CN105646945A - Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction - Google Patents
Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction Download PDFInfo
- Publication number
- CN105646945A CN105646945A CN201610189461.7A CN201610189461A CN105646945A CN 105646945 A CN105646945 A CN 105646945A CN 201610189461 A CN201610189461 A CN 201610189461A CN 105646945 A CN105646945 A CN 105646945A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- hours
- reaction
- silicon dioxide
- nano silicon
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by the aid of mercapto-alkene click reaction. The method includes particular steps of 1), carrying out sulfhydrylation treatment on nanometer silicon dioxide; 2), carrying out acidification treatment on carbon fibers; 3), carrying out amination treatment on the surfaces of the carbon fibers; 4), preparing allyl glycidyl ether grafted carbon fibers; 5), preparing the nanometer silicon dioxide grafted carbon fiber reinforcements by the aid of the mercapto-alkene click reaction. The method has the advantages that the surface roughness can be improved after the nanometer silicon dioxide is grafted on the surfaces of the carbon fibers, the carbon fiber and resin wettability can be obviously improved, the method is favorable for increasing interface binding force between the carbon fibers and resin matrixes, and mechanical properties of carbon fiber reinforcement composite materials can be improved; the heat stability of the carbon fibers can be obviously improved after the nanometer silicon dioxide is grafted on the surfaces of the carbon fibers; the method is short in reaction period, high in yield and favorable for large-scale production, and byproducts are harmless.
Description
Technical field
The present invention relates to a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement.
Background technology
Carbon fiber is a kind of new material with advantages such as low-density, high specific strength, high ratio modulus, endurance, heat conduction, conductions, has been widely used for the fields such as Aeronautics and Astronautics, stationery sports goods and textile machine. But due to carbon fiber own structural characteristics so that it is poor with the caking property of resin matrix, firm not with resin matrix compound tense interface, a lot of excellent properties of composite can not be brought into play well. Therefore, the key issue that to be carbon fiber to carbon fiber surface modification encountered in polymer matrix composite is applied.
Traditional surface treatment of carbon fibers technology is higher to the requirement of equipment and technique, and treatment effect is not good. Utilizing sulfydryl-alkene click-reaction that inorganic material surface is modified is work as the method for modifying that former is new, and the method has the advantages such as applied range, productivity is high, by-product is harmless, the response time is short. The method avoids the tradition method of modifying process time long, process is toxic, it is difficult to the problems such as industrialized mass production. After nano silicon being grafted to carbon fiber surface by sulfydryl-alkene click-reaction, the interface binding power between carbon fiber and resin matrix can be significantly improved, improve the thermal stability of carbon fiber simultaneously.
Summary of the invention
It is an object of the invention to provide a kind of method simply, quickly preparing nano silicon grafting carbon fiber reinforcement, the party's ratio juris is mainly based upon sulfydryl-alkene click-reaction, this reaction time is short, productivity is high, and prepared nano silicon grafting carbon fiber reinforcement has the advantages such as surface roughness is big and resin wellability is good, thermal stability is good.
The present invention is achieved like this, the preparation method of nano silicon grafting carbon fiber reinforcement, it is characterized in that method step is:
The first step: 1g nano silicon and 0.4g deionized water are joined in 30 ~ 60mL ethanol, ultrasonic Treatment adds 2 ~ 4g containing mercaptosilane coupling agents after 60 ~ 120 minutes, put in oil bath pan 60��75 DEG C of back flow reaction 4 ~ 6 hours, reaction terminate after with ethanol purge 4 times remove non-grafted on containing mercaptosilane coupling agents, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing mercaptosilane coupling agents engrafted nanometer silicon dioxide;
Second step: 5g carbon fiber is immersed in 100 ~ 160mL nitration mixture, ultrasonic Treatment 60 ~ 120 minutes, then move in oil bath pan 80 ~ 100 DEG C to react 2 ~ 4 hours, it is washed till neutrality after completion of the reaction with deionized water, it is subsequently placed in 100 DEG C of vacuum drying ovens dry 24 hours, namely obtains acid treatment carbon fiber;
3rd step: 5g acid treatment carbon fiber is dispersed in 150 ~ 200mL mixed solvent, with second acid for adjusting pH value to 4 ~ 5, ultrasonic Treatment adds 10 ~ 30g containing amino silicane coupling agent after 30 ~ 60 minutes, 60 DEG C are reacted 2 ~ 4 hours, reaction clean 4 times with the mixed solution of ethanol, acetone and deionized water after terminating remove non-grafted on containing amino silicane coupling agent, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing amino silicane coupling agent grafting carbon fiber;
4th step: 2g grafting carbon fiber containing amino silicane coupling agent is dispersed in 30��60mL ethanol, it is subsequently adding 4 ~ 8g allyl glycidyl ether, room temperature magnetic agitation 48 ~ 72 hours, with ethanol purge 4 times, then dry 24 hours in 40 DEG C of vacuum drying ovens, allyl glycidyl ether grafting carbon fiber can be obtained;
5th step: 0.4g is dispersed in the dimethylformamide of 30 ~ 60mL containing mercaptosilane coupling agents engrafted nanometer silicon dioxide and 1g allyl glycidyl ether grafting carbon fiber, ultrasonic Treatment 60 ~ 120 minutes, it is subsequently adding the light trigger of 0.1g, the irradiation under ultraviolet ray adopting wavelength to be 365nm 1 ~ 2 hour, then ethanol purge is used 4 times, 80 DEG C of vacuum drying ovens dry 24 hours, nano silicon grafting carbon fiber reinforcement can be obtained.
Described is the one in ��-mercaptopropyl trimethoxysilane, ��-mercapto hydroxypropyl methyl dimethoxysilane or gamma-mercaptopropyltriethoxysilane containing mercaptosilane coupling agents.
Described nitration mixture is that ratio for 3:1 mixes by volume by the concentrated nitric acid that mass percent concentration is 65% and concentrated sulphuric acid that mass percent concentration is 96%.
Described mixed solvent is to be mixed by the ratio that dehydrated alcohol and deionized water are 4:1 by volume.
Described is the one in gamma-aminopropyl-triethoxy-silane, ��-aminopropyltriethoxy diethoxy silane or ��-aminopropyltrimethoxysilane containing amino silicane coupling agent.
Described light trigger is the one in benzoin dimethylether or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The solution have the advantages that: it is big that nano silicon grafting carbon fiber reinforcement provided by the invention has surface roughness, nano silicon percent grafting is high, good with resin matrix caking property, the advantages such as thermal stability is good.
Detailed description of the invention
Embodiment 1:
This example demonstrates that a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement provided by the invention.
The first step: 1g nano silicon and 0.4g deionized water are joined in 30mL ethanol, ultrasonic Treatment adds 2g containing mercaptosilane coupling agents (��-mercapto hydroxypropyl methyl dimethoxysilane) after 120 minutes, put in oil bath pan 70 DEG C of back flow reaction 5 hours, reaction terminate after with ethanol purge 4 times remove non-grafted on containing mercaptosilane coupling agents, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing mercaptosilane coupling agents engrafted nanometer silicon dioxide;
Second step: 5g carbon fiber is immersed in 160mL nitration mixture, ultrasonic Treatment 60 minutes, then moves in oil bath pan 80 DEG C and reacts 4 hours, be washed till neutrality with deionized water after completion of the reaction, it is subsequently placed in 100 DEG C of vacuum drying ovens dry 24 hours, namely obtains acid treatment carbon fiber;
3rd step: 5g acid treatment carbon fiber is dispersed in 180mL mixed solvent, with second acid for adjusting pH value to 4, ultrasonic Treatment adds 10g containing amino silicane coupling agent (gamma-aminopropyl-triethoxy-silane) after 45 minutes, 60 DEG C are reacted 3 hours, reaction clean 4 times with the mixed solution of ethanol, acetone and deionized water after terminating remove non-grafted on containing amino silicane coupling agent, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing amino silicane coupling agent grafting carbon fiber;
4th step: 2g grafting carbon fiber containing amino silicane coupling agent is dispersed in 45mL ethanol, it is subsequently adding 4g allyl glycidyl ether, room temperature magnetic agitation 48 hours, with ethanol purge 4 times, then dry 24 hours in 40 DEG C of vacuum drying ovens, allyl glycidyl ether grafting carbon fiber can be obtained;
5th step: 0.4g is dispersed in the dimethylformamide of 30mL containing mercaptosilane coupling agents engrafted nanometer silicon dioxide and 1g allyl glycidyl ether grafting carbon fiber, ultrasonic Treatment 120 minutes, it is subsequently adding the benzoin dimethylether of 0.1g, the irradiation under ultraviolet ray adopting wavelength to be 365nm 1 hour, then ethanol purge is used 4 times, 80 DEG C of vacuum drying ovens dry 24 hours, nano silicon grafting carbon fiber reinforcement can be obtained.
Embodiment 2:
This example demonstrates that a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement provided by the invention.
The first step: 1g nano silicon and 0.4g deionized water are joined in 60mL ethanol, ultrasonic Treatment adds 3g containing mercaptosilane coupling agents (gamma-mercaptopropyltriethoxysilane) after 60 minutes, put in oil bath pan 75 DEG C of back flow reaction 6 hours, reaction terminate after with ethanol purge 4 times remove non-grafted on containing mercaptosilane coupling agents, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing mercaptosilane coupling agents engrafted nanometer silicon dioxide;
Second step: 5g carbon fiber is immersed in 120mL nitration mixture, ultrasonic Treatment 90 minutes, then moves in oil bath pan 100 DEG C and reacts 2 hours, be washed till neutrality with deionized water after completion of the reaction, it is subsequently placed in 100 DEG C of vacuum drying ovens dry 24 hours, namely obtains acid treatment carbon fiber;
3rd step: 5g acid treatment carbon fiber is dispersed in 150mL mixed solvent, with second acid for adjusting pH value to 5, ultrasonic Treatment adds 20g containing amino silicane coupling agent (��-aminopropyltrimethoxysilane) after 60 minutes, 60 DEG C are reacted 4 hours, reaction clean 4 times with the mixed solution of ethanol, acetone and deionized water after terminating remove non-grafted on containing amino silicane coupling agent, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing amino silicane coupling agent grafting carbon fiber;
4th step: 2g grafting carbon fiber containing amino silicane coupling agent is dispersed in 30mL ethanol, it is subsequently adding 6g allyl glycidyl ether, room temperature magnetic agitation 72 hours, with ethanol purge 4 times, then dry 24 hours in 40 DEG C of vacuum drying ovens, allyl glycidyl ether grafting carbon fiber can be obtained;
5th step: 0.4g is dispersed in the dimethylformamide of 60mL containing mercaptosilane coupling agents engrafted nanometer silicon dioxide and 1g allyl glycidyl ether grafting carbon fiber, ultrasonic Treatment 60 minutes, it is subsequently adding the 2-hydroxy-2-methyl-1-phenyl-1-acetone of 0.1g, the irradiation under ultraviolet ray adopting wavelength to be 365nm 2 hours, then ethanol purge is used 4 times, 80 DEG C of vacuum drying ovens dry 24 hours, nano silicon grafting carbon fiber reinforcement can be obtained.
Embodiment 3:
This example demonstrates that a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement provided by the invention.
The first step: 1g nano silicon and 0.4g deionized water are joined in 45mL ethanol, ultrasonic Treatment adds 4g containing mercaptosilane coupling agents (��-mercaptopropyl trimethoxysilane) after 90 minutes, put in oil bath pan 60 DEG C of back flow reaction 4 hours, reaction terminate after with ethanol purge 4 times remove non-grafted on containing mercaptosilane coupling agents, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing mercaptosilane coupling agents engrafted nanometer silicon dioxide;
Second step: 5g carbon fiber is immersed in 100mL nitration mixture, ultrasonic Treatment 120 minutes, then moves in oil bath pan 90 DEG C and reacts 3 hours, be washed till neutrality with deionized water after completion of the reaction, it is subsequently placed in 100 DEG C of vacuum drying ovens dry 24 hours, namely obtains acid treatment carbon fiber;
3rd step: 5g acid treatment carbon fiber is dispersed in 200mL mixed solvent, with second acid for adjusting pH value to 4, ultrasonic Treatment adds 30g containing amino silicane coupling agent (��-aminopropyltriethoxy diethoxy silane) after 30 minutes, 60 DEG C are reacted 2 hours, reaction clean 4 times with the mixed solution of ethanol, acetone and deionized water after terminating remove non-grafted on containing amino silicane coupling agent, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing amino silicane coupling agent grafting carbon fiber;
4th step: 2g grafting carbon fiber containing amino silicane coupling agent is dispersed in 60mL ethanol, it is subsequently adding 8g allyl glycidyl ether, room temperature magnetic agitation 60 hours, with ethanol purge 4 times, then dry 24 hours in 40 DEG C of vacuum drying ovens, allyl glycidyl ether grafting carbon fiber can be obtained;
5th step: 0.4g is dispersed in the dimethylformamide of 45mL containing mercaptosilane coupling agents engrafted nanometer silicon dioxide and 1g allyl glycidyl ether grafting carbon fiber, ultrasonic Treatment 90 minutes, it is subsequently adding the benzoin dimethylether of 0.1g, the irradiation under ultraviolet ray adopting wavelength to be 365nm 1 hour, then ethanol purge is used 4 times, 80 DEG C of vacuum drying ovens dry 24 hours, nano silicon grafting carbon fiber reinforcement can be obtained.
Claims (6)
1. one kind utilizes the method that sulfydryl-alkene click-reaction prepares nano silicon grafting carbon fiber reinforcement, it is characterised in that said method comprising the steps of:
The first step: 1g nano silicon and 0.4g deionized water are joined in 30 ~ 60mL ethanol, ultrasonic Treatment adds 2 ~ 4g containing mercaptosilane coupling agents after 60 ~ 120 minutes, put in oil bath pan 60��75 DEG C of back flow reaction 4 ~ 6 hours, reaction terminate after with ethanol purge 4 times remove non-grafted on containing mercaptosilane coupling agents, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing mercaptosilane coupling agents engrafted nanometer silicon dioxide;
Second step: 5g carbon fiber is immersed in 100 ~ 160mL nitration mixture, ultrasonic Treatment 60 ~ 120 minutes, then move in oil bath pan 80 ~ 100 DEG C to react 2 ~ 4 hours, it is washed till neutrality after completion of the reaction with deionized water, it is subsequently placed in 100 DEG C of vacuum drying ovens dry 24 hours, namely obtains acid treatment carbon fiber;
3rd step: 5g acid treatment carbon fiber is dispersed in 150 ~ 200mL mixed solvent, with second acid for adjusting pH value to 4 ~ 5, ultrasonic Treatment adds 10 ~ 30g containing amino silicane coupling agent after 30 ~ 60 minutes, 60 DEG C are reacted 2 ~ 4 hours, reaction clean 4 times with the mixed solution of ethanol, acetone and deionized water after terminating remove non-grafted on containing amino silicane coupling agent, it is placed in 100 DEG C of vacuum drying ovens dry 24 hours, can obtain containing amino silicane coupling agent grafting carbon fiber;
4th step: 2g grafting carbon fiber containing amino silicane coupling agent is dispersed in 30��60mL ethanol, it is subsequently adding 4 ~ 8g allyl glycidyl ether, room temperature magnetic agitation 48 ~ 72 hours, with ethanol purge 4 times, then dry 24 hours in 40 DEG C of vacuum drying ovens, allyl glycidyl ether grafting carbon fiber can be obtained;
5th step: 0.4g is dispersed in the dimethylformamide of 30 ~ 60mL containing mercaptosilane coupling agents engrafted nanometer silicon dioxide and 1g allyl glycidyl ether grafting carbon fiber, ultrasonic Treatment 60 ~ 120 minutes, it is subsequently adding the light trigger of 0.1g, the irradiation under ultraviolet ray adopting wavelength to be 365nm 1 ~ 2 hour, then ethanol purge is used 4 times, 80 DEG C of vacuum drying ovens dry 24 hours, nano silicon grafting carbon fiber reinforcement can be obtained.
2. a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement as claimed in claim 1, it is characterised in that described is the one in ��-mercaptopropyl trimethoxysilane, ��-mercapto hydroxypropyl methyl dimethoxysilane or gamma-mercaptopropyltriethoxysilane containing mercaptosilane coupling agents.
3. a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement as claimed in claim 1, it is characterised in that described nitration mixture is that ratio for 3:1 mixes by volume by the concentrated nitric acid that mass percent concentration is 65% and concentrated sulphuric acid that mass percent concentration is 96%.
4. a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement as claimed in claim 1, it is characterised in that described mixed solvent is that ratio for 4:1 mixes by volume by dehydrated alcohol and deionized water.
5. a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement as claimed in claim 1, it is characterised in that described is the one in gamma-aminopropyl-triethoxy-silane, ��-aminopropyltriethoxy diethoxy silane or ��-aminopropyltrimethoxysilane containing amino silicane coupling agent.
6. a kind of method utilizing sulfydryl-alkene click-reaction to prepare nano silicon grafting carbon fiber reinforcement as claimed in claim 1, it is characterised in that described light trigger is the one in benzoin dimethylether or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610189461.7A CN105646945B (en) | 2016-03-30 | 2016-03-30 | A method of it preparing nano silicon dioxide using sulfydryl-alkene click-reaction and is grafted carbon fiber reinforcement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610189461.7A CN105646945B (en) | 2016-03-30 | 2016-03-30 | A method of it preparing nano silicon dioxide using sulfydryl-alkene click-reaction and is grafted carbon fiber reinforcement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105646945A true CN105646945A (en) | 2016-06-08 |
| CN105646945B CN105646945B (en) | 2018-07-17 |
Family
ID=56495814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610189461.7A Expired - Fee Related CN105646945B (en) | 2016-03-30 | 2016-03-30 | A method of it preparing nano silicon dioxide using sulfydryl-alkene click-reaction and is grafted carbon fiber reinforcement |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646945B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519301A (en) * | 2016-11-26 | 2017-03-22 | 四川理工学院 | Preparation of SiO2-helical carbon nanofiber double-phase filler and application of double-phase filler in rubber reinforcement |
| CN106521970A (en) * | 2016-10-28 | 2017-03-22 | 南昌航空大学 | Method for preparing polythioether polymer grafted carbon fibers on basis of thiol-ene photopolymerization |
| CN107099035A (en) * | 2017-02-28 | 2017-08-29 | 朱光明 | Include SiO2Shape-memory polymer of particle and polycaprolactone and preparation method thereof |
| CN107353499A (en) * | 2017-08-04 | 2017-11-17 | 武汉理工大学 | A kind of carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN108084744A (en) * | 2017-12-22 | 2018-05-29 | 江南大学 | A kind of method that self-dispersing nano carbon black is prepared based on sulfydryl-alkene click-reaction |
| CN108486867A (en) * | 2018-04-08 | 2018-09-04 | 四川大学 | A kind of aromatic polymer fiber of high composite performance and preparation method thereof suitable for opposed polarity range matrix resin |
| CN108822553A (en) * | 2018-07-10 | 2018-11-16 | 合肥工业大学 | A kind of the self-reinforcing heat-conducting insulating silicon rubber material and preparation method of filling crosslinking function conduction powder |
| CN109331805A (en) * | 2018-11-15 | 2019-02-15 | 南昌航空大学 | A kind of preparation method of carbon fiber loaded nano titanium dioxide photocatalysis composite material |
| CN109401322A (en) * | 2018-10-19 | 2019-03-01 | 歌尔股份有限公司 | The preparation method and electronic product of silastic material |
| CN109576987A (en) * | 2018-11-15 | 2019-04-05 | 南昌航空大学 | A method of graphene oxide grafting carbon fiber is prepared based on mercapto alkene chemical reaction |
| CN109796725A (en) * | 2018-12-17 | 2019-05-24 | 南京航空航天大学 | A kind of carbon fiber surface chemical graft Nano-meter SiO_22Reinforced polyether ether ketone composite material and preparation method |
| CN110028636A (en) * | 2019-04-29 | 2019-07-19 | 厦门理工学院 | Sulfydryl-tourmaline of the alkene clicking chemistry preparation containing anthraquinone compounds method and application |
| CN110040842A (en) * | 2019-04-29 | 2019-07-23 | 厦门理工学院 | A kind of redox mediators are grafted on the method and application of inorganic filler surface |
| CN110669347A (en) * | 2019-10-28 | 2020-01-10 | 北京盛广拓再生科技股份有限公司 | Wheel-sticking-free high-viscosity emulsified asphalt |
| CN111154289A (en) * | 2019-07-31 | 2020-05-15 | 盐城工学院 | Preparation method and application of self-dispersion nano bismuth vanadate |
| CN111548573A (en) * | 2020-05-09 | 2020-08-18 | 中国船舶重工集团公司第七二五研究所 | Fiber-reinforced phenolic resin composite hollow sphere and preparation method thereof |
| CN113529242A (en) * | 2021-07-29 | 2021-10-22 | 吉祥三宝高科纺织有限公司 | Method for preparing anti-cutting gloves by using carbon fiber composite material |
| CN113831648A (en) * | 2021-11-08 | 2021-12-24 | 重庆会通科技有限公司 | Ultrahigh molecular weight polyethylene reinforced polypropylene composite material and preparation method thereof |
| CN115302895A (en) * | 2022-07-11 | 2022-11-08 | 张家港飞腾复合新材料股份有限公司 | Light composite board with stable application and production process thereof |
| CN115703892A (en) * | 2021-08-09 | 2023-02-17 | 中南民族大学 | High-performance degradable epoxy resin-carbon fiber composite material and preparation method thereof |
| CN116355468A (en) * | 2023-03-28 | 2023-06-30 | 中科融志国际科技(北京)有限公司 | Anti-icing coating and fan blade |
| CN116396620A (en) * | 2023-05-24 | 2023-07-07 | 东莞市华岳导热科技有限公司 | Heat conducting fin and preparation method thereof |
| CN116768569A (en) * | 2023-06-19 | 2023-09-19 | 宿迁华美新材料有限公司 | Method for preparing concrete square pile by utilizing nickel slag and fly ash to be mixed |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739794A (en) * | 2013-12-24 | 2014-04-23 | 太原理工大学 | Preparation method of hyperbranched polymer-modified nano-silicon dioxide hybrid material |
| CN104499270A (en) * | 2014-12-22 | 2015-04-08 | 哈尔滨工业大学 | Surface modification method for carbon fibers by nano silicon dioxide |
| CN105084862A (en) * | 2015-08-05 | 2015-11-25 | 苏州赛斯德工程设备有限公司 | Preparation method of modified phenolic resin friction material |
| CN105418969A (en) * | 2015-12-04 | 2016-03-23 | 南昌航空大学 | Click chemistry based preparation method of carbon nanotube grafted carbon fiber reinforcement |
-
2016
- 2016-03-30 CN CN201610189461.7A patent/CN105646945B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739794A (en) * | 2013-12-24 | 2014-04-23 | 太原理工大学 | Preparation method of hyperbranched polymer-modified nano-silicon dioxide hybrid material |
| CN104499270A (en) * | 2014-12-22 | 2015-04-08 | 哈尔滨工业大学 | Surface modification method for carbon fibers by nano silicon dioxide |
| CN105084862A (en) * | 2015-08-05 | 2015-11-25 | 苏州赛斯德工程设备有限公司 | Preparation method of modified phenolic resin friction material |
| CN105418969A (en) * | 2015-12-04 | 2016-03-23 | 南昌航空大学 | Click chemistry based preparation method of carbon nanotube grafted carbon fiber reinforcement |
Non-Patent Citations (1)
| Title |
|---|
| 温笑菁: "《材料科学基础-高分子材料分册》", 31 January 2015 * |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521970B (en) * | 2016-10-28 | 2019-02-01 | 南昌航空大学 | A kind of preparation method based on sulfydryl-alkene photopolymerization polysulfide polymers grafting carbon fiber |
| CN106521970A (en) * | 2016-10-28 | 2017-03-22 | 南昌航空大学 | Method for preparing polythioether polymer grafted carbon fibers on basis of thiol-ene photopolymerization |
| CN106519301A (en) * | 2016-11-26 | 2017-03-22 | 四川理工学院 | Preparation of SiO2-helical carbon nanofiber double-phase filler and application of double-phase filler in rubber reinforcement |
| CN106519301B (en) * | 2016-11-26 | 2018-06-26 | 四川理工学院 | A kind of preparation of SiO2/ spiral nanometer carbon fibers dual phase filler and its application in reinforcing rubber |
| CN107099035A (en) * | 2017-02-28 | 2017-08-29 | 朱光明 | Include SiO2Shape-memory polymer of particle and polycaprolactone and preparation method thereof |
| CN107353499A (en) * | 2017-08-04 | 2017-11-17 | 武汉理工大学 | A kind of carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN108084744A (en) * | 2017-12-22 | 2018-05-29 | 江南大学 | A kind of method that self-dispersing nano carbon black is prepared based on sulfydryl-alkene click-reaction |
| CN108486867A (en) * | 2018-04-08 | 2018-09-04 | 四川大学 | A kind of aromatic polymer fiber of high composite performance and preparation method thereof suitable for opposed polarity range matrix resin |
| CN108822553A (en) * | 2018-07-10 | 2018-11-16 | 合肥工业大学 | A kind of the self-reinforcing heat-conducting insulating silicon rubber material and preparation method of filling crosslinking function conduction powder |
| CN109401322A (en) * | 2018-10-19 | 2019-03-01 | 歌尔股份有限公司 | The preparation method and electronic product of silastic material |
| CN109331805A (en) * | 2018-11-15 | 2019-02-15 | 南昌航空大学 | A kind of preparation method of carbon fiber loaded nano titanium dioxide photocatalysis composite material |
| CN109576987A (en) * | 2018-11-15 | 2019-04-05 | 南昌航空大学 | A method of graphene oxide grafting carbon fiber is prepared based on mercapto alkene chemical reaction |
| CN109331805B (en) * | 2018-11-15 | 2021-06-15 | 南昌航空大学 | Preparation method of carbon fiber loaded nano titanium dioxide photocatalytic composite material |
| CN109576987B (en) * | 2018-11-15 | 2021-04-09 | 南昌航空大学 | Method for preparing graphene oxide grafted carbon fiber based on thiol chemical reaction |
| CN109796725A (en) * | 2018-12-17 | 2019-05-24 | 南京航空航天大学 | A kind of carbon fiber surface chemical graft Nano-meter SiO_22Reinforced polyether ether ketone composite material and preparation method |
| CN110028636A (en) * | 2019-04-29 | 2019-07-19 | 厦门理工学院 | Sulfydryl-tourmaline of the alkene clicking chemistry preparation containing anthraquinone compounds method and application |
| CN110040842A (en) * | 2019-04-29 | 2019-07-23 | 厦门理工学院 | A kind of redox mediators are grafted on the method and application of inorganic filler surface |
| WO2020221240A1 (en) * | 2019-04-29 | 2020-11-05 | 厦门理工学院 | Method for preparing tourmaline containing anthraquinone compound by means of thiol-ene click chemistry and application thereof |
| CN110040842B (en) * | 2019-04-29 | 2020-06-16 | 厦门理工学院 | Method for grafting redox mediator on surface of inorganic filler and application |
| CN111154289A (en) * | 2019-07-31 | 2020-05-15 | 盐城工学院 | Preparation method and application of self-dispersion nano bismuth vanadate |
| CN110669347A (en) * | 2019-10-28 | 2020-01-10 | 北京盛广拓再生科技股份有限公司 | Wheel-sticking-free high-viscosity emulsified asphalt |
| CN111548573B (en) * | 2020-05-09 | 2023-04-07 | 中国船舶重工集团公司第七二五研究所 | Fiber-reinforced phenolic resin composite hollow sphere and preparation method thereof |
| CN111548573A (en) * | 2020-05-09 | 2020-08-18 | 中国船舶重工集团公司第七二五研究所 | Fiber-reinforced phenolic resin composite hollow sphere and preparation method thereof |
| CN113529242A (en) * | 2021-07-29 | 2021-10-22 | 吉祥三宝高科纺织有限公司 | Method for preparing anti-cutting gloves by using carbon fiber composite material |
| CN115703892B (en) * | 2021-08-09 | 2024-06-11 | 中南民族大学 | High-performance degradable epoxy resin-carbon fiber composite material and preparation method thereof |
| CN115703892A (en) * | 2021-08-09 | 2023-02-17 | 中南民族大学 | High-performance degradable epoxy resin-carbon fiber composite material and preparation method thereof |
| CN113831648A (en) * | 2021-11-08 | 2021-12-24 | 重庆会通科技有限公司 | Ultrahigh molecular weight polyethylene reinforced polypropylene composite material and preparation method thereof |
| CN113831648B (en) * | 2021-11-08 | 2023-08-04 | 重庆会通科技有限公司 | Ultra-high molecular weight polyethylene reinforced polypropylene composite material and preparation method thereof |
| CN115302895A (en) * | 2022-07-11 | 2022-11-08 | 张家港飞腾复合新材料股份有限公司 | Light composite board with stable application and production process thereof |
| CN116355468A (en) * | 2023-03-28 | 2023-06-30 | 中科融志国际科技(北京)有限公司 | Anti-icing coating and fan blade |
| CN116396620A (en) * | 2023-05-24 | 2023-07-07 | 东莞市华岳导热科技有限公司 | Heat conducting fin and preparation method thereof |
| CN116396620B (en) * | 2023-05-24 | 2023-12-19 | 东莞市华岳导热科技有限公司 | Heat conducting fin and preparation method thereof |
| CN116768569A (en) * | 2023-06-19 | 2023-09-19 | 宿迁华美新材料有限公司 | Method for preparing concrete square pile by utilizing nickel slag and fly ash to be mixed |
| CN116768569B (en) * | 2023-06-19 | 2023-12-15 | 宿迁华美新材料有限公司 | Method for preparing concrete square pile by utilizing nickel slag and fly ash to be mixed |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646945B (en) | 2018-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105646945A (en) | Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction | |
| CN105418969B (en) | A kind of preparation method of the carbon nanotube grafting carbon fiber reinforcement based on click chemistry | |
| CN105778153B (en) | A kind of preparation method of cage type polysilsesquioxane grafting carbon fiber reinforcement | |
| CN105440583B (en) | A kind of Dopaminergics are compound-modified or nanometer particle-modified polymer composites of package and preparation method thereof | |
| CN103409985B (en) | Preparation method of carbon nano tube loaded carbon fiber | |
| CN102409528A (en) | Preparation method of carbon fiber reinforcement grafted by graphene oxide | |
| CN109796725B (en) | Nano SiO chemically grafted on carbon fiber surface2Reinforced polyether-ether-ketone composite material and preparation method thereof | |
| CN102153835A (en) | Modified graphene/epoxy resin composite material and preparation method thereof | |
| CN104130597A (en) | Hollow glass micro-spheres surface modification method | |
| CN102140179A (en) | Method for preparing styrene grafted silicon dioxide superhydrophobic thin film | |
| CN104151581A (en) | Preparation method of composite carbon fiber/graphene oxide/organosilicone resin multidimensional hybrid material | |
| CN102286234B (en) | Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ | |
| CN104131455B (en) | A kind of preparation method of the preliminary treatment aramid fiber short fibre for rubber | |
| CN109576987B (en) | Method for preparing graphene oxide grafted carbon fiber based on thiol chemical reaction | |
| CN106744900A (en) | A kind of preparation method of polymolecularity Graphene | |
| CN108570212B (en) | Method for manufacturing carbon fiber bulk molding material | |
| CN102807835B (en) | A kind of hydrolyzable ultraviolet curing glue and preparation method thereof | |
| KR20130083649A (en) | Cement compound with carbon nanotube, method for manufacturing the cement mortar, and method for manufacturing cement structure using the cement compound | |
| CN110408238A (en) | A kind of method of modifying for the hollow glass micropearl being used to prepare lightweight epoxy resin-polyurethane composite material | |
| CN105175781A (en) | Carbon nanotube rodlike nanocomposite material modified by organic spherical silica and preparation method thereof | |
| CN106276844A (en) | High Strength Carbon Nanotubes thin film, its preparation method and application | |
| CN102153750A (en) | Octa-polysilsesquioxane reinforced polybenzimidazole compound and preparation method thereof | |
| CN104650432A (en) | Modification method of nano white carbon black used as rubber additive | |
| CN105713353A (en) | Novel composite aging-resistant textile material and preparing method thereof | |
| CN105688851B (en) | A kind of preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180717 Termination date: 20200330 |