CN102086246B - Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization - Google Patents
Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization Download PDFInfo
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- CN102086246B CN102086246B CN 201010563631 CN201010563631A CN102086246B CN 102086246 B CN102086246 B CN 102086246B CN 201010563631 CN201010563631 CN 201010563631 CN 201010563631 A CN201010563631 A CN 201010563631A CN 102086246 B CN102086246 B CN 102086246B
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Abstract
The invention discloses a method for preparing nanosilica-fluorine-containing acrylic resin through in-situ solution polymerization, which comprises the following steps of: preparing double bond-modified nanosilica; under the action of ultrasonic waves, dispersing the modified nanosilica into monomers and a solvent, reacting double bond on a monomer chain with double bond on the surface of the nanosilica and generating in-situ polymerization, so that the nanosilica particles which are easy to agglomerate achieve nano-scale dispersion in a polymeric matrix. The system is stable and the nanosilica is not precipitated and separated. The nano silica-fluorine-containing acrylic resin composite material prepared by the method fully combines the rigidity, hardness, wear resistance and thermal and chemical stability of the nanosilica and the flexibility, weather resistance and dirt resistance of fluorine-containing acrylic resin, and the impact resistance and thermal stability of the composite material are greatly improved than those of pure fluorine-containing acrylic resin.
Description
Technical field
The invention belongs to the technical field of high molecule nano composite material, be specifically related to the method that a kind of in-situ solution polymerization prepares nano silicon/fluoroacrylic resin matrix material.
Background technology
Nano silicon is a kind of extremely important nano inorganic novel material, because of it has unique volume effect, surface effects, quantum effect and characteristics such as excellent mechanical property and thermo-chemical stability, and is widely used in the modification of polymer materials.Obtain the nano composite material of high comprehensive performance; The problem of its most critical is how to guarantee nanoparticle effectively stable dispersion in polymeric matrix; If disperse badly, not only do not reach intended purposes, also might destroy the original performance of polymer materials.
At present, the method for preparing nano silicon/polymer composites mainly contains blending method, sol-gel method, graft process and situ aggregation method.Blending method is easy and simple to handle; But be difficult to make nano-silicon dioxide particle to obtain good dispersion effect; Because the specific surface area of nanoparticle is big, surface energy is high, very easily to reunite, limited shearing force is difficult to break up the nanoparticle coacervate; Many nanoparticles still are the reunion shape in polymeric matrix reads, and makes many excellent specific properties of nanoparticle to demonstrate fully out; Nano composite material that sol-gel method the is prepared transparency is poor, be prone to contraction embrittlement and be separated; The graft process narrow application range, the layered inorganic material that only suitable polynite is a type; When adopting situ aggregation method, monomer is polymerization reaction take place in the gap of the silicon-dioxide primary particle of reuniting, and the reaction liberated heat makes that the primary particle of reuniting is dissociated; Interparticle distance increases gradually; Thereby realize that the nano level of nano silicon in polymeric matrix disperses, simultaneously, because " nail anchor " effect; The dispersive nano silicon plays enhancing, toughness reinforcing effect to matrix material as " anchor point " equally with the molecular chain around it or segment " nail anchor " together.
Patent CNl844179A discloses a kind of in-situ preparation method of nano SiO 2/boron modified phenolic resin resin nano composite material, and its nano composite material that makes has good thermal property, mechanical property, frictional behaviour and ablation resistance; Patent CNl417246A makes the inorganic nano-particle with extremely strong autohemagglutination effect can be well dispersed in the epoxy matrix material through original position and parcel polymerization; Patent CNl597775A discloses a kind of preparation technology of epoxide resin nano silicon dioxide composite material, and prepared nano composite material all is improved largely on shock strength, tensile strength, elongation at break; Patent CNl844242A discloses the in-situ polymerization of a kind of nylon 6/ epoxy resin/silicon dioxide nano composite material; The purer nylon 6 of the tensile strength of the nano composite material that it makes improves about 30%; Shock strength is 3～5 times of pure nylon 6: people such as Xu Xiangmin are middle report in " matrix material journal " [2008,25 (4), P56-61]; Adopt nano-silicon dioxide modified nylon 66; Can make the tensile strength of matrix material improve 11.2%, the springform leather improves 30.1%, and decomposition peak's temperature improves 14 ℃; People such as Wu Han arch are at " thermosetting resin " [2010; 25 (4); P17-20] middle report, adopt nano silicon that bad epoxy resins of phenolic aldehyde is carried out modification, the adding of nano silicon can effectively improve poach, xanthochromia, hardness, water-intake rate and the salt water resistance corrodibility of coating; People such as Jiang Yumei are in " polymer material science and engineering " [2010; 26 (3); P134-137] in reported the preparation and the performance of a kind of epoxy resin/hyper-branched polyester/nanometer Si02 matrix material; When the massfraction of nanometer Si02 was 1%, the shock strength of nano composite material had improved 10.48KJ/m than pure epoxy resin., the initial heat decomposition temperature of material has also improved 27 ℃.Although existing above-mentioned report about nano-silicon dioxide modified fluoropolymer resin, relevant patent, the paper for preparing nano silicon/fluoroacrylic resin matrix material through the in-situ solution polymerization also is not seen in report.
Summary of the invention
Technical problem: the objective of the invention is to be to provide a kind of in-situ solution polymerization to prepare the method for nano silicon-fluoroacrylic resin matrix material.
Technical scheme: the method that in-situ solution polymerization according to the invention prepares nano silicon-fluoroacrylic resin matrix material may further comprise the steps:
1) 50～100ml absolute ethyl alcohol, 1～10ml deionized water, 1～10ml ammoniacal liquor and 1～20m1 vinyl silicane coupling agent are joined in the four-hole boiling flask that prolong, electric mixer, tap funnel and TM are housed, be warming up to 30～100.C is added drop-wise to the positive tetraethyl orthosilicate of 10～60ml in the flask through tap funnel then, and the control rate of addition makes it dropwise at 2～3h; Stir speed (S.S.) is controlled at 100～600r/min; Drip continued reaction 4～12h, obtain the nano silicon gel of two key modifications
2) step 1) is prepared nano silicon gel is transferred in the hydrothermal reaction kettle; Behind 100～160 ℃ of following ageing 12～48h, obtain the nano silicon deposition; Deposition promptly gets the nano silicon dioxide particles of two key modifications after filtration, washing, vacuum-drying, grinding
3) with step 2) after the nano silicon of prepared two key modifications and monomer, initiator, the solvent; Under the UW effect, disperse O.5～2h; Under the protection of rare gas element; Be heated to 75～100 ℃ of initiated polymerizations, ask 4～12h during reaction, obtain nano silicon/fluoroacrylic resin matrix material.
Among the present invention, the vinyl silanes described in the step 1) is a kind of in vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyl silane triisopropoxide, vinyl three tert.-butoxy silane, the vinyltriacetoxy silane.
Among the present invention, the monomer described in the step 3) comprises fluorochemical monomer and fluorochemical monomer not; Said fluorochemical monomer is one or more in trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, methylacrylic acid ten difluoro heptyl esters, the methylacrylic acid ten trifluoro monooctyl esters;
Said not fluorochemical monomer is one or more in TEB 3K, Jia Jibingxisuanyizhi, ethyl propenoate, Bing Xisuandingzhi, Rocryl 400, Rocryl 410, the vinylbenzene.
Among the present invention, the solvent described in the step 3) is one or more in toluene, YLENE, vinyl acetic monomer, the N-BUTYL ACETATE.
Among the present invention, the add-on of the nano silicon of two key modifications is 0.5～10% of a resin total mass described in the step 31.
Beneficial effect: the present invention has following advantage: (1) is through the nano silicon of the two key modifications of single stage method preparation; Promptly in the preparation nano silicon, reach the effect of two key modifications; Traditional hydrophilic nano silicon-dioxide for preparing earlier wants much easy to its method of carrying out surface-treated again, and modified effect will be got well; (2) during the in-situ solution polymerization; Two keys that nano-silica surface is contained and the two keys on the monomer chain react; Nanoparticle and polymkeric substance are got in touch through the chemical bond of high bond energy; Can guarantee nanoparticle effectively stable dispersion in polymeric matrix, and the dispersive nano silicon as " anchor point " equally with the molecular chain around it or segment " nail anchor " together, matrix material is played enhancing, toughness reinforcing effect; (3) nano silicon/fluoroacrylic resin matrix material has fully combined snappiness, weathering resistance, the contamination resistance of rigidity, hardness, wear resistance, thermo-chemical stability and the fluoroacrylic resin of nano silicon, and the purer fluoroacrylic resin of its shock resistance and thermostability all is improved largely.
Embodiment
Following embodiment further specifies of the present invention, rather than limits scope of the present invention.
Embodiment 1:
Step (1): 80ml absolute ethyl alcohol, 5ml deionized water, 5ml ammoniacal liquor and 10ml vinyltriethoxysilane are joined in the four-hole boiling flask that prolong, electric mixer, tap funnel and TM are housed; Be warming up to 60 ℃; Then the positive tetraethyl orthosilicate of 40ml is added drop-wise in the flask through tap funnel, the control rate of addition makes it dropwise at 2～3h, and stir speed (S.S.) is controlled at 200r/min; Drip continued reaction 8h, obtain the nano silicon gel of two key modifications.
Step (2): the nano silicon gel that step (1) is prepared is transferred in the hydrothermal reaction kettle; Behind 120 ℃ of following ageing 24h, obtain the nano silicon deposition; With sedimentation and filtration, filter cake with washing with alcohol three times after, 80 ℃ of following vacuum-drying 24h; Grind then, promptly get the nano silicon dioxide particles of two key modifications.
Step (3): the Diisopropyl azodicarboxylate behind 12g TEB 3K, 23g Bing Xisuandingzhi, 8g methylacrylic acid ten difluoro heptyl esters, 7g Rocryl 400 and the 1g recrystallization is dissolved in the mixed solvent of 25m1 vinyl acetic monomer and 15ml N-BUTYL ACETATE; The nano silicon dioxide particles that adds two key modifications prepared in the 1g step (2) then disperses lh under the effect of 40kHz UW; Under the protection of high pure nitrogen; Through tap funnel it is added drop-wise in the reactor drum with the bottoming of 20m1 N-BUTYL ACETATE, the dropping time is 3h, and control reaction temperature is 85 ℃; Stirring velocity is 400r/min; After dropwising, continue insulation reaction 7h, obtain the nano silicon massfraction and be nano silicon/fluoroacrylic resin matrix material of 2%.
The shock resistance of reference standard GB/T 1732-1993 test nano silicon/fluoroacrylic resin matrix materials; The shock strength that records matrix material is 84Kg.cm; The shock strength of pure fluoroacrylic resin is 52Kg.cm under the equal test condition, and shock strength improves 62%; Thermogravimetric analysis shows that the purer fluoroacrylic resin of the thermostability of matrix material improves 20 ℃.
Embodiment 2:
Step (1): 50ml absolute ethyl alcohol, 3ml deionized water, 3ml ammoniacal liquor and 5m1 vinyl trichloro silane are joined in the four-hole boiling flask that prolong, electric mixer, tap funnel and TM are housed; Be warming up to 40 ℃; Then the positive tetraethyl orthosilicate of 20ml is added drop-wise in the flask through tap funnel, the control rate of addition makes it dropwise at 2～3h, and stir speed (S.S.) is controlled at 100r/min; Drip continued reaction 5h, obtain the nano silicon gel of two key modifications.
Step (2): the nano silicon gel that step (1) is prepared is transferred in the hydrothermal reaction kettle; Behind 100 ℃ of following ageing 48h, obtain the nano silicon deposition; With sedimentation and filtration, filter cake with washing with alcohol three times after, 80 ℃ of following vacuum-drying 24h; Grind then, promptly get the nano silicon dioxide particles of two key modifications.
Step (3): the Diisopropyl azodicarboxylate behind 11g TEB 3K, 19g Bing Xisuandingzhi, 8g methylacrylic acid ten trifluoro monooctyl esters, 7g Rocryl 410,5g vinylbenzene and the 1g recrystallization is dissolved in the mixed solvent of 20m1 vinyl acetic monomer and 10ml N-BUTYL ACETATE; The nano silicon dioxide particles that adds two key modifications prepared in the 0.25g step (2) then disperses 0.5h under the effect of 40kHz UW; Under the protection of high pure nitrogen; Through tap funnel it is added drop-wise in the reactor drum with the bottoming of 20ml N-BUTYL ACETATE, the dropping time is 3h, and control reaction temperature is 75 ℃; Stirring velocity is 400r/min; After dropwising, continue insulation reaction 8h, obtain the nano silicon massfraction and be nano silicon/fluoroacrylic resin matrix material of 0.5%.
Embodiment 3:
Step (1): lOOml absolute ethyl alcohol, 8ml deionized water, 7.5ml ammoniacal liquor and 18.5m1 γ-(methacryloxy) propyl trimethoxy silicane is joined in the four-hole boiling flask that prolong, electric mixer, tap funnel and TM are housed; Be warming up to 75 ℃; Then the positive tetraethyl orthosilicate of 60ml is added drop-wise in the flask through tap funnel; The control rate of addition makes it dropwise at 2～3h; Stir speed (S.S.) is controlled at 350r/min, drips continued reaction 1Oh, obtains the nano silicon gel of two key modifications.
Step (2): the nano silicon gel that step (1) is prepared is transferred in the hydrothermal reaction kettle; Behind 140 ℃ of following ageing 12h, obtain the nano silicon deposition; With sedimentation and filtration, filter cake with washing with alcohol three times after, 80 ℃ of following vacuum-drying 24h; Grind then, promptly get the nano silicon dioxide particles of two key modifications.
Step (3): the Diisopropyl azodicarboxylate behind 9.5g Jia Jibingxisuanyizhi, 20.5g ethyl propenoate, 8.5g methylacrylic acid hexafluoro butyl ester, 7.5g Rocryl 410,4g vinylbenzene and the 1.5g recrystallization is dissolved in the mixed solvent of 30ml vinyl acetic monomer and 25m1 N-BUTYL ACETATE; The nano silicon dioxide particles that adds two key modifications prepared in the 3g step (2) then disperses 1.5h under the effect of 40kHz UW; Under the protection of high pure nitrogen; Through tap funnel it is added drop-wise in the reactor drum with the bottoming of 25ml N-BUTYL ACETATE, the dropping time is 3.5～4h, and control reaction temperature is 90 ℃; Stirring velocity is 400rl/min; After dropwising, continue insulation reaction 6h, obtain the nano silicon massfraction and be nano silicon/fluoroacrylic resin matrix material of 6%.
Claims (4)
1. an in-situ solution polymerization prepares the method for nano silicon-fluoroacrylic resin, it is characterized in that, may further comprise the steps:
1) 50～100ml absolute ethyl alcohol, 1～10ml deionized water, 1～10ml ammoniacal liquor and 1～20ml vinyl silicane coupling agent are joined in the container that prolong, electric mixer, tap funnel and TM are housed; Be warming up to 30～100 ℃; Then the positive tetraethyl orthosilicate of 10～60ml is added drop-wise in the container through tap funnel; The control rate of addition makes it dropwise at 2～3h; Stir speed (S.S.) is controlled at 100～600r/min, drips continued reaction 4～12h, obtains the nano silicon gel of two key modifications;
2) step 1) is prepared nano silicon gel is transferred in the hydrothermal reaction kettle; Behind 100～160 ℃ of following ageing 12～48h, obtain the nano silicon deposition; The nano silicon deposition promptly gets the nano silicon dioxide particles of two key modifications after filtration, washing, vacuum-drying, grinding;
3) with step 2) after the nano silicon of prepared two key modifications and monomer, initiator, the solvent; Under the UW effect, disperse 0.5～2h; Under the protection of rare gas element, be heated to 75～100 ℃ of initiated polymerizations, reaction times 4～12h; Obtain nano silicon/fluoroacrylic resin matrix material
Monomer in the said step 3) comprises fluorochemical monomer and fluorochemical monomer not,
Said fluorochemical monomer is one or more in trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, methylacrylic acid ten difluoro heptyl esters or the methylacrylic acid ten trifluoro monooctyl esters;
Said not fluorochemical monomer is one or more in TEB 3K, Jia Jibingxisuanyizhi, ethyl propenoate, Bing Xisuandingzhi, Rocryl 400, Rocryl 410 or the vinylbenzene.
2. in-situ solution polymerization according to claim 1 prepares the method for nano silicon-fluoroacrylic resin, it is characterized in that: the vinyl silanes in the said step 1) is a kind of in vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyl silane triisopropoxide, vinyl three tert.-butoxy silane or the vinyltriacetoxy silane.
3. in-situ solution polymerization according to claim 1 prepares the method for nano silicon-fluoroacrylic resin, it is characterized in that: the solvent in the said step 3) is one or both in toluene, YLENE, vinyl acetic monomer or the N-BUTYL ACETATE.
4. in-situ solution polymerization according to claim 1 prepares the method for nano silicon-fluoroacrylic resin, it is characterized in that: in the said step 3), the add-on of the nano silicon of two key modifications is 0.5～10% of a resin total mass.
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| US9695263B2 (en) * | 2013-03-06 | 2017-07-04 | Unimatec Co., Ltd. | Fluorine-containing oligomer, nano-silica composite particles using the same, and methods for producing both |
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| CN108250371B (en) * | 2016-12-28 | 2020-06-02 | 北京化工大学 | Bonding type polymer/silicon dioxide hybrid material and preparation method thereof |
| CN108395799A (en) * | 2018-03-26 | 2018-08-14 | 福建瑞森新材料股份有限公司 | Novel fluoropolymers anti-pollution flashover coating and preparation method |
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| CN113388273A (en) * | 2021-06-11 | 2021-09-14 | 广东轻工职业技术学院 | Fluorinated silica nanoparticles and applications |
| CN114195960A (en) * | 2021-12-09 | 2022-03-18 | 盐城工学院 | Synthetic method of water-repellent fluorine-containing polyacrylate/silicon dioxide composite material |
| CN115322703B (en) * | 2022-08-30 | 2023-06-16 | 江阴伟韬塑料新材料有限公司 | Hot melt adhesive film and preparation method thereof |
| CN116285590A (en) * | 2023-04-24 | 2023-06-23 | 陕西科技大学 | Fluorinated silica/water-based epoxy resin composite anticorrosive paint and preparation method thereof |
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