CN104003877B - A kind of 8 functionality aliphatic epoxy acrylate and preparation method thereof and application - Google Patents
A kind of 8 functionality aliphatic epoxy acrylate and preparation method thereof and application Download PDFInfo
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- CN104003877B CN104003877B CN201410172967.8A CN201410172967A CN104003877B CN 104003877 B CN104003877 B CN 104003877B CN 201410172967 A CN201410172967 A CN 201410172967A CN 104003877 B CN104003877 B CN 104003877B
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- aliphatic epoxy
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- epoxy acrylate
- acrylate
- catalyst
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- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 39
- 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 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000003112 inhibitor Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 18
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 18
- 229940014800 succinic anhydride Drugs 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 12
- 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 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- -1 N-diethylbenzylamine Chemical compound 0.000 claims description 4
- 239000002879 Lewis base Substances 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000976 ink Substances 0.000 claims description 2
- GCNKJQRMNYNDBI-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(2-methylprop-2-enoyloxymethyl)butyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CC)COC(=O)C(C)=C GCNKJQRMNYNDBI-UHFFFAOYSA-N 0.000 claims 3
- 239000011248 coating agent Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 6
- 238000000016 photochemical curing Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract 1
- 229940059574 pentaerithrityl Drugs 0.000 abstract 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 16
- 238000001723 curing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 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 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention belongs to Material Field, relate to a kind of 8 functionality aliphatic epoxy acrylate and preparation method thereof and application.First under catalyzer, stopper effect, obtain the 2 functionality acrylate intermediates (I) containing 1 carboxyl with TriMethylolPropane(TMP) two (methyl) acrylate reactions by Succinic anhydried, intermediate (I) and tetramethylolmethane glycidyl ether be obtained 8 functionality aliphatic epoxy acrylate under the effect of catalyzer, stopper.After 8 functionality UV photocuring aliphatic epoxy acrylate solidifications prepared by the present invention, have that hardness is high, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc. be excellent, can apply at the raw material as UV coating, ink, tackiness agent.
Description
Technical Field
The invention belongs to the field of materials, and relates to 8-functionality aliphatic epoxy acrylate and a preparation method and application thereof.
Background
With the rapid development of science and technology and the strict limitation of environmental regulations on solvents, UV light-cured polymer materials are receiving more and more attention from people. The UV light curing material has the excellent performances of fast curing, low energy consumption, less pollution, high efficiency and the like, so the UV light curing material is widely applied to the fields of coatings, printing, electronic industry and the like, and is rapidly developed in recent years. Epoxy Acrylate (EA) is prepared by ring-opening esterification of a compound containing an epoxy group and acrylic acid or methacrylic acid, is an important photocurable oligomer, has excellent properties such as low irritation, high curing speed, high transparency and high hardness, is widely used in the fields of photocurable ink, coating, adhesive and the like, and is widely applied in developed countries of the united states, japan and europe. In recent years, with the rise of ultraviolet curing technology in China, the novel light curing material has wider and wider application as a raw material of UV coating, printing ink and adhesive, and the usage amount is increased year by year.
Disclosure of Invention
The object of the present invention is to provide an 8-functional aliphatic epoxy acrylate in view of the above-mentioned disadvantages of the prior art.
Another object of the present invention is to provide a method for preparing the 8-functionality aliphatic epoxy acrylate.
It is a further object of the present invention to provide the use of the 8-functional aliphatic epoxy acrylates.
The purpose of the invention can be realized by the following technical scheme:
an 8-functionality aliphatic epoxy acrylate prepared by the following method: firstly, succinic anhydride (CASNO.108-30-5, the Chinese name is succinic anhydride, the molecular formula is C4H4O3Molecular weight 100.07) with trimethylolpropane di (methyl) acrylate under the action of catalyst and inhibitor to obtain 2-functional acrylate intermediate (I) containing 1 carboxyl, wherein the intermediate (I) reacts with pentaerythritol glycidyl ether (CAS:3126-63-4, molecular formula: c17H28O8Molecular weight: 360.3994) under the action of catalyst and inhibitor to obtain 8-functionality aliphatic epoxy acrylate (aliphatic epoxy octaacrylate).
Wherein,
taking trimethylolpropane diacrylate as an example, the first reaction step is as follows:
the 2-functional acrylate intermediate (I) containing 1 carboxyl group is preferably prepared by the following steps: under the action of a catalyst, trimethylolpropane diacrylate and succinic anhydride react for 1 to 6 hours at a temperature of between 60 and 120 ℃ in a reaction kettle, and then are cooled to a temperature below 50 ℃ to prepare a 2-functionality acrylate intermediate (I) containing 1 carboxyl; wherein the mol ratio of the trimethylolpropane diacrylate to the succinic anhydride is preferably 1 (0.8-1.5). Under the reaction condition of the invention, ring opening of succinic anhydride generates 1 carboxyl, when the acid value of a reaction system is reduced to be constant, the succinic anhydride completely carries out ring opening reaction to generate carboxyl, and the conversion rate is more than 99.9 percent.
The first-step reaction catalyst is preferably one or a mixture of two or more than two of Lewis bases, quaternary ammonium salts and quaternary phosphonium salts in any proportion; further preferably one or a mixture of two or more of triethylamine, N-dimethylbenzylamine, N-diethylbenzylamine, triphenylphosphine, tributylphosphorus, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, triphenylethylphosphonium bromide and tetrabutylphosphonium bromide in any proportion; the dosage of the catalyst is 0.1-2 wt% of the total mass of the trimethylolpropane diacrylate and the succinic anhydride. The polymerization inhibitor is preferably p-hydroxyanisole or hydroquinone, and the dosage is 100-5000 ppm.
The second step is a reaction formula:
the 8-functionality aliphatic epoxy acrylate is preferably prepared by the following steps: pentaerythritol glycidyl ether reacts with the prepared 2-functionality-degree acrylate intermediate (I) containing 1 carboxyl group for 1-10 hours at the temperature of 60-120 ℃ under the action of a catalyst and a polymerization inhibitor to prepare the 8-functionality-degree aliphatic epoxy acrylate; wherein the molar ratio of the pentaerythritol glycidyl ether to the succinic anhydride is (0.2-0.3): 1.
The 8-functional aliphatic epoxy acrylate is further preferably prepared by the following steps: pentaerythritol glycidyl ether reacts with the prepared 2-functionality acrylate intermediate (I) containing 1 carboxyl group for 3 to 9 hours at 70 to 110 ℃ under the action of a catalyst and a polymerization inhibitor to prepare the 8-functionality aliphatic epoxy acrylate; wherein the molar ratio of the pentaerythritol glycidyl ether to the succinic anhydride is (0.23-0.27): 1.
Wherein the polymerization inhibitor can be p-hydroxyanisole or hydroquinone, and the dosage of the polymerization inhibitor is 100-5000 ppm.
The catalyst for the second step reaction is Lewis bases such as triethylamine, N-dimethylbenzylamine, N-diethylbenzylamine, triphenylphosphine and tributylphosphorus, or quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide and tetrabutylammonium bromide, or one or a mixture of two or more of quaternary phosphonium salts such as triphenylethylphosphonium bromide and tetrabutylphosphonium bromide in any proportion, and the dosage of the catalyst is 0.1-2 wt% of the total mass of the pentaerythritol glycidyl ether and the intermediate (I).
After the first step of reaction is finished, the intermediate is not required to be purified, pentaerythritol glycidyl ether is directly added, and a catalyst and a polymerization inhibitor are added for reaction. Wherein, the amount of the catalyst added in the first step reaction is based on the total mass of reactants succinic anhydride and trimethylolpropane di (methyl) acrylate; the amount of the second-stage reaction catalyst (including the amount of the catalyst added in the first-stage reaction and the amount of the catalyst added in the second-stage reaction) is based on the total mass of the reactants succinic anhydride, trimethylolpropane di (meth) acrylate and pentaerythritol glycidyl ether. The polymerization inhibitor added in the first reaction step also plays a role in the second reaction step like the catalyst, and the dosage of the polymerization inhibitor in the second reaction step is the sum of the addition amount of the polymerization inhibitor in the first reaction step and the additional amount of the polymerization inhibitor in the second reaction step.
The invention relates to application of 8-functionality aliphatic epoxy acrylate in preparation of UV (ultraviolet) coatings, printing ink or adhesives.
Has the advantages that:
the invention discloses a novel 8-functionality UV (ultraviolet) photocuring aliphatic epoxy acrylate and a preparation method thereof. After being cured, the 8-functionality-degree UV photocuring aliphatic epoxy acrylate has high hardness, excellent wear resistance, excellent scratch resistance, excellent heat resistance, excellent weather resistance and the like, and can be applied as a raw material of UV coatings, printing ink and adhesives.
Detailed Description
Example 1:
firstly, 1000 g succinic anhydride (CASNO.108-30-5, molecular formula: C) is put into an 8L reaction kettle4H4O3Molecular weight 100.07), 15 g benzyltriethylammonium chloride, 1.5 g p-hydroxyanisole, 3457 g trimethylolpropane diacrylate (molecular formula: c12H18O5Molecular weight 242, diester content 70%), starting stirring, heating to 70 ℃, preserving heat for 1 hour, heating to 80 ℃, preserving heat for 1 hour, heating to 100 ℃, preserving heat for 3 hours, reacting until the acid value is constant, and then cooling to below 50 ℃ to obtain 4473.5 g of 2-functionality acrylate intermediate (I) containing 1 carboxyl. The second step reaction is directly carried out without separation and purification.
In the second step, 900 g of pentaerythritol glycidyl ether (CAS:3126-63-4, formula: C) was subsequently charged into the 8L reactor of the first reaction17H28O8Molecular weight: 360.3994), 6 g of benzyltriethylammonium chloride and 1 g of p-hydroxyanisole, heating to 70 ℃, preserving heat for 1 hour, heating to 80 ℃, preserving heat for 1 hour, heating to 90 ℃, preserving heat for 1 hour, heating to 100 ℃, preserving heat for 1 hour, heating to 110 ℃, preserving heat for 5 hours, reacting until the acid value is constant, cooling to below 50 ℃, discharging to obtain a crude product, filtering by a 200-mesh filter screen (gauze), and obtaining 5273 g of clear transparent viscous liquid 8-functionality aliphatic epoxy acrylate (aliphatic epoxy octa-acrylate) C81H116O40The structure is shown as formula (II).
1HNMR(400MHz,CD3OD,ppm)：0.90(12H,t,4CH3),1.69(8H,q,4CH2),2.84‐2.86(16H,m,4CH2CH2),3.40(4H,m,4CH2),3.58(4H,brs,4OH),3.65(4H,m,4CH2),
4.00(8H,s,4CH2),4.07(16H,s,8CH2),4.11(4H,m,4CH2),4.14(4H,m,4CH),4.36(4H,m,4CH2),5.59(8H,d,8CH＝CH2),5.80(8H,s,4CH2),6.05(8H,m,8CH＝CH2),
6.27(8H,m,8CH＝CH2)
13CNMR(100MHz,CD3OD,ppm)：7.0(4CH3),22.9(8CH2),29.5(8CH2),35.9(4C),44.8(1C),65.5(4CH2),65.9(4CH2),66.0(8CH2),68.7(4CH),
71.0(4CH2),73.6(4CH2),128.2(8CH),131.3(8CH2),166.5(8CO),173.1(8CO)
Example 2:
firstly, 1000 g succinic anhydride (CASNO.108-30-5, molecular formula: C) is put into an 8L reaction kettle4H4O3Molecular weight 100.07), 10 g benzyltriethylammonium chloride, 5g tetramethylammonium chloride, 1.5 g p-hydroxyanisole, 3457 g trimethylolpropane diacrylate (molecular formula: c12H18O5Molecular weight 242, diester content 70%), starting stirring, heating to 70 ℃, preserving heat for 1 hour, heating to 80 ℃, preserving heat for 1 hour, heating to 100 ℃, preserving heat for 3 hours, reacting until the acid value is constant, and then cooling to below 50 ℃ to obtain 4473.5 g of 2-functionality acrylate intermediate (I) containing 1 carboxyl. The second step reaction is directly carried out without separation and purification.
In a second step, 900 g of pentaerythritol glycidyl ether (CAS:3126-63-4, formula: C) are subsequently introduced into an 8L reactor17H28O8Molecular weight: 360.3994), 6 g of triphenyl phosphine and 1 g of hydroquinone, heating to 70 ℃, preserving heat for 1 hour, heating to 80 ℃, preserving heat for 1 hour, heating to 90 ℃, preserving heat for 1 hour, heating to 100 ℃, preserving heat for 1 hour, heating to 110 ℃, preserving heat for 5 hours, reacting until the acid value is constant, and then obtaining the final productCooling to below 50 deg.C, discharging to obtain crude product, filtering with 200 mesh filter screen (gauze) to obtain 5275 g clear transparent viscous liquid 8-functionality aliphatic epoxy acrylate (aliphatic epoxy octa-acrylate) C81H116O40The structure is shown as formula (II).
Example 3
Raw material
UV resin: the 8-functionality aliphatic epoxy acrylate prepared in example 1; 2-functionality aliphatic urethane acrylates (F5201, science and technology, Inc. of Jiangsu Ritian).
UV monomer: trimethylolpropane triacrylate (TMPTA, science and technology ltd, jiangsu lika); 1, 6-hexanediol diacrylate (HDDA, Kyoto Rida technologies Co., Ltd.); dodecyl acrylate (LA, science and technology Co., Ltd., Jiangsu Ritian).
Photoinitiator (2): photoinitiator 1173, Nanjing Waals chemical technology, Inc.
Auxiliary agent: tego432, Tego92, Germany Digao.
Mixing solvent: butyl acetate, toluene and methyl isobutyl ketone in a mass ratio of 1: 1: 1 and mixing.
Apparatus and device
LT-1002 type ultraviolet curing machine, blue sky lamp development Co., Ltd; QFZ type paint film adhesion tester, Tianjin department union materials testing machine factory; RCA paper tape wear-resisting instrument, Shanghai modern environmental engineering technical research institute; a water bath kettle; and (4) a cold-hot circulating device. Preparation of coating
Weighing a certain mass of UV resin, then adding a UV monomer, a photoinitiator and an auxiliary agent, uniformly stirring, and preparing the coating. The coating formulation is shown in Table I.
Table 1: proportion of coating
Preparation and curing of coating films
Selecting an ABS plastic plate of 10cm multiplied by 10cm, firstly spraying a layer of thermoplastic acrylic resin white primer on the surface of the ABS plastic plate, baking the ABS plastic plate for 3 hours at the temperature of 60 ℃, then spraying UV finish on the surface of the ABS plastic plate, wherein the thickness of the coating film is about 20 mu m, curing the ABS plastic plate on a photocuring machine to ensure that the cured film reaches surface dryness, characterizing the ABS plastic plate by a finger-touch dry method, and recording the curing time.
Performance testing
Curing time: the test was conducted by a dry-to-touch method in which the surface of the paint film was touched with a finger and was considered to be cured if it did not feel sticky.
Pencil hardness: the test is carried out according to a GB 6739-86 coating pencil hardness method.
Adhesion force: the test is carried out according to a GB/T1720-88 coating adhesion test method. The classification is 7 grades, the best grade 1 and the worst grade 7.
Wear resistance: RCA test, 175g, 500. + -. 50 times.
Boiling in water: refer to the national standard GB/T1733 "determination of Water resistance of paint film".
Cold and heat cycle resistance:
(1) scope and description: the tendency of plastic paints to crack, due to damp heat cycles or loss of plasticizer, or both, is determined by the alternating exposure of the paint films to hot and cold chambers, and the extent of cracking.
(2) The instrument comprises the following steps: the device comprises a wet and hot box, a freezing box, a color measuring instrument and a grid drawing device.
(3) The determination method comprises the following steps: putting the test sample into an incubator hot box with the relative temperature of 100% and the temperature of 38 ℃ for 24 hours. The sample plates should be placed at an angle of 0-30 degrees from the vertical and the plates should not touch each other during the test. ② after 24h, immediately transferring the sample plate into a freezer at (-23 +/-1.5) DEG C for 20h, wherein the transfer time is not more than 30S at most. Thirdly, the sample plate is taken out and placed for 4 hours at room temperature, so that 48 hours in total are a cycle, and the period can be subjected to stage evaluation. Fourthly, 15 cycles are carried out, and then the appearance, the color and the adhesive force of the sample plate are tested.
(4) The results show that: the coating should be free of cracking, discoloration, adhesion loss, or other defects.
(5) Reference standard: U.S. Standard AAMA615-02 trade Specification, Performance requirements and test methods for high Performance organic coatings for Plastic profiles.(1)
Results and discussion of the Effect of the resin on coating Performance
The UV resin is the main body of the UV coating, and the performance of the UV resin basically determines the main performance of a coating film after being cured. In the experiment, different formulas are formed by 8-functionality aliphatic epoxy acrylate and 2-functionality aliphatic polyurethane acrylate resin, the dosage of various components is shown in table 1, and the coating performance is shown in table 2.
Table 2: influence of different proportions of 8-membered aliphatic epoxy acrylate and 2-membered aliphatic urethane acrylate on coating performance
Reference documents:
(1) yu yingying, inspection methods and instruments for paint industry are all the same, Beijing: chemical industry publishers, 2007: 525.
description of additional photoinitiator 1173:
the manufacturer: nanjing Wa chemical technology Co Ltd
Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-propanone
English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CASNO：7473-98-5
Molecular formula of C10H12O
Molecular weight 164.2
Chemical structural formula:
the technical indexes are as follows:
appearance: colorless to pale yellow transparent liquid
The purity is more than or equal to 99.0 percent
Boiling point: 80-81 deg.C (centigrade)
The light transmittance is more than or equal to 99.0 percent when the wavelength is 425 nm; 500nm is more than or equal to 99.3 percent
Volatile components: less than or equal to 0.2 percent
Ash content is less than or equal to 0.10 percent.
Claims (8)
1. An 8-functional aliphatic epoxy acrylate, characterized in that said 8-functional aliphatic epoxy acrylate is prepared by the following process: the first step of reaction: firstly, succinic anhydride reacts with trimethylolpropane di (methyl) acrylate under the action of a catalyst and a polymerization inhibitor to prepare a 2-functionality acrylate intermediate (I) containing 1 carboxyl; the second step of reaction: preparing 8-functionality aliphatic epoxy acrylate from the intermediate (I) and pentaerythritol glycidyl ether under the action of a catalyst and a polymerization inhibitor; wherein, the trimethylolpropane di (methyl) acrylate is selected from any one of trimethylolpropane dimethacrylate or trimethylolpropane diacrylate;
trimethylolpropane diacrylate is used as a raw material, and the reaction route is as follows:
the first step reaction formula is:
the second step is a reaction formula:
trimethylolpropane dimethacrylate is used as a raw material, the reaction route corresponds to the reaction route, and the trimethylolpropane diacrylate is replaced by the trimethylolpropane dimethacrylate.
2. The method of preparing an 8-functional aliphatic epoxy acrylate according to claim 1, characterized by comprising the steps of: the first step of reaction: firstly, succinic anhydride reacts with trimethylolpropane di (methyl) acrylate under the action of a catalyst and a polymerization inhibitor to prepare a 2-functionality acrylate intermediate (I) containing 1 carboxyl; the second step of reaction: and (3) preparing the 8-functionality aliphatic epoxy acrylate from the intermediate (I) and pentaerythritol glycidyl ether under the action of a catalyst and a polymerization inhibitor.
3. The method for preparing 8-functionality aliphatic epoxy acrylate according to claim 2, wherein trimethylolpropane diacrylate and succinic anhydride react in a reaction kettle at 60-120 ℃ for 1-6 hours under the action of catalyst and polymerization inhibitor, and then are cooled to below 50 ℃ to prepare 2-functionality acrylate intermediate (I) containing 1 carboxyl; wherein the molar ratio of the trimethylolpropane diacrylate to the succinic anhydride is 1: (0.8 to 1.5).
4. The method for preparing 8-functionality aliphatic epoxy acrylate according to claim 2, wherein pentaerythritol glycidyl ether reacts with the 2-functionality acrylate intermediate (I) containing 1 carboxyl group at 60-120 ℃ for 1-10 hours under the action of a catalyst and a polymerization inhibitor to prepare the 8-functionality aliphatic epoxy acrylate; wherein the molar ratio of the pentaerythritol glycidyl ether to the succinic anhydride is (0.2-0.3): 1.
5. The method for preparing 8-functionality aliphatic epoxy acrylate according to claim 4, wherein the intermediate (I) is not required to be separated and purified after the first step reaction, pentaerythritol glycidyl ether is directly added, and a catalyst and a polymerization inhibitor are added to perform the second step reaction.
6. The method for preparing 8-functional aliphatic epoxy acrylate according to any one of claims 2 to 5, wherein the catalyst is one or a mixture of two or more of Lewis bases, quaternary ammonium salts and quaternary phosphonium salts in any ratio; the dosage of the catalyst is 0.1-2 wt% of the total mass of the reactants; the polymerization inhibitor is p-hydroxyanisole or hydroquinone, and the dosage of the polymerization inhibitor is 100-5000 ppm.
7. The method according to claim 6, wherein the catalyst is one or a mixture of two or more selected from the group consisting of triethylamine, N-dimethylbenzylamine, N-diethylbenzylamine, triphenylphosphine, tributylphosphine, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, triphenylethylphosphonium bromide and tetrabutylphosphonium bromide.
8. Use of the 8-functional aliphatic epoxy acrylate according to claim 1 for the preparation of UV coatings, inks or adhesives.
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| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN102660387A (en) * | 2012-04-12 | 2012-09-12 | 广州市博兴化工科技有限公司 | Acrylic acid ester modified epoxy soybean oil, its preparation method and application thereof |
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| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN102660387A (en) * | 2012-04-12 | 2012-09-12 | 广州市博兴化工科技有限公司 | Acrylic acid ester modified epoxy soybean oil, its preparation method and application thereof |
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