CN117866001A - Fluorine-containing silane coupling agent compound and preparation method and application thereof - Google Patents
Fluorine-containing silane coupling agent compound and preparation method and application thereof Download PDFInfo
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- CN117866001A CN117866001A CN202311751362.XA CN202311751362A CN117866001A CN 117866001 A CN117866001 A CN 117866001A CN 202311751362 A CN202311751362 A CN 202311751362A CN 117866001 A CN117866001 A CN 117866001A
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- fluorine
- silane coupling
- coupling agent
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 50
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- -1 epoxy group siloxane Chemical class 0.000 claims abstract description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 11
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 6
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims description 2
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 claims description 2
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 2
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- MBOOMFWIUMKSNA-UHFFFAOYSA-N isocyanatomethylsilane Chemical compound [SiH3]CN=C=O MBOOMFWIUMKSNA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 2
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 claims description 2
- CXZGQIAOTKWCDB-UHFFFAOYSA-N perfluoropentanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CXZGQIAOTKWCDB-UHFFFAOYSA-N 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- FAVBSCCRVFWZQC-UHFFFAOYSA-N ethoxy(isocyanatomethyl)silane Chemical compound N(=C=O)C[SiH2]OCC FAVBSCCRVFWZQC-UHFFFAOYSA-N 0.000 claims 1
- QRFPECUQGPJPMV-UHFFFAOYSA-N isocyanatomethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CN=C=O QRFPECUQGPJPMV-UHFFFAOYSA-N 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 239000013307 optical fiber Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RETHHFNVIWBDJQ-UHFFFAOYSA-N isocyanic acid;trimethoxy(methyl)silane Chemical compound N=C=O.CO[Si](C)(OC)OC RETHHFNVIWBDJQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000758 substrate Substances 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
Abstract
The invention discloses a fluorine-containing silane coupling agent compound, a preparation method and application thereof; firstly, epoxy group ring-opening reaction is carried out on epoxy group siloxane and fluorine-containing carboxylic acid to generate hydroxyl fluorine-containing intermediate, and then the hydroxyl fluorine-containing intermediate reacts with isocyanate group siloxane to prepare the silane coupling agent with higher siloxane content. The silane coupling agent is used in UV low refractive fiber coating, and has excellent adhesion and water resistance.
Description
Technical Field
The invention relates to the technical field of synthesis of fluorine-containing silane coupling agents, in particular to a fluorine-containing silane coupling agent compound, a preparation method and application thereof, and especially relates to a water-resistant fluorine-containing silane coupling agent compound for low-refractive-index optical fiber coating.
Background
The optical fiber mainly comprises a core layer, a cladding layer, an inner coating layer and an outer coating layer. The inner coating is soft and elastic, and is coated on the surface of the cladding to play a role in buffering external impact; the outer coating has high rigidity and strength, can improve the mechanical strength of the optical fiber, resist external impact and protect the optical fiber from the external environment. Typically, the refractive index of the optical fiber inner coating is in the range of 1.46-1.48, however, some specialty fibers require a low refractive index, high mechanical strength, excellent adhesion inner coating to achieve a larger numerical aperture and less optical signal attenuation. The low refractive index optical fiber coating is a special coating for the inner layer of the optical fiber, is generally designed as an organic fluorine or organic silicon ultraviolet light curing acrylic resin material, and is characterized by having a lower refractive index, and is generally between 1.35 and 1.42. The refractive index of the curing film is low, the numerical aperture of the optical fiber can be increased, the long-distance transmission efficiency of light energy is effectively improved on the premise of ensuring good mechanical properties, and the light loss is reduced. The lower refractive index of the glass material is utilized to form the optical waveguide with the characteristic of high NA value together with the silicon-based glass material.
The low refractive fiber coating consists of fluorine-containing polyurethane acrylate oligomer, a monofunctional fluorine-containing acrylate monomer, a difunctional fluorine-containing acrylate monomer, an initiator, a leveling agent and a silane coupling agent. However, the low refractive index optical fiber coating in China has poor adhesion with glass generally at present, and particularly has poor water boiling resistant adhesion of the optical fiber, so that the optical fiber is easy to have the problems of poor production stability, signal attenuation and the like.
The invention modifies the silane coupling agent in the low-refractive coating, introduces fluorine-containing groups, increases the siloxane content in the coupling agent, ensures the low refractive index of the coating, and simultaneously maintains higher mechanical strength and excellent adhesive force of the water-boiling glass.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a fluorine-containing silane coupling agent compound, a preparation method and application thereof, in particular to a water-resistant fluorine-containing silane coupling agent for low refractive index optical fiber coating and a preparation method thereof, which relate to the technical field of fluorine-containing silane coupling agent synthesis; specifically, epoxy group siloxane and fluorine-containing carboxylic acid are utilized to generate hydroxyl fluorine-containing intermediate after epoxy group ring-opening reaction, and then the hydroxyl fluorine-containing intermediate is reacted with isocyanate group siloxane to prepare the adhesive with strong boiling resistance.
The aim of the invention is realized by the following technical scheme:
the invention relates to a fluorine-containing silane coupling agent compound, which has a structural formula shown in a formula (A):
wherein m=1 to 8; n=1 to 5;
r1 is-OCH 3 、-OCH 3 CH 2 One of the following;
r2 is-OCH 3 、-OCH 3 CH 2 、-CH 3 、-CH 3 CH 2 One of the following;
r3 is (CH) 2 ) a 、(CH 2 CH 2 ) b 、(CH 2 O) c 、(CH 2 CH 2 O) d 、、C 6 H 9 One of the following; wherein the values of a, b, c and d are respectively 1-3;
r4 is-OCH 3 、-OCH 3 CH 2 One of the following;
r5 is-OCH 3 、-OCH 3 CH 2 、-CH 3 、-CH 3 CH 2 One of them.
The invention also provides a preparation method of the fluorine-containing silane coupling agent compound, which comprises the following steps:
s1, mixing epoxy siloxane and fluorine-containing carboxylic acid, adding a catalyst alpha, and heating for reaction to obtain a hydroxyl fluorine-containing intermediate (shown in the following formula B);
s2, mixing the hydroxyl fluorine-containing intermediate (formula B) prepared in the S1 with isocyanate siloxane, and adding a catalyst beta for reaction to obtain the fluorine-containing silane coupling agent compound.
The invention prepares the silane coupling agent with higher siloxane content (improving adhesion) by utilizing epoxy group ring-opening reaction of epoxy group siloxane and fluorine-containing carboxylic acid to generate hydroxyl fluorine-containing intermediate (B) and then reacting with isocyanate group siloxane.
Further, in step S1, the epoxysiloxane comprises one or more of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
Further, in step S1, the fluorine-containing carboxylic acid is one or more of perfluoropropionic acid, perfluorobutyric acid, perfluorovaleric acid, tridecanfluoroheptanoic acid, heptadecafluorononanoic acid.
Further, in the step S1, in the epoxysiloxane and the fluorine-containing carboxylic acid, the molar ratio of the epoxy group to the carboxyl group is 0.9-1.1:1.
further, in step S1, the catalyst α includes one or more of triethylamine, dimethylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N dimethylformamide, N dimethylaniline, tetraethylammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, and triphenylphosphine. The addition amount of the catalyst alpha accounts for 0.5% -3% of the total mass of the substances (total amount of epoxy siloxane and fluorine-containing carboxylic acid) of the whole reaction system.
Further, in the step S1, the temperature of the heating reaction is 90-120 ℃ and the time is 4-10 h.
Further, in step S2, the isocyanate group-containing siloxane includes one or more of 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl methyl diethoxysilane, 3-isocyanatopropyl methyl dimethoxysilane, isocyanate methyl trimethoxysilane, isocyanate methyl ethoxysilane, and 1-dimethoxy (methyl) silylmethyl isocyanate. If the siloxane does not contain isocyanate, it cannot react.
Further, in the step S2, the molar ratio of the hydroxyl-containing fluorine-containing intermediate to the isocyanatosiloxane is 1-1.1:1.
further, in step S2, the catalyst β is one or more of dibutyl tin dilaurate, stannous octoate, dibutyl tin di (dodecyl sulfide), dibutyl tin diacetate, or fluorine-containing organotin. The addition amount of the catalyst beta accounts for 0.03% -1% of the total mass of the substances (the total amount of the hydroxyl-containing fluorine-containing intermediate and the isocyanate-based siloxane) of the whole reaction system.
Further, in the step S2, the reaction temperature is 20-90 ℃ and the reaction time is 2-8h.
The invention also relates to application of the fluorine-containing silane coupling agent compound in preparing low refractive fiber paint, in particular to application in UV low refractive fiber paint.
Compared with the prior art, the invention has the following beneficial effects:
the invention modifies the silane coupling agent in the low-refractive coating, introduces fluorine-containing groups, can improve the compatibility in the system, increases the siloxane content in the coupling agent, ensures the low refractive index of the coating, and simultaneously maintains higher mechanical strength and excellent adhesive force of the water-boiling glass.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
The embodiment relates to synthesis and application of a fluorine-containing silane coupling agent, wherein the synthesis comprises the following steps:
(1) Adding 32.5 g of 3-glycidoxypropyl trimethoxysilane (molecular weight 236.34) and 50.0 g of tridecanfluoroheptanoic acid (molecular weight 364.06) into a drying reaction kettle equipped with a condenser, a thermometer and a stirrer at normal temperature, stirring uniformly, adding 2.475 g of tetraethylammonium bromide, and preserving heat at 80 ℃ for 10 hours to obtain an intermediate (1S);
(2) Then cooled to room temperature (25 ℃ C.), 28.2 g of 3-isocyanatopropyl trimethoxysilane (molecular weight 205.28) was added to the reactor, and after stirring well, 0.554 g of dibutyltin diacetate was added and the reaction was maintained at 50 ℃ C. For 6 hours.
The resulting fluorine-containing silane coupling agent was S1 (the synthesis reaction, the product structure was fixed).
Example 2
The embodiment relates to synthesis and application of a fluorine-containing silane coupling agent, wherein the synthesis comprises the following steps:
(1) 76.5 g of 3-glycidoxypropyl triethoxysilane (molecular weight 278.34) and 50.0 g of tridecanfluoroheptanoic acid (molecular weight 364.06) are added into a drying reaction kettle equipped with a condenser tube, a thermometer and a stirrer at normal temperature, 3.795 g of tetraethylammonium bromide is added after stirring uniformly, and the mixture is kept at 80 ℃ for 10 hours to obtain an intermediate (2S);
(2) Then cooled to room temperature, 28.2 g of 3-isocyanatopropyl trimethoxysilane (molecular weight 205.28) was added to the reactor, and after stirring well, 0.774 g of dibutyltin diacetate was added and the reaction was maintained at 50℃for 6 hours. The obtained fluorine-containing silane coupling agent is S2.
Example 3
The embodiment relates to synthesis and application of a fluorine-containing silane coupling agent, wherein the synthesis comprises the following steps:
(1) Adding 32.5 g of 3-glycidoxypropyl trimethoxysilane (molecular weight 236.34) and 50.0 g of tridecanfluoroheptanoic acid (molecular weight 364.06) into a drying reaction kettle equipped with a condenser, a thermometer and a stirrer at normal temperature, stirring uniformly, adding 2.475 g of tetraethylammonium bromide, and preserving heat at 80 ℃ for 10 hours to obtain an intermediate (3S);
(2) Then cooled to room temperature, 67.9 g of 3-isocyanatopropyl triethoxysilane (molecular weight 247) was added to the reactor, and after stirring uniformly, 0.752 g of dibutyltin diacetate was added, and the temperature was kept at 50℃for 6 hours. The obtained fluorine-containing silane coupling agent is S3.
Example 4
The embodiment relates to synthesis and application of a fluorine-containing silane coupling agent, wherein the synthesis comprises the following steps:
(1) 76.5 g of 3-glycidoxypropyl triethoxysilane (molecular weight 278.34) and 50.0 g of tridecanfluoroheptanoic acid (molecular weight 364.06) were added at room temperature to a drying reaction vessel equipped with a condenser, a thermometer and a stirrer, and after stirring, 3.795 g of tetraethylammonium bromide was added and the mixture was kept at 80℃for 10 hours to obtain an intermediate (4S).
(2) Then cooled to room temperature, 67.9 g of 3-isocyanatopropyl triethoxysilane (molecular weight 247) was added to the reactor, and after stirring uniformly, 0.972 g of dibutyltin diacetate was added, and the reaction was kept at 50℃for 6 hours. The obtained fluorine-containing silane coupling agent is S4.
Comparative example 1
This comparative example relates to the synthesis and use of a silane coupling agent, the synthesis procedure being substantially the same as example 1, except that: trideoxyfluoro is replaced by equimolar heptanoic acid.
Application examples
The fluorine-containing silane coupling agents S1 to S4 obtained in the above example and commercially available silane coupling agents (coupling agents without fluorine) KH560 and KH570 are respectively prepared into low refractive index optical fiber coatings, and the contents of the components are as follows in percentage by weight: 87.5% of fluorine-containing polyurethane acrylate oligomer, 6.8% of monofunctional fluorine-containing acrylate monomer, 5.7% of difunctional fluorine-containing acrylate, 1% of initiator, 1% of flatting agent and 0.5% of silane coupling agent, wherein the sum of the components is 100%. The viscosity at 25℃was measured with a BROOKFIELD DV 2-type rotational viscometer, and the refractive index at 25℃was measured with an Abbe refractometer WZS-1. Coating the coating on a glass substrate, controlling the thickness of the coating to be about 250 micrometers, and performing ultraviolet light curing under a mercury lamp with the curing energy of 1500mJ/cm 2 Curing time was 30 seconds. The curing effect of the test specimens was tested by acupressure. The test pieces were then placed in a water bath at 60℃for 3 days, and the film-forming peel force was measured. The results obtained are shown in Table 1.
TABLE 1
| Peel force N/cm | S1 | S2 | S3 | S4 | KH560 | KH570 |
| 60 ℃/3 days instant | 0.230 | 0.229 | 0.225 | 0.219 | 0.118 | 0.114 |
| After 24 hours at 60 ℃/3 days | 0.338 | 0.352 | 0.361 | 0.314 | 0.206 | 0.192 |
| viscosity/mPa.s at 25 DEG C | 2180 | 2620 | 2490 | 2965 | 2540 | 2485 |
| Refractive index at 25 DEG C | 1.3643 | 1.3640 | 1.3640 | 1.3645 | 1.3651 | 1.3650 |
| Curing effect | + | ++ | ++ | + | +- | - |
+ indicates good cure, ++ -indicates slightly worse cure performance, -indicates poor cure performance.
As is clear from Table 1, the low refractive index optical fiber coatings prepared in examples S1 to S4 synthesized according to the present invention can be prepared in a viscosity range of 2100 to 3000 mPas, and have a refractive index of 1.3640 to 1.3650, and have good curability. The stripping force of the film formed in water bath at 60 ℃ for 3 days is obviously superior to that of comparative examples KH560 and KH570, and the water resistance requirement of the low refractive fiber coating can be better met.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (10)
1. The fluorine-containing silane coupling agent compound is characterized in that the structural formula of the fluorine-containing silane coupling agent compound is shown as a formula (A):
wherein m=1 to 8; n=1 to 5;
r1 is-OCH 3 、-OCH 3 CH 2 One of the following;
r2 is-OCH 3 、-OCH 3 CH 2 、-CH 3 、-CH 3 CH 2 One of the following;
r3 is (CH) 2 ) a 、(CH 2 CH 2 ) b 、(CH 2 O) c 、(CH 2 CH 2 O) d 、、C 6 H 9 One of the following; wherein the values of a, b, c and d are respectively 1-3;
r4 is-OCH 3 、-OCH 3 CH 2 One of the following;
r5 is-OCH 3 、-OCH 3 CH 2 、-CH 3 、-CH 3 CH 2 One of them.
2. A method for preparing the fluorine-containing silane coupling agent compound according to claim 1, comprising the steps of:
s1, mixing epoxy siloxane and fluorine-containing carboxylic acid, adding a catalyst alpha, and heating for reaction to obtain a hydroxyl fluorine-containing intermediate;
s2, mixing the hydroxyl fluorine-containing intermediate prepared in the step S1 with isocyanate siloxane, adding a catalyst beta, and reacting to obtain the fluorine-containing silane coupling agent compound.
3. The preparation method according to claim 2, wherein in the step S1, the epoxysiloxane includes one or more of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxyethyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; the fluorine-containing carboxylic acid is one or more of perfluoropropionic acid, perfluorobutyric acid, perfluorovaleric acid, trideoxyfluoro heptanoic acid and heptadecafluorononanoic acid.
4. The method according to claim 2, wherein in step S1, the molar ratio of epoxy groups to carboxyl groups in the epoxysiloxane and the fluorocarboxylic acid is 0.9 to 1.1:1.
5. the preparation method according to claim 2, wherein in the step S1, the catalyst α comprises one or more of triethylamine, dimethylamine, N-methylpyrrolimide, N-ethylpyrrolidine amide, N dimethylformamide, N dimethylaniline, tetraethylammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, triphenylphosphine.
6. The method according to claim 2, wherein in step S1, the heating reaction is performed at a temperature of 90 to 120 ℃ for a time of 4 to 10 hours.
7. The method of preparing according to claim 2, wherein in step S2, the isocyanate group-containing siloxane comprises one or more of 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl methyldiethoxysilane, 3-isocyanatopropyl methyldimethoxysilane, isocyanatomethyl trimethoxysilane, isocyanatomethyl ethoxysilane, 1-dimethoxy (methyl) silylmethyl isocyanate; the molar ratio of the hydroxyl fluorine-containing intermediate to the isocyanate group siloxane is 1-1.1:1.
8. the preparation method according to claim 2, wherein in step S2, the catalyst β is one or more of dibutyl tin dilaurate, stannous octoate, dibutyl tin di (dodecyl sulfide), dibutyl tin diacetate, and fluorine-containing organotin.
9. The method according to claim 2, wherein in step S2, the reaction is carried out at a temperature of 20 to 90 ℃ for a time of 2 to 8 hours.
10. Use of the fluorine-containing silane coupling agent compound according to claim 1 for preparing a low refractive fiber coating material.
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