CN116445075A - Preparation method of low-refractive-index optical fiber coating - Google Patents
Preparation method of low-refractive-index optical fiber coating Download PDFInfo
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- CN116445075A CN116445075A CN202310458179.4A CN202310458179A CN116445075A CN 116445075 A CN116445075 A CN 116445075A CN 202310458179 A CN202310458179 A CN 202310458179A CN 116445075 A CN116445075 A CN 116445075A
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- fluorine
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 125
- 239000011737 fluorine Substances 0.000 claims abstract description 125
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000003112 inhibitor Substances 0.000 claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims abstract description 13
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 acrylic ester Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005070 sampling Methods 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 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 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 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 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 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
- 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 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 241000282817 Bovidae Species 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 3
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a preparation method of a low-refractive-index optical fiber coating, which comprises the following raw materials: 20 to 50 parts of fluorine-containing oligomer, 2 to 6 parts of photoinitiator, 0.5 to 1.5 parts of polymerization inhibitor, 1.2 to 3.4 parts of accelerator and 2.6 to 4.8 parts of auxiliary agent; adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 65-80 ℃ in the stirring process, preserving heat for reaction for 3-5 h, adding (methyl) acrylic hydroxyl ester and a polymerization inhibitor, continuously reacting for 3-6 h at the temperature, and sampling to determine that the isocyanate content is zero; s2: adding fluorine-containing polyurethane acrylic ester and 2,2' -bisphenol hexafluoropropane into the step S1, continuously stirring for 1-2 h, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is (1-2): (0.001-0.012): (0.2-0.9); s3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), standing for 3-6 hours at the temperature of minus 10-minus 5 ℃, heating to 70-90 ℃ and stirring for reacting for 4-8 hours to obtain the optical fiber coating.
Description
Technical Field
The invention belongs to the technical field of optical fiber coatings, and particularly relates to a preparation method of a low-refractive-index optical fiber coating.
Background
The optical fiber coating is used for protecting optical fiber from external environment and maintaining sufficient mechanical strength and optical performance, and is a multilayer protection system formed by combining a soft buffer layer coated during drawing and forming of optical fiber and a protective layer with harder, tough, wear-resistant, chemical-resistant and other characteristics. The fiber laser is a laser using rare earth element doped glass fiber as a gain medium, and has wide application in the fields of marking, material processing, material bending, laser cutting and the like. In order to restrict the pump light to transmit in the quartz cladding of the optical fiber, the refractive index of the inner coating of the optical fiber for the optical fiber laser is required to be low, and the refractive index of the inner coating is generally 1.35-1.37 according to the numerical aperture requirement of the optical fiber.
The low refractive index optical fiber coating is generally fluorine-containing or silicon-containing photo-curable acrylic resin, but the refractive index of silicon-containing acrylic resin is generally greater than 1.41, so that the fluorine-containing acrylic resin is generally used as the low refractive index optical fiber coating for the optical fiber laser, and the higher the fluorine content of the resin, the lower the refractive index thereof. However, the fluorine-containing raw materials for synthesizing the fluorine-containing acrylic resin are few in variety and high in price, and the compatibility with the fluorine-free raw materials is poor, so that the synthetic technology threshold is high. Besides the refractive index requirement, the low refractive index optical fiber coating for the optical fiber laser also needs to have stronger interface bonding force with glass fibers, and the bonding force is not weakened under the high-temperature and high-humidity environment so as to meet the use scene requirement of the optical fiber laser. The current optical fiber for the optical fiber laser is influenced by the structure of the optical fiber preform, the curing speed of the coating and the interfacial binding force of the coating and the glass fiber, the drawing speed is slower than that of the common optical fiber, the production efficiency is low, but researches and reports on the drawing speed by coating suppliers are few.
In the prior art, the coating uses fluorine-containing polyurethane acrylate oligomer, difunctional fluorine-containing acrylate monomer, long-chain monofunctional fluorine-containing acrylate monomer, initiator, flatting agent and silane coupling agent, the coating has the advantages of ensuring low refractive index, simultaneously keeping high mechanical strength and excellent glass adhesion, wherein the difunctional fluorine-containing acrylate monomer can obviously improve the film forming modulus of the formula. However, fluorine-free silane coupling agents have poor compatibility with fluorine-containing coating systems, resulting in too short a shelf life of the coating and affecting its peel force.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a low-refractive-index optical fiber coating, which comprises the following raw materials in parts by weight: 20 to 50 parts of fluorine-containing oligomer, 2 to 6 parts of photoinitiator, 0.5 to 1.5 parts of polymerization inhibitor, 1.2 to 3.4 parts of accelerator and 2.6 to 4.8 parts of auxiliary agent;
further, the fluorine-containing oligomer comprises the components with the mass ratio of 3-6:1: 1.1 to 1.5 of fluorine-containing polyurethane acrylate, fluorine-containing epoxy acrylate and 2,2' -bisphenol hexafluoropropane.
Further, the fluorine-containing epoxy acrylate is prepared by adopting the following scheme:
1) Adding fluorine-containing epoxy resin and a polymerization inhibitor into a reaction container, gradually heating to 100-120 ℃ in the stirring process, and stirring for 20-30 min, wherein the mass ratio of the fluorine-containing epoxy resin to the polymerization inhibitor is (1-1.5): (0.032 to 0.084).
2) Adding acrylic acid and a catalyst into the step 1), adding the acrylic acid and the catalyst in a dropwise manner, and stirring the mixture at the temperature for reaction for 4 to 6 hours to obtain the fluorine-containing polyurethane acrylate, wherein the mass ratio of the acrylic acid to the catalyst is (1.2 to 2.6): (0.014 to 0.036).
Further, the structural formula of the fluorine-containing epoxy resin is shown as formula I:
wherein, p is 1-3, q is 1-5, and R is C1-C6 alkyl or alkoxy.
The preparation method comprises the following steps:
s1: adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 65-80 ℃ in the stirring process, preserving heat for reaction for 3-5 h, then adding (methyl) acrylic hydroxyl ester and a polymerization inhibitor, continuously reacting for 3-6 h at the temperature, and sampling to determine that the isocyanate content is zero.
S2: adding fluorine-containing polyurethane acrylic ester and 2,2' -bisphenol hexafluoropropane into the step S1, continuously stirring for 1-2 h, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is (1-2): (0.001-0.012): (0.2-0.9).
S3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), then placing the mixture at-10 to-5 ℃ for standing for 3-6 hours, heating the mixture to 70-90 ℃ and stirring the mixture for reacting for 4-8 hours to obtain the optical fiber coating.
Further, the fluorine-containing epoxy resin is selected from any one of 2, 2-bisphenol hexafluoropropane diglycidyl ether, octafluorobiphenyl diglycidyl ether, 1,3- (bis-hexafluoro light propyl) benzene diglycidyl ether and 1, 4-bis (hexafluoro antelope inner) benzene diglycidyl ether.
Further, the fluorine-containing polyol is one or a mixture of more than two of fluorine-containing polyether unit alcohol, fluorine-containing polyether glycol, fluorine-containing polyester unit alcohol and fluorine-containing polyester glycol.
Further, the isocyanate is selected from any one or a mixture of more than two of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).
Further, the photoinitiator comprises one or more of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-phenylbenzyl-2-dimethyl amine-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone and benzoin dimethyl ether.
Further, the accelerator is selected from fluorine-containing silane coupling agents;
the polymerization inhibitor is selected from one of hydroquinone and p-hydroxyanisole;
the catalyst is dibutyl tin dilaurate, N, N-dimethyl cyclohexylamine, bis (2-dimethyl amino ethyl) ether, N, N, N ', N ' -tetramethyl alkylene diamine, triethylamine, N, one or more than two of N-dimethylbenzylamine, triethanolamine and dimethylaminoethanol N, N ' -lutidine;
the auxiliary agent is selected from defoamer, flatting agent, antioxidant and stabilizer.
The invention also has the following beneficial effects:
1. in the invention, the fluorine-containing epoxy resin with chain structure and C1-C6 alkyl or alkoxy is adopted, the refractive index is lower, bisphenol hexafluoropropane contains phenolic hydroxyl group, and is easy to react with oil polyfunctional amine group to form a crosslinked network, so that the mechanical property of the optical fiber coating can be improved.
2. The introduction of the fluorine-containing epoxy acrylate can generally improve the modulus of the optical fiber coating after curing and increase the adhesive force with glass, but when the fluorine-containing epoxy acrylate is excessive, the adhesive force and the drawing speed are reduced instead although the modulus is higher.
3. In the invention, the growth direction and the growth rate of the fiber growth of the resin in the reaction process are effectively controlled by adopting a freezing and thawing mode in the process of preparing the coating, so that the comprehensive performance of the optical fiber coating can be further improved.
Detailed Description
The following detailed description of the embodiments of the present invention is provided on the premise of the technical solution of the present invention, and the detailed implementation manner and specific operation process are provided, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Example 1
The preparation method of the low-refractive-index optical fiber coating comprises the following raw materials in parts by weight: 20 parts of fluorine-containing oligomer, 2 parts of photoinitiator, 0.5 part of polymerization inhibitor, 1.2 parts of accelerator and 2.6 parts of auxiliary agent;
the fluorine-containing oligomer comprises the following components in percentage by mass: 1:1.1, a fluorine-containing urethane acrylate, a fluorine-containing epoxy acrylate and 2,2' -bisphenol-based hexafluoropropane.
The fluorine-containing epoxy acrylate is prepared by adopting the following scheme:
1) Adding fluorine-containing epoxy resin and a polymerization inhibitor into a reaction container, gradually heating to 100 ℃ in the stirring process, and stirring for 20min, wherein the mass ratio of the fluorine-containing epoxy resin to the polymerization inhibitor is 1:0.032.
2) Adding acrylic acid and a catalyst into the step 1), adding the acrylic acid and the catalyst in a dropwise manner, and stirring the mixture at the temperature for reaction for 4 hours to obtain the fluorine-containing polyurethane acrylate, wherein the mass ratio of the acrylic acid to the catalyst is 1.2:0.014.
the structural formula of the fluorine-containing epoxy resin is shown as formula I:
wherein p is an alkyl group having a value of 1, q is a value of 1, and R is a C1.
The preparation method comprises the following steps:
s1: adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 65 ℃ in the stirring process, preserving heat for 3 hours, adding hydroxyl (methyl) acrylate and a polymerization inhibitor, continuously reacting for 3 hours at the temperature, and sampling to determine that the isocyanate content is zero.
S2: adding fluorine-containing polyurethane acrylate and 2,2' -bisphenol hexafluoropropane into the step S1, stirring for 1h, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is 1:0.001:0.2.
s3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), then placing the mixture at the temperature of minus 5 ℃ for standing for 3 hours, and then heating the mixture to the temperature of 70 ℃ for stirring and reacting for 4 hours to obtain the optical fiber coating.
The fluorine-containing epoxy resin is selected from 2, 2-bisphenol hexafluoropropane diglycidyl ether.
The fluorine-containing polyol is fluorine-containing polyether unit alcohol, fluorine-containing polyester unit alcohol and fluorine-containing polyester dihydric alcohol.
The isocyanate is selected from dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI).
The photoinitiator comprises 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone and benzoin dimethyl ether.
The accelerator is selected from fluorine-containing silane coupling agents;
the polymerization inhibitor is selected from hydroquinone;
the catalyst is N, N-dimethyl cyclohexylamine, triethylamine, N-dimethyl benzylamine and triethanolamine;
the auxiliary agent is selected from defoamer, flatting agent, antioxidant and stabilizer.
Example 2
The preparation method of the low-refractive-index optical fiber coating comprises the following raw materials in parts by weight: 50 parts of fluorine-containing oligomer, 6 parts of photoinitiator, 1.5 parts of polymerization inhibitor, 3.4 parts of accelerator and 4.8 parts of auxiliary agent;
the fluorine-containing oligomer comprises the following components in mass ratio of 6:1:1.5 fluorine-containing urethane acrylate, fluorine-containing epoxy acrylate and 2,2' -bisphenol-based hexafluoropropane.
The fluorine-containing epoxy acrylate is prepared by adopting the following scheme:
1) Adding fluorine-containing epoxy resin and a polymerization inhibitor into a reaction container, gradually heating to 120 ℃ in the stirring process, and stirring for 30min, wherein the mass ratio of the fluorine-containing epoxy resin to the polymerization inhibitor is 1.5:0.084.
2) Adding acrylic acid and a catalyst into the step 1), adding the acrylic acid and the catalyst in a dropwise manner, and stirring the mixture at the temperature for reaction for 6 hours to obtain the fluorine-containing polyurethane acrylate, wherein the mass ratio of the acrylic acid to the catalyst is 2.6:0.036.
the structural formula of the fluorine-containing epoxy resin is shown as formula I:
wherein p has a value of 3, q has a value of 5, and R is an alkoxy group.
The preparation method comprises the following steps:
s1: adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 80 ℃ in the stirring process, preserving heat for reaction for 5 hours, then adding (methyl) acrylic hydroxyl ester and a polymerization inhibitor, continuously reacting at the temperature for 6 hours, and sampling to determine that the isocyanate content is zero.
S2: adding fluorine-containing polyurethane acrylate and 2,2' -bisphenol hexafluoropropane into the step S1, stirring for 2 hours, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is 2:0.012:0.9.
s3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), then placing the mixture at the temperature of minus 10 ℃ for standing for 6 hours, and then heating the mixture to the temperature of 90 ℃ for stirring and reacting for 8 hours to obtain the optical fiber coating.
The fluorine-containing epoxy resin is selected from 1,3- (bis-hexafluoro light propyl) benzene diglycidyl ether.
The fluorine-containing polyol is fluorine-containing polyether unit alcohol, fluorine-containing polyester unit alcohol and fluorine-containing polyester dihydric alcohol.
The isocyanate is selected from dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI).
The photoinitiator comprises 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, and 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone.
The accelerator is selected from fluorine-containing silane coupling agents;
the polymerization inhibitor is selected from hydroquinone;
the catalyst is dibutyl tin dilaurate, and dimethylaminoethanol N, N' -lutidine;
the auxiliary agent is selected from defoamer, flatting agent, antioxidant and stabilizer.
Example 3
The preparation method of the low-refractive-index optical fiber coating comprises the following raw materials in parts by weight: 30 parts of fluorine-containing oligomer, 3 parts of photoinitiator, 0.8 part of polymerization inhibitor, 1.9 parts of accelerator and 2.9 parts of auxiliary agent;
the fluorine-containing oligomer comprises the following components in mass ratio of 4:1:1.2 fluorine-containing urethane acrylate, fluorine-containing epoxy acrylate and 2,2' -bisphenol-based hexafluoropropane.
The fluorine-containing epoxy acrylate is prepared by adopting the following scheme:
1) Adding fluorine-containing epoxy resin and a polymerization inhibitor into a reaction container, gradually heating to 105 ℃ in the stirring process, and stirring for 25min, wherein the mass ratio of the fluorine-containing epoxy resin to the polymerization inhibitor is 1.1:0.052.
2) Adding acrylic acid and a catalyst into the step 1), adding the acrylic acid and the catalyst in a dropwise manner, and stirring the mixture at the temperature for reaction for 5 hours to obtain the fluorine-containing polyurethane acrylate, wherein the mass ratio of the acrylic acid to the catalyst is 1.8:0.019.
the structural formula of the fluorine-containing epoxy resin is shown as formula I:
wherein p is an alkyl group having a value of 2, q is a value of 3, and R is a C3.
The preparation method comprises the following steps:
s1: adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 70 ℃ in the stirring process, preserving heat for 4 hours, adding hydroxyl (methyl) acrylate and a polymerization inhibitor, continuously reacting for 4 hours at the temperature, and sampling to determine that the isocyanate content is zero.
S2: adding fluorine-containing polyurethane acrylate and 2,2' -bisphenol hexafluoropropane into the step S1, stirring for 1h, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is 1.2:0.004:0.5.
s3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), then placing the mixture at the temperature of-7 ℃ for standing for 4 hours, and then heating the mixture to the temperature of 75 ℃ for stirring and reacting for 6 hours to obtain the optical fiber coating.
The fluorine-containing epoxy resin is selected from octafluorobiphenyl diglycidyl ether.
The fluorine-containing polyol is fluorine-containing polyester unit alcohol and fluorine-containing polyester dihydric alcohol.
The isocyanate is selected from dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI).
The photoinitiator comprises 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2-phenylbenzyl-2-dimethyl amine-1- (4-morpholinophenyl) butanone.
The accelerator is selected from fluorine-containing silane coupling agents;
the polymerization inhibitor is selected from p-hydroxyanisole;
the catalyst is dibutyl tin dilaurate, N-dimethyl cyclohexylamine, bis (2-dimethylaminoethyl) ether, triethanolamine and dimethylaminoethanol N, N' -dimethylpyridine;
the auxiliary agent is selected from defoamer, flatting agent, antioxidant and stabilizer.
Example 4
The preparation method of the low-refractive-index optical fiber coating comprises the following raw materials in parts by weight: 40 parts of fluorine-containing oligomer, 5 parts of photoinitiator, 1.2 parts of polymerization inhibitor, 2.8 parts of accelerator and 4.2 parts of auxiliary agent;
the fluorine-containing oligomer comprises the following components in mass ratio of 5:1:1.4 fluorine-containing urethane acrylate, fluorine-containing epoxy acrylate and 2,2' -bisphenol-based hexafluoropropane.
The fluorine-containing epoxy acrylate is prepared by adopting the following scheme:
1) Adding fluorine-containing epoxy resin and a polymerization inhibitor into a reaction container, gradually heating to 115 ℃ in the stirring process, and stirring for 25min, wherein the mass ratio of the fluorine-containing epoxy resin to the polymerization inhibitor is 1.4:0.076.
2) Adding acrylic acid and a catalyst into the step 1), adding the acrylic acid and the catalyst in a dropwise manner, and stirring the mixture at the temperature for reaction for 5 hours to obtain the fluorine-containing polyurethane acrylate, wherein the mass ratio of the acrylic acid to the catalyst is 2.4:0.032.
the structural formula of the fluorine-containing epoxy resin is shown as formula I:
wherein p is 3, q is 4, and R is C6 alkyl.
The preparation method comprises the following steps:
s1: adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 75 ℃ in the stirring process, preserving heat for 4 hours, adding hydroxyl (methyl) acrylate and a polymerization inhibitor, continuously reacting at the temperature for 5 hours, and sampling to determine that the isocyanate content is zero.
S2: adding fluorine-containing polyurethane acrylate and 2,2' -bisphenol hexafluoropropane into the step S1, stirring for 2 hours, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is 1.8:0.01:0.8.
s3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), standing at the temperature of-9 ℃ for 5 hours, and then heating to the temperature of 85 ℃ for stirring and reacting for 7 hours to obtain the optical fiber coating.
The fluorine-containing epoxy resin is selected from 2, 2-bisphenol hexafluoropropane diglycidyl ether.
The fluorine-containing polyol is fluorine-containing polyether unit alcohol and fluorine-containing polyether dihydric alcohol.
The isocyanate is selected from Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) and diphenylmethane diisocyanate (MDI).
The photoinitiator comprises 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-phenylbenzyl-2-dimethyl amine-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone and benzoin dimethyl ether.
The accelerator is selected from fluorine-containing silane coupling agents;
the polymerization inhibitor is selected from hydroquinone;
the catalyst is a mixture of dibutyl tin dilaurate and N, N-dimethyl cyclohexylamine;
the auxiliary agent is selected from defoamer, flatting agent, antioxidant and stabilizer.
Performance test:
the following properties were tested for the optical fiber coatings prepared in examples 1 to 4, wherein the glass adhesion test method was as follows:
the liquid coating was cured on a polished glass plate to a cured film having a thickness of 100. Mu.m. Cutting a 150mm multiplied by 25mm sample, peeling off the adhesive surface by 25mm, clamping the adhesive surface by a clamp, fixing the other end of the glass plate on furniture of an electronic pulling machine, starting the pulling machine, pulling the cured film at a speed of 100mm/min, and performing 180-degree peeling test to enable the cured film to be slowly peeled off from the glass plate continuously, and reading the peeling force displayed by the pulling machine, namely the glass adhesive force.
The test results are shown in table 1,
table 1. Test results:
as can be seen from Table 1, the low refractive index optical fiber coatings prepared in examples 1 to 4 of the present invention have excellent overall properties.
Claims (6)
1. The preparation method of the low-refractive-index optical fiber coating is characterized by comprising the following raw materials in parts by weight: 20 to 50 parts of fluorine-containing oligomer, 2 to 6 parts of photoinitiator, 0.5 to 1.5 parts of polymerization inhibitor, 1.2 to 3.4 parts of accelerator and 2.6 to 4.8 parts of auxiliary agent; the fluorine-containing oligomer comprises the following components in percentage by mass of 3-6:1: 1.1 to 1.5 of fluorine-containing polyurethane acrylate, fluorine-containing epoxy acrylate and 2,2' -bisphenol hexafluoropropane;
the fluorine-containing epoxy acrylate is prepared by adopting the following scheme:
1) Adding fluorine-containing epoxy resin and a polymerization inhibitor into a reaction container, gradually heating to 100-120 ℃ in the stirring process, and stirring for 20-30 min, wherein the mass ratio of the fluorine-containing epoxy resin to the polymerization inhibitor is (1-1.5): (0.032 to 0.084);
2) Adding acrylic acid and a catalyst into the step 1), adding the acrylic acid and the catalyst in a dropwise manner, and stirring the mixture at the temperature for reaction for 4 to 6 hours to obtain the fluorine-containing polyurethane acrylate, wherein the mass ratio of the acrylic acid to the catalyst is (1.2 to 2.6): (0.014 to 0.036);
the structural formula of the fluorine-containing epoxy resin is shown as formula I:
wherein, the value of p is 1-3, the value of q is 1-5, and R is C1-C6 alkyl or alkoxy;
the preparation method comprises the following steps:
s1: adding fluorine-containing polyol, isocyanate and a catalyst into a container, heating to 65-80 ℃ in the stirring process, preserving heat for reaction for 3-5 h, then adding (methyl) acrylic hydroxyl ester and a polymerization inhibitor, continuously reacting for 3-6 h at the temperature, and sampling to determine that the isocyanate content is zero;
s2: adding fluorine-containing polyurethane acrylic ester and 2,2' -bisphenol hexafluoropropane into the step S1, continuously stirring for 1-2 h, and cooling to room temperature, wherein the mass ratio of fluorine-containing polyol, catalyst and (methyl) acrylic acid hydroxyl ester is (1-2): (0.001-0.012): (0.2-0.9);
s3: and (2) adding the photoinitiator, the polymerization inhibitor, the accelerator and the auxiliary agent into the step (S2), then placing the mixture at-10 to-5 ℃ for standing for 3-6 hours, heating the mixture to 70-90 ℃ and stirring the mixture for reacting for 4-8 hours to obtain the optical fiber coating.
2. The method for preparing a low refractive index optical fiber coating according to claim 1, wherein the fluorine-containing epoxy resin is selected from any one of 2, 2-bisphenol hexafluoropropane diglycidyl ether, octafluorobiphenyl diglycidyl ether, 1,3- (bishexafluoro light propyl) benzene diglycidyl ether and 1, 4-bis (hexafluoro antelope inner) benzene diglycidyl oil-scavenging ether.
3. The method for preparing a low refractive index optical fiber coating according to claim 1, wherein the fluorine-containing polyol is one or a mixture of more than two of fluorine-containing polyether unit alcohol, fluorine-containing polyether glycol, fluorine-containing polyester unit alcohol and fluorine-containing polyester glycol.
4. The method for preparing the low refractive index optical fiber coating according to claim 1, wherein the isocyanate is selected from any one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).
5. The method for preparing a low refractive index optical fiber coating according to claim 1, wherein the photoinitiator comprises one or more of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-phenylbenzyl-2-dimethyl amine-1- (4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, benzoin dimethyl ether.
6. The method of preparing a low refractive index optical fiber coating according to claim 1, wherein the accelerator is selected from the group consisting of fluorine-containing silane coupling agents;
the polymerization inhibitor is selected from one of hydroquinone and p-hydroxyanisole;
the catalyst is one or more than two of dibutyl tin dilaurate, N, N-dimethyl cyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N ' -tetramethyl alkylene diamine, triethylamine, N, N-dimethylbenzylamine, triethanolamine and dimethylaminoethanol N, N ' -dimethylpyridine;
the auxiliary agent is selected from defoamer, flatting agent, antioxidant and stabilizer.
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