CN115403716A - Ultraviolet-curing acrylic resin composition and preparation and application thereof - Google Patents
Ultraviolet-curing acrylic resin composition and preparation and application thereof Download PDFInfo
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- CN115403716A CN115403716A CN202211117985.7A CN202211117985A CN115403716A CN 115403716 A CN115403716 A CN 115403716A CN 202211117985 A CN202211117985 A CN 202211117985A CN 115403716 A CN115403716 A CN 115403716A
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 42
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 47
- 239000011737 fluorine Substances 0.000 claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 8
- -1 isocyano ethyl Chemical group 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 24
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000013307 optical fiber Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- QWYSJTTWCUXHQO-UHFFFAOYSA-N [F].OC(=O)C=C Chemical compound [F].OC(=O)C=C QWYSJTTWCUXHQO-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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Abstract
The invention relates to the technical field of acrylic resin, and particularly provides an ultraviolet-curing acrylic resin composition, and a preparation method and an application thereof. The oligomer has mild conditions in the synthesis process, does not need to introduce a solvent, has no byproducts, avoids raw material waste, saves resources, has simple post-treatment, does not generate wastes, and is safe and environment-friendly. And the oligomers have good compatibility with each other and the refractive indexes of the oligomers are close to each other, so that the fluorine-containing acrylate composition has the advantages of high performance, high transparency, low refractive index and the like.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to an ultraviolet-curing acrylic resin composition and application thereof, and particularly relates to a low-refractive-index ultraviolet-curing acrylic resin composition with controllable modulus and viscosity, and preparation and application thereof.
Background
The F element has large electronegativity and low polarizability, so that the fluorine-containing polymer has the optical characteristic of low refractive index. The fluorine-containing acrylate polymer has low refractive index, high transparency in the ultraviolet light to infrared light region of an electromagnetic spectrum and UV photocuring characteristic, so that the fluorine-containing acrylate polymer is widely applied to the fields of optics, dust prevention, fog prevention, graffiti prevention, biomedicine and the like, particularly to the application on special optical fibers, and the fluorine-containing acrylate polymer is often used as a main raw material for preparing a low-refractive-index coating. For example, in the optical fiber coating resin with low refractive index provided by patent CN105273613B, the refractive index of prepolymer a is 1.362, and prepolymer B is a monofunctional fluorine-containing acrylate polymer, and the activity in the photocuring process is low, and the fluorinated acrylate containing terminal hydroxyl groups used in prepolymer a and prepolymer B is expensive, the yield is limited, and the production and application are limited. In addition, the fluoroacrylate polymers, when applied, need to adhere to the coated substrate by the action of various additives, as proposed in patent application CN107418423A, which has the problem of poor storage stability or poor transport stability due to poor compatibility of the additives with the raw materials such as fluoroacrylate polymers.
In view of this, the present invention is proposed.
Disclosure of Invention
The invention provides an ultraviolet light curing acrylic resin composition and preparation and application thereof, aiming at solving the defects of poor compatibility, unstable performance, complex process and the like of a fluorine-containing acrylate polymer in the preparation and application processes in the prior art.
The invention provides an ultraviolet light curing acrylic resin composition, which comprises the following components: oligomer A and oligomer B;
the structural formula of oligomer A is:
in the structural formula of oligomer A, R 1 is-CH 3 or-H; r 2 is-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH(CH 3 )-；R f Is composed of
-(CH 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20;
the structural formula of oligomer B is:
in the structural formula of oligomer B, R 1 is-CH 3 or-H; r f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20.
On the basis, the oligomer A with one end being siloxane group and the other end being an acrylate double bond is mixed with the oligomer B, and the oligomer A has double functions of the fluorine-containing acrylate polymer and a silane coupling agent, can be photocured to form a film and also has the role of the silane coupling agent, so that the adhesion of the system to a substrate is effectively improved, and the problem that the conventional silane coupling agent is generally incompatible with the fluorine-containing acrylate with low refractive index can be solved; in addition, the oligomer A and the oligomer B designed by the invention both contain polyether chain segments and have acrylate double bond functional groups at the end parts, so that the compatibility and the refractive index of the composition meet the use requirements.
According to the ultraviolet curing acrylic resin composition provided by the invention, the preparation process of the oligomer A is as follows: one end hydroxyl of the fluorine-containing polyether glycol reacts with isocyano ethyl (methyl) acrylate, and the other end hydroxyl reacts with isocyanate silane coupling agent to generate fluorine-containing acrylate polymer with double bonds at one end and silicon alkoxy at the other end.
The synthetic route of oligomer A is shown in FIG. 1.
The preparation process of the oligomer B comprises the following steps: the difunctional fluorine-containing acrylate polymer is generated by one-step end capping of fluorine-containing polyether diol by isocyano ethyl (methyl) acrylate.
The synthetic route of oligomer B is shown in fig. 2.
In the prior art, the preparation process of the fluorine-containing acrylate polymer is complex, for example, a large amount of solvent is introduced in the preparation process of the fluorine-containing polyurethane acrylate prepolymer A in the patent application CN111057462A, the post-treatment is difficult, and the solvent waste is serious. The oligomer has mild conditions in the synthesis process, does not need to introduce a solvent, has no byproducts, and ensures that the ultraviolet light curing acrylic resin composition has low refractive index.
According to the ultraviolet light curing acrylic resin composition provided by the invention, the mass percent of the oligomer A is 5-15%, and the mass percent of the oligomer B is 40-90%.
The ultraviolet-curing acrylic resin composition provided by the invention further comprises an oligomer C and/or an oligomer D;
the structural formula of the oligomer C is as follows:
in the structural formula of oligomer C, R 1 is-CH 3 or-H; r 3 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、
R f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20;
the structural formula of oligomer D is:
in the structural formulas of oligomer C and oligomer D, R 1 is-CH 3 or-H; r is 4 Is composed of
R f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20.
With the increasing use of fluoroacrylate polymers, the number of ultra-low refractive index curable coatings currently available on the market has also emerged, as disclosed in patent US8552083B1, by way of introduction
D10H and 2-methacryloyloxyethyl isocyanate are synthesized into fluorine-containing bifunctional acrylate polymer AF, and then the fluorine-containing bifunctional acrylate polymer AF is mixed with commercially available fluorine-containing acrylate polymer, acrylic acid monomer, acrylic acid fluorine-containing monomer and lightInitiator and some other assistants to prepare a series of low-refraction curable coatings with refractive indexes varying from 1.32 to 1.40, and the refractive index span of the coatings is large. However, since the requirements for performance are different in different applications, in addition to the refractive index as a first consideration, the viscosity and modulus of the coating in production applications have a great influence on the application range, and the AF viscosity provided by patent US8552083B1 is small and only 650cPs at 25 ℃, and even when mixed with various commercially available fluoroacrylate polymers, there is a problem that the control of the modulus and viscosity is difficult. In another example of a low refractive index optical fiber inner coating and a method for preparing the same, as provided in patent application CN111187568A, a fluorinated urethane acrylate oligomer a with high viscosity has a refractive index of 1.387, which is too high, while a fluorinated bifunctional monomer a has a suitable refractive index, but has a viscosity of only 50cps (25 ℃), which is too low, and there is a problem that it is difficult to balance the viscosity and refractive index of the optical fiber coating resin. The viscosity and modulus of the commercially available fluorine-containing acrylate polymer are often not satisfactory, most products are customized products and are expensive, and the chemical structures of the products are different, so that the problem of difficult regulation is solved.
According to the invention, on the basis of a composition formed by an oligomer A and an oligomer B, an oligomer C and/or an oligomer D are further added, wherein the main chain of the oligomer C contains a longer polyether structure, so that the viscosity of the oligomer C is high, the oligomer C belongs to a high-viscosity low-modulus fluorine-containing acrylate polymer, the oligomer D has three functional groups, a cross-linking structure can be formed during curing, and the viscosity and the hardness of the oligomer D are both high and are high-viscosity high-modulus fluorine-containing acrylate polymer; according to the invention, a series of fluorine-containing acrylate compositions with the modulus range of 10-80 MPa, the viscosity range of 1000-10000 mPa.s and the like can be prepared by introducing high-viscosity low-modulus oligomer C and/or high-viscosity high-modulus oligomer D into a fluorine-containing acrylate polymer system according to different combinations and proportions; more importantly, the chemical structures of the oligomers in the invention are similar, the main chains are all perfluoropolyether structures, the mutual compatibility is good, and the refractive indexes of the oligomers are close, so that the fluorine-containing acrylate composition can have a plurality of performance advantages such as high performance, high transparency, low refractive index and the like.
According to the ultraviolet curing acrylic resin composition provided by the invention, the preparation process of the oligomer C is as follows: the fluorine-containing polyether diol is subjected to chain extension by diisocyanate to generate a hydroxyl-terminated fluorine-containing polymer with two functional groups, and then the fluorine-containing polymer is reacted with isocyano ethyl (methyl) acrylate to generate a bifunctional fluorine-containing acrylate polymer.
The synthetic route for oligomer C is shown in fig. 3.
The oligomer C of the invention extends the chain of the polyether structure main chain through diisocyanate, so that the polyether structure main chain is longer, and the viscosity of the oligomer C is increased.
According to the ultraviolet curing acrylic resin composition provided by the invention, the preparation process of the oligomer D is as follows: the fluorine-containing polyether diol is subjected to chain extension through triisocyanate to generate a trifunctional hydroxyl-terminated polymer, and then the trifunctional fluorine-containing acrylate polymer is generated through reaction with (methyl) isocyanoethyl acrylate.
The synthetic route of oligomer D is shown in FIG. 4.
The oligomer D provided by the invention is used for chain extension and crosslinking of a polyether structure main chain through triisocyanate, so that the oligomer D has three functional groups and a crosslinking structure, and the viscosity and hardness of the oligomer D are increased.
According to the ultraviolet-curing acrylic resin composition provided by the invention, the mass percentage of the oligomer C in the composition is less than or equal to 50%.
According to the ultraviolet-curable acrylic resin composition provided by the invention, the mass percentage of the oligomer D in the composition is less than or equal to 50%.
The preparation method of the ultraviolet curing acrylic resin composition provided by the invention comprises the steps of weighing raw materials according to the mass percentage of each component, uniformly mixing, filtering and defoaming to obtain the ultraviolet curing acrylic resin composition.
The oligomer has mild conditions in the synthesis process, does not need to introduce a solvent, has no byproducts, avoids raw material waste, saves resources, has simple post-treatment, does not generate wastes, and is safe and environment-friendly.
The invention provides application of the ultraviolet curing acrylic resin composition in a coating.
The ultraviolet light curing acrylic resin composition formed by the oligomer can adjust the modulus and viscosity of a system according to different application requirements on the premise of ensuring low refraction; because of its low refractive index, good adhesion with glass base material and ultraviolet light solidifying, it is specially suitable for special optical fiber.
According to the ultraviolet-curing acrylic resin composition and the preparation and application thereof, the oligomer A with one end being siloxane group and the other end being acrylate double bond is mixed with the low-viscosity low-modulus fluorine-containing acrylate polymer (oligomer B), so that the adhesion of a system to a substrate is effectively improved, and the problem that the conventional silane coupling agent is generally incompatible with the low-refractive-index fluorine-containing acrylate is solved. On the basis of the composition formed by the oligomer A and the oligomer B, the oligomer C with high viscosity and low modulus and/or the oligomer D with high viscosity and high modulus are introduced, and a series of fluorine-containing acrylate compositions with modulus ranging from 10 to 80MPa, viscosity ranging from 1000 to 10000mPa & s and the like can be prepared according to different combinations and proportions; more importantly, the chemical structures of the oligomers in the invention are similar, the main chains are all perfluoropolyether structures, the mutual compatibility is good, and the refractive indexes of the oligomers are close, so that the fluorine-containing acrylate composition can have a plurality of performance advantages such as high performance, high transparency, low refractive index and the like.
The oligomer has mild conditions in the synthesis process, does not need to introduce a solvent, has no byproducts, avoids raw material waste, saves resources, has simple post-treatment, does not generate wastes, and is safe and environment-friendly.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a scheme for the synthesis of oligomer A;
FIG. 2 is a scheme of synthesis for oligomer B;
FIG. 3 is a scheme for the synthesis of oligomer C;
figure 4 is a scheme for the synthesis of oligomer D.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
The liquid refractive index was measured with a digital Abbe refractometer according to the Community Standard T/CEMIA 009-2018.
The viscosity was measured with a digital rotational viscometer, according to the group standard T/CEMIA 009-2018.
Elongation at break, tensile strength and specific modulus (2.5% elongation) were measured and calculated using a universal tensile machine with reference to the group standard T/CEMIA 009-2018 and the national standards GBT 1040.1-2006, GBT 1040.2-2006, GBT 1040.3-2006.
The stable storage time is the longest time for stable storage at room temperature, keeping clear and transparent appearance and avoiding phenomena of turbidity, whitening, crystallization, delamination and the like.
Preparation of oligomer A
The synthesis method of the oligomer A comprises the following steps: the fluorine-containing polymer is added into a reactor with mechanical stirringEther diols
E10-H525.6 g, 2-isocyanatoethyl methacrylate 46.55g and dibutyltin dilaurate 0.29g were reacted under nitrogen at 60 ℃ until the NCO value was < 0.1, then 3-isocyanatopropyltrimethoxysilane 61.58g and dibutyltin dilaurate 0.31g were added and the reaction was terminated until the NCO ester was < 0.1, whereupon the resulting oligomer A had a refractive index of 1.353 (25 ℃ C.) and a viscosity of 1100 mPas (25 ℃ C.).
Preparation of oligomer B
The synthesis method of the oligomer B comprises the following steps: adding fluorine-containing polyether diol into a reactor with mechanical stirring
E10-H525.6 g, 2-isocyanatoethyl methacrylate 93.9g and dibutyltin dilaurate 0.61g, and the reaction was terminated when the NCO value was < 0.1 in a nitrogen atmosphere at 60 ℃. The resulting oligomer B was found to have a refractive index of 1.352 (25 ℃ C.) and a viscosity of 1000 mPas (25 ℃ C.).
Preparation of oligomer C
The synthesis method of the oligomer C comprises the following steps: adding fluorine-containing polyether diol into a reactor with mechanical stirring
E10-H525.6 g, 4-diisocyanate dicyclohexylmethane 39.35g and dibutyltin dilaurate 0.23g, when NCO value is less than 0.1 in nitrogen atmosphere and 60 ℃; subsequently, 46.55g of 2-isocyanatoethyl methacrylate and 0.26g of dibutyltin dilaurate were added, and the reaction was terminated when the NCO value was < 0.1 by reaction under a nitrogen atmosphere at 60 ℃. The resulting oligomer C was tested to have a refractive index of 1.356 (25 ℃ C.), and a viscosity of 23000 mPas (25 ℃ C.).
Preparation of oligomer D
The synthesis method of the oligomer D comprises the following steps: adding fluorine-containing polyether glycol into a reactor with mechanical stirring
E10-H525.6 g, hexamethylene diisocyanate based polyisocyanate 57.9g and dibutyltin dilaurate 0.29g, under nitrogen atmosphere and 60 ℃, when the NCO value is less than 0.1; subsequently, 46.55g of 2-isocyanatoethyl methacrylate and 0.31g of dibutyltin dilaurate were added, and the reaction was terminated when the NCO value was < 0.1 by reaction under a nitrogen atmosphere at 60 ℃. The resulting oligomer D was tested to have a refractive index of 1.357 (25 ℃ C.) and a viscosity of 35000 mPas (25 ℃ C.).
Example 1
An ultraviolet light curing acrylic resin composition comprises the following components in percentage by mass: 10% of oligomer A, 46% of oligomer B, 40% of oligomer C, 2% of hexafluorobutyl acrylate and 1173% of photoinitiator, wherein the preparation method comprises the following steps:
weighing the raw materials according to the mass percentage of the components, mechanically stirring at the rotating speed of 300 r/min for 1h at the temperature of 50 ℃, filtering twice by using a filter element with the diameter of 1 mu m, standing for 24h and defoaming to obtain the finished product.
Example 2
An ultraviolet light curing acrylic resin composition comprises the following components in percentage by mass: oligomer A10%, oligomer B46%, oligomer C20%, oligomer D20%, hexafluorobutyl acrylate 2%, and photoinitiator 1173%, which were prepared in the same manner as in example 1.
Example 3
An ultraviolet light curing acrylic resin composition comprises the following components in percentage by mass: oligomer A10%, oligomer B46%, oligomer D40%, hexafluorobutyl acrylate 2%, and photoinitiator 1173%, prepared by the same method as in example 1.
Example 4
An ultraviolet light curing acrylic resin composition comprises the following components in percentage by mass: 10% of oligomer A, 76% of oligomer B, 10% of oligomer C, 2% of hexafluorobutyl acrylate and 1173% of photoinitiator, and the preparation method is the same as in example 1.
Example 5
An ultraviolet light curing acrylic resin composition comprises the following components in percentage by mass: oligomer A10%, oligomer B76%, oligomer D10%, hexafluorobutyl acrylate 2%, and photoinitiator 1173%, prepared by the same method as in example 1.
Example 6
An ultraviolet light curing acrylic resin composition comprises the following components in percentage by mass: oligomer A10%, oligomer B86%, hexafluorobutyl acrylate 2%, and photoinitiator 11732%, and the preparation method is the same as example 1.
Comparative example 1
An acrylic resin composition comprises the following components in percentage by mass: 54% of oligomer B, 20% of oligomer C, 20% of oligomer D, 2% of gamma-methacryloxypropyltrimethoxysilane, 2% of hexafluorobutyl acrylate and 1173% of a photoinitiator, the preparation method of the oligomer B is the same as that of example 1.
Comparative example 2
An acrylic resin composition comprises the following components in percentage by mass: 55% of oligomer B, 20% of oligomer C, 20% of oligomer D, 1% of gamma-methacryloxypropyltrimethoxysilane, 2% of hexafluorobutyl acrylate and 1173% of a photoinitiator, and the preparation method is the same as in example 1.
Comparative example 3
The acrylic resin composition comprises the following components in percentage by mass: 55% of oligomer B, 20% of oligomer C, 20% of oligomer D, 1% of perfluorooctylethyltrimethoxysilane, 2% of hexafluorobutyl acrylate and 1173% of photoinitiator, and the preparation method is the same as that of example 1.
The acrylate compositions of examples 1 to 6 and comparative examples 1 to 3 were tested for properties such as refractive index, viscosity, elongation at break, tensile strength, specific modulus (2.5% elongation), etc., and the test results are shown in Table 1.
TABLE 1
It can be seen from the above table that a series of low refractive index, storage stable fluoroacrylate compositions of different viscosities and different moduli can be prepared by different combinations and ratios of the four oligomers; from examples 1 to 6 and comparative examples 1 to 3, it was revealed that the silane coupling agent was poor in compatibility with the fluorine-containing resin and the formulated coating material could not be stably stored for a long period of time.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An ultraviolet-curable acrylic resin composition, comprising: oligomer A and oligomer B;
the structural formula of oligomer A is:
in the structural formula of the oligomer A, R 1 is-CH 3 or-H; r is 2 is-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -or-CH 2 CH(CH 3 )-；R f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20;
the structural formula of oligomer B is:
in the structural formula of oligomer B, R 1 is-CH 3 or-H; r is f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20.
2. The UV-curable acrylic resin composition according to claim 1, wherein the oligomer A is prepared by the following steps: one end of hydroxyl of the fluorine-containing polyether diol reacts with isocyano ethyl (meth) acrylate, and the other end of hydroxyl reacts with an isocyanate silane coupling agent to generate a fluorine-containing acrylate polymer with a double bond at one end and a silicon alkoxy at the other end.
3. The UV-curable acrylic resin composition according to claim 1, wherein the oligomer A is present in an amount of 5 to 15% by mass and the oligomer B is present in an amount of 40 to 90% by mass.
4. The UV-curable acrylic resin composition according to claim 1, further comprising an oligomer C and/or an oligomer D;
the structural formula of oligomer C is:
in the structural formula of oligomer C, R 1 is-CH 3 or-H; r is 3 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、
R f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20;
the structural formula of oligomer D is:
in the structural formulae of oligomer C and oligomer D, R 1 is-CH 3 or-H; r is 4 Is composed of
R f Is- (CH) 2 CH 2 O) x CH 2 CF 2 O(CF 2 CF 2 O) y (CF 2 O) z CF 2 CH 2 (OCH 2 CH 2 ) x -, wherein x, y and z are integers of 1 to 20.
5. The UV-curable acrylic resin composition according to claim 4, wherein the oligomer C is prepared by the following steps: the fluorine-containing polyether diol is subjected to chain extension by diisocyanate to generate a hydroxyl-terminated fluorine-containing polymer with two functional groups, and then the fluorine-containing polymer is reacted with isocyano ethyl (methyl) acrylate to generate a bifunctional fluorine-containing acrylate polymer.
6. The UV-curable acrylic resin composition according to claim 4, wherein the oligomer D is prepared by the following steps: the fluorine-containing polyether glycol is subjected to chain extension through triisocyanate to generate a trifunctional hydroxyl-terminated polymer, and then the trifunctional hydroxyl-terminated polymer is reacted with (methyl) isocyano ethyl acrylate to generate the trifunctional fluorine-containing acrylate polymer.
7. The UV-curable acrylic resin composition according to claim 4, wherein the oligomer C is present in an amount of 50% by mass or less.
8. The UV-curable acrylic resin composition according to claim 4, wherein the oligomer D is present in an amount of 50% by mass or less.
9. The method for preparing the ultraviolet-curable acrylic resin composition of any one of claims 1 to 8, wherein the ultraviolet-curable acrylic resin composition is prepared by weighing raw materials in percentage by mass, mixing uniformly, and then filtering and defoaming.
10. Use of the uv-curable acrylic resin composition according to any one of claims 1 to 8 in a coating.
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| CN111057462A (en) * | 2019-12-16 | 2020-04-24 | 中昊北方涂料工业研究设计院有限公司 | Ultra-low refractive index high fluorine content UV curing polyurethane acrylate coating |
| CN111187568A (en) * | 2020-02-26 | 2020-05-22 | 上海维凯光电新材料有限公司 | Low-refractive-index optical fiber inner layer coating and preparation method thereof |
| CN113355017A (en) * | 2021-05-06 | 2021-09-07 | 武汉长盈鑫科技有限公司 | Low-refractive-index optical fiber coating resin with high glass transition temperature |
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| CN111057462A (en) * | 2019-12-16 | 2020-04-24 | 中昊北方涂料工业研究设计院有限公司 | Ultra-low refractive index high fluorine content UV curing polyurethane acrylate coating |
| CN111187568A (en) * | 2020-02-26 | 2020-05-22 | 上海维凯光电新材料有限公司 | Low-refractive-index optical fiber inner layer coating and preparation method thereof |
| CN113355017A (en) * | 2021-05-06 | 2021-09-07 | 武汉长盈鑫科技有限公司 | Low-refractive-index optical fiber coating resin with high glass transition temperature |
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| 冯裕智;谢小娜;邢杰慧;唐旭东;: "多硅氧烷改性全氟聚醚涂覆剂的制备与性能", 有机硅材料, no. 03, pages 198 - 202 * |
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