
The first step of reaction: the first reaction step was carried out as in example 1.
And the second step of reaction: 222g of isophorone diisocyanate, 0.3g of p-hydroxyanisole and 0.3g of dibutyltin laurate are added into a 1L three-neck flask, the mixture is mechanically stirred and heated to 45 ℃, 68g of the polyol synthesized in the first step is dropwise added by using a constant pressure dropping funnel for 0.5h, and the reaction is continued for 1h after the dropwise addition is completed; then heating to 80 ℃, adding 130g of hydroxypropyl acrylate dropwise by using a constant pressure dropping funnel for 0.5h, and continuing to react for 1h after the dropwise addition is finished, cooling and discharging.
Comparative example 1 Synthesis of tris (epoxypropyl) isocyanurate acrylate
300g of tris (epoxypropyl) isocyanurate and 0.5g of polymerization inhibitor p-hydroxyanisole are added into a 1L three-neck flask, and the mixture is heated to 80 ℃; after the raw materials are dissolved, adding 2g of catalyst N, N-dimethylaniline, and then heating to 105 ℃; slowly dripping 216g of acrylic acid, reacting for 3 hours after the dripping is finished, and cooling and discharging.
Comparative example 2 Synthesis of urethane acrylate oligomer Using tris (2-hydroxyethyl) isocyanurate as a chain extender
222g of isophorone diisocyanate, 0.3g of p-hydroxyanisole and 0.3g of dibutyltin laurate are added into a 1L three-neck flask, the mixture is mechanically stirred and heated to 45 ℃, 87g of tris (2-hydroxyethyl) isocyanuric acid is dropwise added by using a constant pressure dropping funnel for 0.5h, and the reaction is continued for 1h after the dropwise addition is completed; then heating to 80 ℃, adding 116g of hydroxyethyl acrylate dropwise by using a constant pressure dropping funnel for 0.5h, and continuing to react for 1h after the dropwise addition is finished, cooling and discharging.
Performance testing
The viscosities of the oligomers of examples 1 to 5, the tris (epoxypropyl) isocyanurate acrylate of comparative example 1, and the urethane acrylate oligomer of comparative example 2 were measured at 60℃using a NDJ-5S type rotational viscometer according to the method prescribed in national Standard "GB T10247-2008 viscosity measurement method", respectively, and the test results are shown in Table 1.
According to a known method, 65% of the hyperbranched urethane acrylate oligomer obtained in examples 1 to 5, the tris (epoxypropyl) isocyanurate acrylate of comparative example 1 and the urethane acrylate oligomer of comparative example 2 are respectively mixed with 5% of a photoinitiator and 30% of a diluent, and are subjected to photocuring to prepare a cured film; wherein the diluent is selected from HDDA (1, 6-hexanediol diacrylate), DPGDA (dipropylene glycol diacrylate), TPGDA (tripropylene glycol diacrylate).
Measuring the glossiness of the cured film by using a BGD516/3 intelligent gloss meter according to the stipulated method of national standard GB/T9754-2007 determination of 20 DEG, 60 DEG and 85 DEG specular gloss of paint films of paint and varnish containing no metal pigment; testing pencil hardness of the cured film according to a stipulated method of national Standard GB/T6739-2006 paint and varnish pencil method for measuring paint film hardness; the adhesion of the cured films was tested according to the method prescribed by the national Standard "Cross-cut test of paint and varnish films of GB/T9286-1998"; testing the wear resistance of the cured film according to the method specified in the national standard GB/T1768-2006 method for measuring the wear resistance of paint and varnish by a rotary rubber grinding wheel method; baking the mixture for 4 hours at the temperature of 250 ℃ in an oven, observing cracking conditions, and measuring high temperature resistance; the aluminum substrate was bent 180 ° to observe whether or not the cured film had cracks, and flexibility was measured.
The results of the performance tests of examples 1 to 5 and comparative examples 1 and 2 are shown in Table 1.
TABLE 1
From the above table, it can be seen that the hyperbranched urethane acrylate oligomers of examples 1 to 5 of the present invention have lower viscosity, and the cured film is excellent in hardness, adhesion, abrasion resistance, high temperature resistance and flexibility.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all modifications or equivalent arrangements using the teachings of this invention, or direct or indirect application in other related arts, are included within the scope of this invention.
Claims (9)
1. The hyperbranched polyurethane acrylic ester taking the isocyanuric acid as the core is characterized by being prepared by the reaction of the following substances:
(a) An isocyanuric acid-based polyol;
(b) At least one diisocyanate; and (3) with
(c) At least one hydroxy acrylate;
the polyatomic alcohol taking the isocyanuric acid as the core is prepared by taking triglycidyl isocyanurate and diethanolamine as raw materials through reaction; the molar ratio of triglycidyl isocyanurate to diethanolamine was 1:3.
2. The isocyanuric acid-cored hyperbranched urethane acrylate of claim 1 wherein the isocyanuric acid-cored polyol has 9 hydroxyl groups.
3. The isocyanuric acid-based hyperbranched urethane acrylate according to claim 1, wherein the diisocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
4. The isocyanuric acid-based hyperbranched urethane acrylate according to claim 1 wherein the hydroxy acrylate is selected from the group consisting of hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, trimethylol propane diacrylate and pentaerythritol triacrylate.
5. A process for the preparation of hyperbranched polyurethane acrylates with a core of isocyanuric acid as defined in any of claims 1 to 4, characterized in that the process is carried out as follows:
sequentially adding diisocyanate, a catalyst and a polymerization inhibitor into a reactor, heating to a certain temperature, slowly dropwise adding polyol with isocyanuric acid as a core, heating to a certain temperature after the reaction is finished, dropwise adding hydroxyl acrylate, cooling, and discharging after the reaction is complete, thereby obtaining the hyperbranched polyurethane acrylate with isocyanuric acid as the core.
6. The process for preparing an isocyanuric acid-cored hyperbranched urethane acrylate according to claim 5, wherein the process for preparing an isocyanuric acid-cored polyol comprises:
heating triglycidyl isocyanurate to melt, dropwise adding diethanolamine into triglycidyl isocyanurate under the stirring condition, carrying out heat preservation reaction for a certain time after the dropwise adding is finished, and cooling and discharging to obtain the polyol taking the isocyanuric acid as a core.
7. The method for preparing hyperbranched urethane acrylate with isocyanuric acid as a core according to claim 5, wherein the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, o-methyl hydroquinone, phenothiazine and di-tert-butyl hydroquinone; the dosage of the polymerization inhibitor is 0.05 to 0.1 percent of the total mass of the reaction materials.
8. The method for preparing hyperbranched urethane acrylate with isocyanuric acid as a core according to claim 5, wherein the catalyst is at least one of triethanolamine, triethylenediamine, dibutyltin laurate, stannous octoate and lead naphthenate; the dosage of the catalyst is 0.05 to 0.1 percent of the total mass of the reaction materials.
9. The process for producing hyperbranched urethane acrylate with isocyanuric acid as a core according to claim 6, wherein the temperature of the heat-insulating reaction is 80 to 90℃and the reaction time is 1 to 2 hours.
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