CN112300367A - Photo-thermal dual-curing epoxy resin - Google Patents
Photo-thermal dual-curing epoxy resin Download PDFInfo
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- CN112300367A CN112300367A CN202011137322.2A CN202011137322A CN112300367A CN 112300367 A CN112300367 A CN 112300367A CN 202011137322 A CN202011137322 A CN 202011137322A CN 112300367 A CN112300367 A CN 112300367A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 77
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 39
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 238000001723 curing Methods 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000000016 photochemical curing Methods 0.000 claims abstract description 14
- 230000009977 dual effect Effects 0.000 claims abstract description 12
- 238000001029 thermal curing Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 5
- 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 36
- 239000011248 coating agent Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 20
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 16
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008199 coating composition Substances 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims 1
- 150000004696 coordination complex Chemical class 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000010146 3D printing Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 17
- 239000001384 succinic acid Substances 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 13
- 238000009472 formulation Methods 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 9
- 239000007888 film coating Substances 0.000 description 8
- 238000009501 film coating Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- -1 hydroxypropyl Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical compound CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本发明利用生物基衣康酸与环氧树脂一步反应制备了光热双重固化环氧树脂，该树脂两端具有环氧基团，中间主链上具有双键，可同时参与热固化和光固化反应。所述合成反应原料绿色环保，合成工艺简单高效适用于工业大规模生产，固化后的材料玻璃化转变温度高，储能模量高，强度大，适用于光‑热双重固化的应用领域，如涂料、3D打印、胶黏剂等等。In the invention, the photothermal dual curing epoxy resin is prepared by one-step reaction of bio-based itaconic acid and epoxy resin. The resin has epoxy groups at both ends and double bonds in the middle main chain, and can participate in thermal curing and photocuring reactions at the same time. . The synthetic reaction raw materials are green and environmentally friendly, the synthesis process is simple and efficient, and is suitable for industrial large-scale production. The cured material has high glass transition temperature, high storage modulus and high strength, and is suitable for the application field of light-thermal dual curing, such as Coatings, 3D printing, adhesives, and more.
Description
Technical Field
The invention relates to aSynthesis ofTechnique ofRadiation curable materialThe technical field is as follows.
Background
The photo-thermal dual curing means that the photo-curing is performed to partially crosslink the system, so that the material has certain properties, and then the thermal curing is performed to completely react the thermal crosslinking groups in the material to form the cured material. In photo-thermal dual curing, a double bond, an epoxy group, and the like are common groups that can be photo-cured. Groups capable of undergoing thermal curing such as carboxyl groups, hydroxyl groups, isocyanate groups, epoxy groups, and the like. The photo-thermal dual curing has the following advantages: curing of adhesives among complex parts, reduction of shrinkage of a photocuring system, pre-shaping of materials, improvement of material performance and the like. Widely used in 3D printing and adhesive industry. At present, a plurality of methods are used for preparing a photo-thermal dual-curing system, for example, a reactive diluent or oligomer for photo-curing, an epoxy resin or polyurethane resin for thermal curing and a corresponding curing agent are added into the system, but the reaction is only simple raw material blending, the material performance is unstable, and the preparation process error is large. And the other method is that acrylic acid consumes part of epoxy groups in the epoxy resin to synthesize the resin containing double bonds and epoxy groups, and then corresponding initiator and epoxy group curing agent are added. But the raw material acrylic acid used by the method is a volatile carcinogen, does not meet the requirements of the existing green production process, and has brittle material performance and narrow application range. This patent introduces double bonds with bio-based itaconic acid, and the synthesized resin molecule has both epoxy groups and double bonds. The prepared material has stable and reliable performance and is suitable for large-scale production.
For example, in patent CN 110791196 a, epoxy resin E51 and terminal hydroxypropyl polydimethylsiloxane are used to synthesize a first component matrix resin with polyhydroxy main chain belt, isophorone diisocyanate, trimethylolpropane, hydroxyethyl acrylate and hexamethylene diisocyanate trimer are used to synthesize a second component curing agent, and then a photo-thermal dual curing system is prepared. And isophorone diisocyanate and organotin catalysts used in the synthesis process are toxic substances.
For example, in patent CN 110643318A, several acrylate reactive diluents are used, and then the method of adding thermal initiator and photoinitiator in the formulation cannot control how many proportion of groups in the system to perform photocuring and thermocuring, the properties of the pre-cured material cannot be accurately controlled, and the prepared material has low modulus and narrow application range.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a photo-thermal dual-curing epoxy resin, which has the following structure:
wherein M represents
wherein R1 and R2 represent hydrogen atom or methyl, R3 represents hydrogen atom or glycidyl, R4 represents benzene ring or cyclohexane structure, and the symbol is the position of the connecting point of the groups.
In one embodiment, the resin structure is as follows:
the second purpose of the invention is to provide a preparation method of the photo-thermal dual-curing epoxy resin, which comprises the following steps: fully mixing difunctional epoxy oligomer or epoxy resin, itaconic acid, a catalyst and a polymerization inhibitor to obtain the photo-thermal dual-curing epoxy resin under high-temperature reaction;
in one embodiment, the epoxy resin comprises a material having the structure
Wherein R1 represents a benzene ring or cyclohexane structure, R2 represents a hydrogen atom or a methyl group, and n represents an integer of 1-3.
In one embodiment, the epoxy resin comprises a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a difunctional novolac epoxy resin, a difunctional glycidyl ether, or a difunctional epoxy oligomer; the difunctional epoxy oligomer includes diglycidyl ether, bisphenol a diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, and polydiglycidyl ether.
The epoxy group of the difunctional epoxy oligomer or epoxy resin can react with the carboxyl group of itaconic acid to generate the photothermal dual curing epoxy resin.
In one embodiment of the method of the present invention,
40 to 99 parts by weight of a difunctional epoxy oligomer or epoxy resin;
0.2-30 parts by weight of itaconic acid;
0.5-1.5 parts by weight of catalyst;
0.05 to 0.2 portion of polymerization inhibitor.
In one embodiment, the specific method is as follows: fully mixing difunctional epoxy oligomer or epoxy resin, itaconic acid, a catalyst and a polymerization inhibitor, wherein the reaction starting temperature is 95-105 ℃, heating to 105-120 ℃ after reacting for 0.5 hour, titrating the acid value at an interval of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g to obtain the photo-thermal dual-curing epoxy resin.
In one embodiment, the catalyst includes triphenylphosphine, triethylamine, tetrabutylammonium bromide, acetylacetonato metal complexes, phosphorus pentoxide, aluminum oxide, phosphines, amine catalysts, and the like; the polymerization inhibitor comprises p-methoxyphenol, hydroquinone and phenols.
The third purpose of the invention is to provide an application of the photo-thermal dual-curing epoxy resin, wherein the application comprises the following steps: as a photo-thermal dual-cure coating composition, the composition comprising: photo-thermal dual-curing epoxy resin, a photo-curing reactive diluent, an epoxy resin curing agent, a thermal curing initiator and a photo-curing initiator.
In one embodiment, the photocurable reactive diluent comprises tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), 1, 6-hexanediol diacrylate (HDDA); the epoxy resin curing agent comprises methyl hexahydrophthalic anhydride (MHHPA), polyetheramine (D230) and polyetheramine (D400); catalysts for the thermal curing reaction include 1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN); the photo-curing initiator includes 1173, 819, TPO, 184, etc.
In one embodiment, the coating composition is coated on a steel plate, and is cured under an ultraviolet lamp to form a partially cross-linked coating film, and then the coating film is placed in an oven at a temperature of 130-150 ℃ for curing for 4-6 hours to obtain a completely cured coating film.
In one embodiment, the irradiation wavelength range is 250nm to 600nm, and the light intensity is 400 to 1200mJ/cm2。
Has the advantages that:
according to the invention, bio-based itaconic acid and epoxy resin are reacted in one step to prepare photo-thermal dual-curing epoxy resin, epoxy groups are arranged at two ends of the resin, a photo-curable double bond is arranged on the middle main chain, and then succinic acid and the modified epoxy resin prepared by the epoxy resin through the one-step reaction are used for comparison to show that the introduction of a double bond group can improve the crosslinking density of the material, so that the modulus, the glass transition temperature, the hardness of a coating film and the like of the material are improved. The synthetic reaction is simple and efficient, the raw materials are green and environment-friendly, and the material obtained after the synthetic resin is cured has high glass transition temperature, high energy storage modulus and excellent performance. The epoxy resin synthesized from itaconic acid has both epoxy group and double bond on the molecule, thus avoiding the defect of unstable material performance caused by simple blending of raw materials. The double bond of the patent refers to and uses bio-based itaconic acid, has no toxicity and volatility, the generated resin molecules have double bonds and epoxy groups, and the prepared formula is uniform and stable, so that the prepared material has uniform and stable performance, and is suitable for large-scale industrial production.
Drawings
Description of the meanings indicated in the figures
FIG. 1: synthetic schemes for E51-Ita in examples 1-3
FIG. 2: synthetic schemes for E51-Sua in examples 1-3
FIG. 3: resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and the resins are characterized by an infrared spectrum and compared with a raw material E51 to illustrate the successful synthesis of the resins.
FIG. 4: resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and nuclear magnetic spectrum representation is carried out on the resins to be compared with a raw material E51 to illustrate successful synthesis of the resins.
FIG. 5: characterization of DMA phase angle for resin synthesized in example 2 specimens cured according to the formulation of table 4.
FIG. 6: characterization of DMA storage modulus for the resin synthesized in example 2 specimens cured according to the formulation of table 4.
Detailed Description
Illustrating according to what is contained in the claims
Example 1:
weighing the epoxy resin E51: 26g, itaconic acid (Ita): 1g, Triphenylphosphine (TPP): 0.2g, p-Methoxyphenol (MEHQ): adding 0.03g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath kettle, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Ita-1, and the synthetic route is shown in figure 1.
In addition, for comparison, the double bond-free modified epoxy resin was synthesized from the double bond-free succinic acid by the following synthetic process: weighing the epoxy resin E51: 26g, succinic acid (Sua): 1g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Sua-1, and the synthetic route is shown in figure 2.
The synthesized resin was formulated according to the following table
Table 1: example 1 formulation scale units: g
The two formulations were cured under an F300 UVA ultraviolet lamp (total light intensity 1600 mJ/cm)2) The track speed of the ultraviolet exposure machine is 4.5m min-1The cured samples were designated E51-Sua-1-F-UV and E51-Ita-1-F-UV. Similarly, the above formulation is added after UV exposureHeat was applied for 4.5 hours at 130 ℃. The cured samples were designated E51-Sua-1-F-UV-Heat and E51-Ita-1-F-UV-Heat.
Characterization was performed:
1. tensile test
Table 2: tensile Properties of the samples of example 1
From the above results, it can be seen that the epoxy resin modified with itaconic acid (Ita) has a higher crosslinking density than the epoxy resin modified with succinic acid (Sua), and therefore, the tensile strength and Young's modulus are significantly improved, and the elongation at break of the itaconic acid group is higher than that of the succinic acid group when only photocuring is performed, but the elongation at break of the itaconic acid group after thermal curing is lower than that of the succinic acid group.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 3: film coating Properties of example 1 sample
As can be seen from table 3, the epoxy resin modified with itaconic acid has more excellent coating properties than the succinic acid-modified epoxy resin because the introduction of itaconic acid provides more crosslinking sites, thereby increasing the crosslinking density.
Example 2:
weighing the epoxy resin E51: 26g, itaconic acid (Ita): 3g, Triphenylphosphine (TPP): 0.2g of p-Methoxyphenol (MEHQ) and 0.03g of p-Methoxyphenol (MEHQ) are added into a three-neck flask, a mechanical stirring paddle and a hollow glass plug are additionally arranged, the three-neck flask is fixed in an oil bath pot, the initial temperature is 95 ℃, the temperature is increased to 105 ℃ after reaction for half an hour, the acid value is titrated at intervals of half an hour, the reaction is stopped until the acid value is less than 1mgKOH/g, the synthesized resin is E51-Ita-3, and the synthetic route is shown in figure 1.
For comparison, a modified epoxy resin containing no double bond was synthesized from succinic acid by the following procedure: weighing the epoxy resin E51: 26g, succinic acid (Sua): 3g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting the temperature to be 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Sua-3.
Resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and the resins are characterized by an infrared spectrum and compared with a raw material E51 to illustrate the successful synthesis of the resins, and the figure is shown in FIG. 3.
Resins synthesized by modifying epoxy resin with itaconic acid and succinic acid are respectively E51-Ita-3 and E51-Sua-3, and nuclear magnetic spectrum characterization is carried out on the resins to compare with a raw material E51 to illustrate successful synthesis of the resins, and the figure is shown in FIG. 4.
The synthesized resin was formulated according to the following table
Table 4: example 2 formulation scale units: g
The two formulations were cured under an F300 UVA ultraviolet lamp (total light intensity 1600 mJ/cm)2) The track speed of the ultraviolet exposure machine is 4.5m min-1The cured samples were designated E51-Sua-3-F-UV and E51-Ita-3-F-UV. Again, the above formulation was heated for an additional 4.5 hours after UV exposure at 130 ℃. The cured samples were designated E51-Sua-3-F-UV-Heat and E51-Ita-3-F-UV-Heat.
Characterization was performed:
1. tensile test
Table 5: tensile Properties of the samples of example 2
From the above results, it can be seen that the epoxy resin modified with itaconic acid (Ita) has a higher crosslinking density than the epoxy resin modified with succinic acid (Sua), and therefore, the tensile strength and Young's modulus are significantly improved, and the elongation at break of the itaconic acid group, which is only photo-cured, is improved, but the elongation at break after thermal curing is reduced.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 6: example 2 film coating Properties of samples
As can be seen from table 7, the epoxy resin modified with itaconic acid has more excellent coating properties than the succinic acid-modified epoxy resin because the introduction of itaconic acid provides more crosslinking sites, thereby increasing the crosslinking density.
DMA characterization
The samples were subjected to DMA characterization for glass transition temperature and storage modulus. The results are shown in FIGS. 5 and 6
The result shows that the glass transition temperature and the storage modulus of the itaconic acid modified epoxy resin E51-Ita-3-F-UV are higher than those of the succinic acid modified epoxy resin E51-Sua-3-F-UV when only the photocuring is carried out. The glass transition temperature and the storage modulus of the E51-Ita-3-F-UV-Heat after photo-curing and thermal curing are higher than those of the E51-Sua-3-F-UV-Heat, and the results also show that the itaconic acid can improve the crosslinking density.
Example 3:
weighing the epoxy resin E51: 26g, itaconic acid (Ita): 5g, Triphenylphosphine (TPP): 0.2g of p-Methoxyphenol (MEHQ) and 0.03g of p-Methoxyphenol (MEHQ) are added into a three-neck flask, a mechanical stirring paddle and a hollow glass plug are additionally arranged, the three-neck flask is fixed in an oil bath pot, the initial temperature is 95 ℃, the temperature is increased to 105 ℃ after reaction for half an hour, the acid value is titrated at intervals of half an hour, the reaction is stopped until the acid value is less than 1mgKOH/g, the synthesized resin is E51-Ita-5, and the synthetic route is shown in figure 1.
For comparison, a modified epoxy resin containing no double bond was synthesized from succinic acid by the following procedure: weighing the epoxy resin E51: 26g, succinic acid (Sua): 5g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is E51-Sua-5.
The synthesized resin was formulated according to the following table
Table 7: example 3 formulation scale units: g
Characterization was performed:
1. tensile test
Table 8: tensile Properties of the samples of example 3
From the above results, it can be seen that the epoxy resin modified with itaconic acid (Ita) has a higher crosslinking density than the epoxy resin modified with succinic acid (Sua), and therefore, the tensile strength and Young's modulus are significantly improved, and the elongation at break of the itaconic acid group is higher than that of the succinic acid group when only photocuring is performed, but the elongation at break after thermal curing is lower than that of the succinic acid group.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 9: example 3 film coating Properties of samples
As can be seen from table 9, the epoxy resin modified with itaconic acid has more excellent coating properties than the succinic acid-modified epoxy resin because the introduction of itaconic acid provides more crosslinking sites, thereby increasing the crosslinking density.
Example 4:
weighing 1, 4-butanediol diglycidyl ether (DDE): 26g, itaconic acid (Ita): 5g, Triphenylphosphine (TPP): 0.2g of p-Methoxyphenol (MEHQ) and 0.03g of p-Methoxyphenol (MEHQ) are added into a three-neck flask, a mechanical stirring paddle and a hollow glass plug are additionally arranged, the three-neck flask is fixed in an oil bath pot, the initial temperature is 95 ℃, the temperature is increased to 105 ℃ after reaction for half an hour, the acid value is titrated at intervals of half an hour, the reaction is stopped until the acid value is less than 1mgKOH/g, and the synthesized resin is DDE-Ita-7.
For additional comparison, a modified epoxy resin was synthesized using 1, 4-butanediol diglycidyl ether (DDE) by the following procedure: weighing diglycidyl ether (DDE): 12g, tetronic acid (Sua): 5g, Triphenylphosphine (TPP): adding 0.2g of the mixture into a three-neck flask, additionally installing a mechanical stirring paddle and a hollow glass plug, fixing the three-neck flask into an oil bath pan, starting at the temperature of 95 ℃, heating to 105 ℃ after reacting for half an hour, titrating the acid value at intervals of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g, wherein the synthesized resin is DDE-Sua-7.
The synthesized resin was formulated according to the following table
Table 10: example 4 formulation scale units: g
Characterization was performed:
1. tensile test
Table 11: tensile Properties of the samples of example 3
From the above results, it can be seen that, compared with the epoxy resin modified with itaconic acid and 1, 4-butanediol diglycidyl ether (DDE), the diglycidyl ether (DDE) and the succinic acid-modified epoxy resin have a high tensile elongation at break and excellent flexibility due to an increase in the crosslinking density of the material.
2. Film coating performance
The basic performance of the coating film is tested after the sample is prepared into the coating film, and the thickness of the coating film is measured by a coating thickness measuring instrument. The adhesion of the coating was measured by cross-seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using the ASTM D4366 and ASTM D3363 standards. Impact resistance is characterized by the ASTM D2794 standard.
Table 12: example 3 film coating Properties of samples
As can be seen from Table 12, compared with the epoxy resin modified with 1, 4-butanediol diglycidyl ether (DDE), the epoxy resin modified with succinic acid and diglycidyl ether (DDE) has excellent flexibility of the material, the adhesion of the coating film is 5B, and the impact resistance is excellent.
Claims (10)
1. The photo-thermal dual-curing epoxy resin is characterized by having the following structure:
wherein M represents
wherein R1 and R2 represent hydrogen atom or methyl, R3 represents hydrogen atom or glycidyl, R4 represents benzene ring or cyclohexane structure, and the symbol is the position of the connecting point of the groups.
2. The photo-thermal dual-curing epoxy resin as claimed in claim 1, wherein the resin has the following structure:
3. the method of claim 1, wherein the epoxy resin is obtained by mixing the difunctional epoxy oligomer or epoxy resin with itaconic acid, a catalyst and a polymerization inhibitor, and reacting at a high temperature.
4. The method of claim 3, wherein the epoxy resin comprises a material having the following structure
Wherein R1 represents a benzene ring or cyclohexane structure, R2 represents a hydrogen atom or a methyl group, and n represents an integer of 0-3.
5. The method of claim 3, wherein the epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, difunctional novolac epoxy resin, difunctional glycidyl ether or difunctional epoxy oligomer; the difunctional epoxy oligomer includes diglycidyl ether, bisphenol a diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly (propylene glycol) diglycidyl ether, and polydiglycidyl ether.
6. The method for preparing a photothermal dual curing epoxy resin according to claim 3,
40 to 99 parts by weight of a difunctional epoxy oligomer or epoxy resin;
0.2-30 parts by weight of itaconic acid;
0.5-1.5 parts by weight of catalyst;
0.05 to 0.2 portion of polymerization inhibitor.
7. The preparation method of the photothermal dual curing epoxy resin according to claim 3, is characterized by comprising the following steps: fully mixing difunctional epoxy oligomer or epoxy resin, itaconic acid, a catalyst and a polymerization inhibitor, wherein the reaction starting temperature is 95-105 ℃, heating to 105-120 ℃ after reacting for 0.5 hour, titrating the acid value at an interval of half an hour, and stopping the reaction until the acid value is less than 1mgKOH/g to obtain the photo-thermal dual-curing epoxy resin.
8. The method for preparing a photothermal dual cure epoxy resin according to any one of claims 3 to 7, wherein the catalyst comprises triphenylphosphine, triethylamine, tetrabutylammonium bromide, acetylacetonato-based metal complex, phosphorus pentoxide, aluminum oxide, phosphines, amine-based catalysts, etc.; the polymerization inhibitor comprises p-methoxyphenol, hydroquinone and phenols.
9. Use of the photothermal dual curing epoxy resin according to claim 1 or 2 or prepared by the method according to any one of claims 3 to 7, as a photothermal dual curing coating composition comprising: photo-thermal dual-curing epoxy resin, a photo-curing reactive diluent, an epoxy resin curing agent, a thermal curing initiator and a photo-curing initiator.
10. The application of the photo-thermal dual-curing epoxy resin as claimed in claim 9, wherein the coating composition is coated on a steel plate, and is cured under an ultraviolet lamp to form a partially cross-linked coating film, and then the coating film is placed in an oven at a temperature of 130-150 ℃ to be cured for 4-6 hours to obtain a fully cured coating film.
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| CN117430505B (en) * | 2023-10-23 | 2025-01-24 | 广东炎墨方案科技股份有限公司 | Itaconic acid derived glycidyl ether photocurable epoxy resin and preparation method and application thereof |
| CN118165195B (en) * | 2024-05-14 | 2024-08-02 | 北京极溯光学科技有限公司 | Dual-cure resin, 3D printing method and 3D printed product |
| CN120025737A (en) * | 2025-04-23 | 2025-05-23 | 湖南初源新材料股份有限公司 | Single-component photo-thermal dual-curing epoxy resin three-proofing coating |
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| JP2514017B2 (en) * | 1987-01-21 | 1996-07-10 | ダイセル化学工業株式会社 | Method for producing unsaturated epoxy ester resin |
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