CN102086246A - 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
- Publication number
- CN102086246A CN102086246A CN 201010563631 CN201010563631A CN102086246A CN 102086246 A CN102086246 A CN 102086246A CN 201010563631 CN201010563631 CN 201010563631 CN 201010563631 A CN201010563631 A CN 201010563631A CN 102086246 A CN102086246 A CN 102086246A
- Authority
- CN
- China
- Prior art keywords
- nano silicon
- solution polymerization
- vinyl
- nanosilica
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
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 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, easily shrink embrittlement and be separated; The graft process narrow application range, the layered inorganic material of only suitable polynite one class; When adopting situ aggregation method, monomer is polymerization reaction take place in the gap of the silicon-dioxide primary particle of reuniting, 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 " 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 characteristics, 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 by 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/ Resins, epoxy/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 at " matrix material journal " [2008,25 (4), P56-61] middle report, 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 Resins, epoxy/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 by the in-situ solution polymerization prepare the nano silicon/patent of fluoroacrylic resin matrix material, paper yet there are no all reports.
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 of the present invention prepares nano silicon-fluoroacrylic resin matrix material may further comprise the steps:
1) 50～100ml dehydrated 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, dropping funnel and thermometer are housed, be warming up to 30～100.C is added drop-wise to the positive tetraethyl orthosilicate of 10～60ml in the flask by dropping 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 the back and continue 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 precipitation, precipitation after filtration, after the washing, vacuum-drying, grinding, promptly get the nano silicon dioxide particles of pair key modifications
3) with step 2) after the nano silicon of prepared two key modifications and monomer, initiator, the solvent; under the ultrasonic wave 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; Described fluorochemical monomer is one or more in trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters, the methacrylic acid ten trifluoro monooctyl esters;
Described not fluorochemical monomer is one or more in methyl methacrylate, Jia Jibingxisuanyizhi, ethyl propenoate, butyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, the vinylbenzene.
Among the present invention, the solvent described in the step 3) is one or more in toluene, dimethylbenzene, 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 by 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 modification 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 by the chemical bond of high bond energy, can guarantee nanoparticle effectively stable dispersion in polymeric matrix, and the dispersive nano silicon as " anchor point " with the molecular chain around it or segment " nail anchor " together, and matrix material is played enhancing, toughness reinforcing effect; (3) nano silicon/fluoroacrylic resin matrix material fully combines 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
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
Step (1): 80ml dehydrated alcohol, 5ml deionized water, 5ml ammoniacal liquor and 10ml vinyltriethoxysilane are joined in the four-hole boiling flask that prolong, electric mixer, dropping funnel and thermometer are housed, be warming up to 60 ℃, then the positive tetraethyl orthosilicate of 40ml is added drop-wise in the flask by dropping funnel, the control rate of addition makes it dropwise at 2～3h, stir speed (S.S.) is controlled at 200r/min, drip the back and continue 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 precipitation, with sedimentation and filtration, after the filter cake usefulness washing with alcohol three times, 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 methyl methacrylate, 23g butyl acrylate, 8g methacrylic acid ten difluoro heptyl esters, 7g hydroxyethyl methylacrylate 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 ultrasonic wave; Under the protection of high pure nitrogen; by dropping funnel it is added drop-wise in the reactor that feels secure with the 20m1 N-BUTYL ACETATE; the dropping time is 3h; 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 dehydrated alcohol, 3ml deionized water, 3ml ammoniacal liquor and 5m1 vinyl trichloro silane are joined in the four-hole boiling flask that prolong, electric mixer, dropping funnel and thermometer are housed, be warming up to 40 ℃, then the positive tetraethyl orthosilicate of 20ml is added drop-wise in the flask by dropping funnel, the control rate of addition makes it dropwise at 2～3h, stir speed (S.S.) is controlled at 100r/min, drip the back and continue 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 precipitation, with sedimentation and filtration, after the filter cake usefulness washing with alcohol three times, 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 methyl methacrylate, 19g butyl acrylate, 8g methacrylic 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 ultrasonic wave; Under the protection of high pure nitrogen; by dropping funnel it is added drop-wise in the reactor that feels secure with the 20ml N-BUTYL ACETATE; the dropping time is 3h; 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 dehydrated 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, dropping funnel and thermometer are housed, be warming up to 75 ℃, then the positive tetraethyl orthosilicate of 60ml is added drop-wise in the flask by dropping funnel, the control rate of addition makes it dropwise at 2～3h, stir speed (S.S.) is controlled at 350r/min, drip the back and continue reaction 1Oh, 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 140 ℃ of following ageing 12h, obtain the nano silicon precipitation, with sedimentation and filtration, after the filter cake usefulness washing with alcohol three times, 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 methacrylic 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 ultrasonic wave; Under the protection of high pure nitrogen; by dropping funnel it is added drop-wise in the reactor that feels secure with the 25ml N-BUTYL ACETATE; the dropping time is 3.5～4h; 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 (5)
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 dehydrated 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, dropping funnel and thermometer are housed, be warming up to 30～100 ℃, then the positive tetraethyl orthosilicate of 10～60ml is added drop-wise in the container by dropping funnel, the control rate of addition makes it dropwise at 2～3h, stir speed (S.S.) is controlled at 100～600r/min, drip the back and continue 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 precipitation, nano silicon precipitation after filtration, after the washing, vacuum-drying, grinding, promptly get the nano silicon dioxide particles of pair key modifications;
3) with step 2) after the nano silicon of prepared two key modifications and monomer, initiator, the solvent; under the ultrasonic wave effect, disperse O.5～2h; under the protection of rare gas element; be heated to 75～100 ℃ of initiated polymerizations; reaction times 4～12h obtains nano silicon/fluoroacrylic resin matrix material.
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 described 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 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 monomer in the described step 3) comprises fluorochemical monomer and fluorochemical monomer not;
Described fluorochemical monomer is one or more in trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters or the methacrylic acid ten trifluoro monooctyl esters;
Described not fluorochemical monomer is one or more in methyl methacrylate, Jia Jibingxisuanyizhi, ethyl propenoate, butyl acrylate, hydroxyethyl methylacrylate, Rocryl 410 or the vinylbenzene.
4. 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 described step 3) is one or both in toluene, dimethylbenzene, vinyl acetic monomer or the N-BUTYL ACETATE.
5. in-situ solution polymerization according to claim 1 prepares the method for nano silicon-fluoroacrylic resin, it is characterized in that: in the described step 3), the add-on of the nano silicon of two key modifications is 0.5～10% of a resin total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010563631 CN102086246B (en) | 2010-11-29 | 2010-11-29 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010563631 CN102086246B (en) | 2010-11-29 | 2010-11-29 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102086246A true CN102086246A (en) | 2011-06-08 |
| CN102086246B CN102086246B (en) | 2012-12-26 |
Family
ID=44098267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010563631 Active CN102086246B (en) | 2010-11-29 | 2010-11-29 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102086246B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558450A (en) * | 2011-12-21 | 2012-07-11 | 北京工商大学 | Preparation method of high-melt-strength polypropylene |
| CN103450416A (en) * | 2013-09-18 | 2013-12-18 | 段宝荣 | Preparation method of cold-resistant acrylate resin paint |
| CN104231147A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex |
| CN104558447A (en) * | 2014-12-12 | 2015-04-29 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
| CN105209507A (en) * | 2013-03-06 | 2015-12-30 | 优迈特株式会社 | Fluorine-containing oligomer, nano-silica composite particles using same, and preparation method for both |
| CN105331237A (en) * | 2015-11-26 | 2016-02-17 | 蚌埠市禹会区贵宾装饰材料商行 | Polyacrylic acid amino baking paint for aluminum-plastic panel photo frame |
| CN108250371A (en) * | 2016-12-28 | 2018-07-06 | 北京化工大学 | Bonding type polymer/silicon dioxide hybrid materials 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 |
| CN108743403A (en) * | 2018-05-09 | 2018-11-06 | 蚌埠佳美仕义齿有限公司 | A kind of basal seat area composite material that can constantly discharge anion |
| CN111592819A (en) * | 2020-06-08 | 2020-08-28 | 福建省固牌新型建材有限公司 | Production process of high-performance polyurethane waterproof paint |
| 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 |
| CN115322703A (en) * | 2022-08-30 | 2022-11-11 | 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 |
| CN116716003A (en) * | 2023-04-23 | 2023-09-08 | 深圳市力合云记新材料有限公司 | Antibacterial antiviral mildew-proof matte whiteboard coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824699A (en) * | 2006-02-10 | 2006-08-30 | 华东理工大学 | Method of lowering acrylate material surface energy |
| CN1847305A (en) * | 2005-04-12 | 2006-10-18 | 触媒化成工业株式会社 | Composition for forming film with low refracting index and base material with curing film |
-
2010
- 2010-11-29 CN CN 201010563631 patent/CN102086246B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847305A (en) * | 2005-04-12 | 2006-10-18 | 触媒化成工业株式会社 | Composition for forming film with low refracting index and base material with curing film |
| CN1824699A (en) * | 2006-02-10 | 2006-08-30 | 华东理工大学 | Method of lowering acrylate material surface energy |
Non-Patent Citations (1)
| Title |
|---|
| 《高分子学报》 20080331 姚丽等 纳米SiO2/含氟丙烯酸酯共聚物复合乳液的制备与性能及聚合动力学研究 221-226 1-5 , 第3期 2 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558450A (en) * | 2011-12-21 | 2012-07-11 | 北京工商大学 | Preparation method of high-melt-strength polypropylene |
| CN105209507A (en) * | 2013-03-06 | 2015-12-30 | 优迈特株式会社 | Fluorine-containing oligomer, nano-silica composite particles using same, and preparation method for both |
| CN103450416A (en) * | 2013-09-18 | 2013-12-18 | 段宝荣 | Preparation method of cold-resistant acrylate resin paint |
| CN103450416B (en) * | 2013-09-18 | 2015-05-13 | 段宝荣 | Preparation method of cold-resistant acrylate resin paint |
| CN104231147A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex |
| CN104558447A (en) * | 2014-12-12 | 2015-04-29 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
| CN104558447B (en) * | 2014-12-12 | 2017-03-22 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
| CN105331237A (en) * | 2015-11-26 | 2016-02-17 | 蚌埠市禹会区贵宾装饰材料商行 | Polyacrylic acid amino baking paint for aluminum-plastic panel photo frame |
| 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 |
| CN108250371A (en) * | 2016-12-28 | 2018-07-06 | 北京化工大学 | Bonding type polymer/silicon dioxide hybrid materials 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 |
| CN108743403A (en) * | 2018-05-09 | 2018-11-06 | 蚌埠佳美仕义齿有限公司 | A kind of basal seat area composite material that can constantly discharge anion |
| CN108743403B (en) * | 2018-05-09 | 2021-09-21 | 蚌埠佳美仕义齿有限公司 | False tooth base composite material capable of continuously releasing negative ions |
| CN111592819A (en) * | 2020-06-08 | 2020-08-28 | 福建省固牌新型建材有限公司 | Production process of high-performance polyurethane waterproof paint |
| CN111592819B (en) * | 2020-06-08 | 2021-08-06 | 福建省固牌新型建材有限公司 | Production process of high-performance polyurethane waterproof paint |
| 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 |
| CN115322703A (en) * | 2022-08-30 | 2022-11-11 | 江阴伟韬塑料新材料有限公司 | Hot melt adhesive film and preparation method thereof |
| 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 |
| CN116716003A (en) * | 2023-04-23 | 2023-09-08 | 深圳市力合云记新材料有限公司 | Antibacterial antiviral mildew-proof matte whiteboard coating 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102086246B (en) | 2012-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102086246B (en) | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization | |
| CN102816275B (en) | Textile deepening agent and preparation method thereof | |
| CN105273556A (en) | Preparation method of polyacrylate/nano silicon dioxide composite emulsion coating material | |
| CN103387645B (en) | Fluorinated copolymer Grafted Nano-scale TiO 2composite particles and preparation method thereof | |
| CN103613700B (en) | A kind of Pickering emulsion polymerization prepares the method for polyacrylic ester/Nano-ZnO Hybrid Coatings printing adhesive | |
| CN106010036B (en) | A kind of heat-insulated water paint of double Shell microcapsules and preparation method thereof | |
| CN102911530A (en) | Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer | |
| CN1824699A (en) | Method of lowering acrylate material surface energy | |
| CN1323092C (en) | Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 | |
| CN102492073A (en) | Quantum dot-based multifunctional magnetic fluorescent microsphere and its preparation method | |
| CN101899128A (en) | Hollow nano silica microsphere modified polyacrylate nuclear shell structure composite emulsion and thin film | |
| CN103272544B (en) | Core-shell type raspberry-shaped intelligent composite microsphere sensitive to both temperature and pH, and preparation method thereof | |
| JP2010516860A5 (en) | ||
| CN105958047A (en) | Honeycomb porous silicon/carbon composite material and preparation method thereof | |
| CN108440717A (en) | A kind of graphene oxide cladding poly (glycidyl methacrylate) microballoon composite anticorrosion coating auxiliary agent and preparation method thereof | |
| CN102532951A (en) | Method for toughening epoxy resin by adopting modified wollastonite | |
| CN102295823A (en) | Epoxy resin lightweight high-strength composite material easy to disperse carbon nano-tubes, and preparation method thereof | |
| CN101475179B (en) | Preparation of organic-inorganic hybridization silicon oxide nanosphere | |
| CN109762301A (en) | A kind of preparation method of polymer graphite alkene modified epoxy | |
| CN102731734A (en) | Method for grafting polymer on nano-grade SiO2 surface | |
| CN102007187A (en) | Anorganic nanoparticles and polymer composites created with same | |
| CN102585289A (en) | Dendritic macromolecular functional titanium dioxide micro particle toughening agent and epoxy resin | |
| CN103059180B (en) | Suspension polymerization preparation method of polystyrene/meerschaum particle | |
| CN107501853B (en) | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof | |
| CN101798443B (en) | Method for preparing nano ceric oxide/epoxy resin composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220413 Address after: No.8, Huangguan Road, high tech Zone, Anqing City, Anhui Province Patentee after: Anhui footprint New Material Technology Co.,Ltd. Address before: 213034 Baizhang Industrial Park, Xinbei District, Changzhou City, Jiangsu Province Patentee before: JIANGSU FOOTMARK PAINT CO.,LTD. |