CN110563896A - Free radical and cation dual-polymerization UV (ultraviolet) light-cured resin and preparation method thereof - Google Patents
Free radical and cation dual-polymerization UV (ultraviolet) light-cured resin and preparation method thereof Download PDFInfo
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- CN110563896A CN110563896A CN201910873253.2A CN201910873253A CN110563896A CN 110563896 A CN110563896 A CN 110563896A CN 201910873253 A CN201910873253 A CN 201910873253A CN 110563896 A CN110563896 A CN 110563896A
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- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 title claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 26
- 150000003254 radicals Chemical class 0.000 title claims abstract description 25
- 150000001768 cations Chemical class 0.000 title abstract description 22
- 238000002360 preparation method Methods 0.000 title description 11
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- -1 aromatic diazonium salt Chemical class 0.000 claims description 5
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 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 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- GOSUEHGEXLVDBV-UHFFFAOYSA-N 2-methylbuta-1,3-diene;prop-2-enoic acid Chemical compound CC(=C)C=C.OC(=O)C=C GOSUEHGEXLVDBV-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- YZPGVFQTPWEQDA-UHFFFAOYSA-N 4-hydroxy-3-(hydroxymethyl)-2-methylbut-2-enoic acid Chemical compound OC(=O)C(C)=C(CO)CO YZPGVFQTPWEQDA-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- LKFAPHHHWRMPGC-UHFFFAOYSA-N butan-1-ol prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C LKFAPHHHWRMPGC-UHFFFAOYSA-N 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 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 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000010146 3D printing Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 238000003848 UV Light-Curing Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010538 cationic polymerization reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a free radical and cation dual polymerization UV light-cured resin which is prepared from the following raw materials in percentage by mass: 30-70% of modified oligomer, 25-60% of monomer, 0.1-0.9% of photoinitiator, 0.1-1% of dye and the balance of auxiliary agent. The resin synthesized by the invention has the advantages of no toxicity, small smell, nonflammability, high polymerization rate, small polymer volume shrinkage, no inhibition of oxygen, and the like, and is more widely applied; the viscosity of the resin can be freely adjusted from 200-100000cps, and the resin is suitable for different sizing processes, and has wide prospect in 3D printing.
Description
Technical Field
the invention relates to the technical field of high polymer materials, in particular to a free radical and cation dual polymerization UV (ultraviolet) light curing resin and a preparation method thereof.
Background
The UV curing resin is also called as UV glue or shadowless glue and generally consists of four parts, namely a prepolymer, a monomer, a photoinitiator and an auxiliary agent, wherein the principle is that the photoinitiator generates active cations or free radicals under the irradiation of ultraviolet rays so as to initiate the rapid polymerization of the monomer, so that the resin is changed from a liquid state to a solid state in a very short time;
The UV light-cured adhesive has the advantages of high curing speed, simple curing equipment, wide bonding range, no solvent, suitability for an automatic flow production line and the like, is widely applied to many fields, such as the optical product manufacturing industry of LCD (liquid crystal display) manufacturing industry, cameras and the like, optical disk manufacturing, watch manufacturing, jewelry design, buzzer, assembly of mobile phone keys, assembly of electronic circuit boards (PCB), optical fibers, glass furniture and artware, toys and ornaments and the like, and particularly the UV cured resin as the photosensitive resin is widely applied to the 3D printing industry which is rapidly developed at present, so that strong development momentum is shown;
since the compatibility of the free radical polymerization system and the cationic polymerization system is poor, and the problem of delamination is difficult to solve, so far, all reports adopt the acrylic free radical polymerization or the epoxy resin cationic polymerization to prepare the UV adhesive respectively, and the two methods respectively have advantages and disadvantages: the free radical polymerization has the advantages of high speed, good cohesion of the product and high strength, but is affected by oxygen inhibition in the polymerization process, has large volume shrinkage, and is not suitable for the industry with high precision of size; cationic polymerization has the unique advantages of small shrinkage volume, no oxygen inhibition, small smell, full curing and the like, but has the advantages of low photocuring speed, low product strength and high initiator price.
disclosure of Invention
Solves the technical problem
aiming at the defects of the prior art, the invention provides the free radical and cation dual-polymerization UV light-cured resin and the preparation method thereof, and solves the problem of poor compatibility of two systems of free radical polymerization and cation polymerization in the prior art.
Technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
A free radical and cation dual polymerization UV light-cured resin is composed of the following raw materials in percentage by mass:
30-70% of modified oligomer, 25-60% of monomer, 0.1-0.9% of photoinitiator, 0.1-1% of dye and the balance of auxiliary agent.
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then the obtained bisphenol A epoxy resin oligomer and methacrylic acid are reacted according to the molar ratio of 1: 1.
The modified oligomer can simultaneously carry out free radical polymerization and cationic ring-opening polymerization, not only solves the problem of system stability, but also has the advantages of two kinds of polymerization, and widens the application range of products;
The monomer is two or more of dimethylol methacrylic acid, 2-ethylhexyl acrylate, tert-butyl acrylate, propylene oxide, ethylene oxide, methyl methacrylate, glycidyl methacrylate, isobornyl acrylate, isoprene acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate (TMPTA), isodecyl acrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate and hydroxymethyl propane triacrylate.
the photoinitiator is an HIS system or two or more of the following compounds: benzoin and derivatives thereof, acetophenone, aromatic ketone, acylphosphine oxide, aromatic diazonium salt, aromatic sulfonium salt and iodonium salt, ferrocenium salt, two or more of 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (IHT-PI 910), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), Methyl Benzoylformate (MBF), diaryliodonium salts, triaryliodonium salts.
The auxiliary agent comprises a flatting agent, a wetting agent, a polymerization inhibitor, a thixotropic agent, a defoaming agent and a dispersing agent.
A preparation method of a free radical and cation dual polymerization UV light curing resin comprises the following steps:
Adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 15-25min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 1.8-2.5h under a vacuum state, discharging through 400-mesh filter cloth, and storing in a dark place and in a freezing way.
the invention has the advantages that:
The invention adopts a novel free radical/cation hybrid initiation system which consists of camphorquinone, diaryl iodonium salt and amine, and can finally generate two free radicals and one cation under the irradiation of ultraviolet light, thereby greatly improving the polymerization efficiency;
The resin synthesized by the invention has the advantages of no toxicity, small smell, nonflammability, high polymerization rate, small polymer volume shrinkage, no inhibition of oxygen, and the like, and is more widely applied;
The invention has obvious synergistic effect of free radical curing and cationic curing in the reaction process: the curing rate of free radicals is high, crosslinking can be completed firstly, then cationic polymerization can continue crosslinking and filling in gaps of the crosslinked polymer, the strength of the resin is further enhanced, the volume shrinkage is remarkably reduced, the volume shrinkage is below 3%, and the method is suitable for places with strict requirements on the size of materials;
The viscosity of the resin can be freely adjusted from 200-100000cps, and the resin is suitable for different sizing processes, and has wide prospect in 3D printing.
drawings
FIG. 1 is a schematic view of an apparatus for preparing a modified oligomer according to the present invention;
FIG. 2 is a schematic diagram of the synthesis of a modified oligomer according to the present invention;
FIG. 3 is a schematic diagram of the mechanism of the hybrid free radical/cation initiation system (HIS) of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
the composition of the free radical and cation dual polymerization UV curing resin comprises the following raw materials in parts by mass
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then reacting the obtained bisphenol A epoxy resin oligomer with methacrylic acid according to a molar ratio of 1:1 to obtain the modified oligomer, wherein the preparation device of the modified oligomer is shown in figure 1; the principle of the synthesis of the modified oligomer is shown in FIG. 2;
the monomers were 20g tripropylene glycol diacrylate and 20g of methylol propane triacrylate.
the photoinitiator was 0.05g of 184 and 0.05g of diaryliodonium salt.
The auxiliary agent is 7.8g of silicon dioxide and 2g of coupling agent trimethoxy silane.
the preparation method of the free radical and cation dual polymerization UV curing resin comprises the following steps:
Adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 21min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 2h under a vacuum state, discharging through 400-mesh filter cloth, and keeping out of the sun and freezing for storage, wherein the mechanism of a free radical/cation Hybrid Initiation System (HIS) is shown in figure 3.
Example 2
the composition of the free radical and cation dual polymerization UV curing resin comprises the following raw materials in parts by mass
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then the obtained bisphenol A epoxy resin oligomer and methacrylic acid are reacted according to the molar ratio of 1: 1.
the monomers are 10g of each of isoprene acrylate, hydroxypropyl methacrylate and hydroxyethyl methacrylate.
The photoinitiator was 0.1g of triaryliodonium salt and 0.1g of TPO.
The auxiliary agent comprises 5g of titanium dioxide, 0.1g of dye and 4.7g of sodium dodecyl sulfate.
the preparation method of the free radical and cation dual polymerization UV curing resin comprises the following steps:
Adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 22min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 2.2h under a vacuum state, discharging through 400-mesh filter cloth, and storing in a dark place and in a freezing way.
example 3
the composition of the free radical and cation dual polymerization UV curing resin comprises the following raw materials in parts by mass
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then the obtained bisphenol A epoxy resin oligomer and methacrylic acid are reacted according to the molar ratio of 1: 1.
The monomers are 10g of dimethylolmethacrylic acid, 10g of 2-ethylhexyl acrylate and 15g of tert-butyl acrylate.
The photoinitiator was 0.1g of triaryliodonium salt and 0.05g of TPO and 0.05g of 184.
the auxiliary agent comprises 3.2g of fumed silica, 4.5g of organic bentonite and 2g of hydroquinone.
the preparation method of the free radical and cation dual polymerization UV curing resin comprises the following steps:
Adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 20min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 2h under a vacuum state, discharging through 400-mesh filter cloth, and storing in a dark place and in a freezing way.
Example 4
The composition of the free radical and cation dual polymerization UV curing resin comprises the following raw materials in parts by mass
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then the obtained bisphenol A epoxy resin oligomer and methacrylic acid are reacted according to the molar ratio of 1: 1.
The monomer is 38g of glycidyl methacrylate;
the photoinitiator was 0.1g of an aromatic sulfonium salt and 0.05g of TPO and 0.05g of 184.
The auxiliary agent comprises 3.2g of fumed silica, 4.5g of organic bentonite, 0.1g of dye and 2g of hydroquinone.
The preparation method of the free radical and cation dual polymerization UV curing resin comprises the following steps:
adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 15min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 2.5h under a vacuum state, discharging through 400-mesh filter cloth, and storing in a dark place and in a freezing way.
Example 5
The composition of the free radical and cation dual polymerization UV curing resin comprises the following raw materials in parts by mass
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then the obtained bisphenol A epoxy resin oligomer and methacrylic acid are reacted according to the molar ratio of 1: 1.
The monomer is 45g of glycidyl methacrylate;
The photoinitiator was 0.1g camphorquinone and 0.05g diaryliodonium salt and 0.05g p-dimethylaminobenzoic acid.
The auxiliary agent comprises 3.2g of fumed silica, 4.5g of organic bentonite, 0.1g of dye and 2g of hydroquinone.
the preparation method of the free radical and cation dual polymerization UV curing resin comprises the following steps:
adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 15min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 1.8h under a vacuum state, discharging through 400-mesh filter cloth, and storing in a dark place and in a freezing way.
The performance test data for the products of examples 1-5 above are shown in Table one:
Watch 1
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The UV light-cured resin is characterized by being prepared from the following raw materials in percentage by mass:
30-70% of modified oligomer, 25-60% of monomer, 0.1-0.9% of photoinitiator, 0.1-1% of dye and the balance of auxiliary agent.
2. The radically and cationically photopolymerizable UV-curable resin according to claim 1, characterized in that;
The modified oligomer is bisphenol A epoxy resin oligomer prepared by reacting epichlorohydrin with bisphenol A; then the obtained bisphenol A epoxy resin oligomer and methacrylic acid are reacted according to the molar ratio of 1: 1.
3. The radically and cationically photopolymerizable UV-curable resin according to claim 1, characterized in that;
The monomer is two or more of dimethylol methacrylic acid, 2-ethylhexyl acrylate, tert-butyl acrylate, propylene oxide, ethylene oxide, methyl methacrylate, glycidyl methacrylate, isobornyl acrylate, isoprene acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate (TMPTA), isodecyl acrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate and hydroxymethyl propane triacrylate.
4. The radically and cationically photopolymerizable UV-curable resin according to claim 1, characterized in that;
the photoinitiator is an HIS system or two or more of the following compounds: benzoin and derivatives thereof, acetophenone, aromatic ketone, acylphosphine oxide, aromatic diazonium salt, aromatic sulfonium salt and iodonium salt, ferrocenium salt, two or more of 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (IHT-PI 910), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), Methyl Benzoylformate (MBF), diaryliodonium salts, triaryliodonium salts.
5. The UV light-curable resin for free radical and cationic double polymerization according to claim 1, wherein the auxiliary agent comprises a leveling agent, a wetting agent, a polymerization inhibitor, a thixotropic agent, an antifoaming agent and a dispersing agent.
6. A method for preparing a radically and cationically photopolymerizable UV-curable resin according to any of claims 1 to 5, characterized in that it comprises the following steps:
Adding the modified oligomer into a reaction kettle, starting stirring, then adding the dye, stirring for 15-25min at 30 ℃ to fully dissolve the dye into the resin, finally sequentially adding the monomer, the photoinitiator and the auxiliary agent, stirring for 1.8-2.5h under a vacuum state, discharging through 400-mesh filter cloth, and storing in a dark place and in a freezing way.
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| CN116640261A (en) * | 2023-05-10 | 2023-08-25 | 华南农业大学 | A kind of silicon-containing vegetable oil-based dual UV curing material and its preparation method and application |
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| CN116640261A (en) * | 2023-05-10 | 2023-08-25 | 华南农业大学 | A kind of silicon-containing vegetable oil-based dual UV curing material and its preparation method and application |
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