CN106520040A - Preparation method for modified graphene oxide, MGO-SiO2 nano-hybrid material and MGO-SiO2 modified phenolic resin hot melting adhesive film - Google Patents
Preparation method for modified graphene oxide, MGO-SiO2 nano-hybrid material and MGO-SiO2 modified phenolic resin hot melting adhesive film Download PDFInfo
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- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a preparation method for modified graphene oxide, an MGO-SiO2 nano-hybrid material and an MGO-SiO2 modified phenolic resin hot melting adhesive film. The preparation method includes the following steps that (1c), the MGO-SiO2 nano-hybrid material is added into a solvent, then ultrasonic dispersion is performed, and MGO-SiO2 dispersion liquid is obtained; (2c), a film forming agent is added into a thermosetting phenolic resin solution, stirring is performed, and a mixed solution D is obtained; (3c), the MGO-SiO2 dispersion liquid obtained in the step (1c) is added into the mixed solution D obtained in the step (2c), stirring is performed so that the MGO-SiO2 dispersion liquid can be evenly dispersed in the mixed solution D, and a mixed solution E is obtained; and (4c), the mixed solution E is subjected to a vacuum constant-temperature stirring reaction at the temperature of 25-80 DEG C, a redundant solvent in the solution E is removed, when viscosity of reaction products is larger than or equal to a preset value, the reaction products are poured out, and the MGO-SiO2 modified phenolic resin hot melting adhesive film is obtained. The phenolic resin hot melting adhesive film prepared through the preparation method has excellent heat resistance and film forming performance, is low in cost, and can be applicable to a dry method prepreg forming process.
Description
Technical field
The invention belongs to the phenolic resin for being applied to sweat connecting material technique prepares technical field, it is related to a kind of modified oxidized
Graphene, MGO-SiO2Nano-hybrid material and MGO-SiO2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film.
Background technology
There is oxidizable group (phenolic hydroxyl group, methylene) in traditional phenolic resin curing thing structure, make its thermostability
It is affected, the poor process industrial art performance of phenolic resin also significantly limit its development in addition.Additionally, in dry method prepreg
In moulding process, phenolic resin film have the shortcomings that fragility it is big, and fiber wetness it is poor, and the conventional wet method prepreg of industry
Moulding process is difficult to accurately control resin content, high cost, and the drawback such as pollution environment seriously constrains high-performance composite materials
Development, in order to adapt to the needs of the high-technology fields such as automobile, electronics, Aeronautics and Astronautics and national defense industry, using various methods pair
Phenolic resin is modified, it has also become the core content of phenolic resin research.
Graphene is because of its excellent electric, hot and mechanical property, and the features such as high-specific surface area, has been considered to one kind
It is very promising, multipurpose, the multi-functional basic material for preparing composite.It can be added to as multi-functional filler
In resin, the combination property of resin is improved.But Graphene high-specific surface area and the model ylid bloom action power from stiffness of the body so as to easily
In reunion, being difficult to be uniformly dispersed in resin matrix has had a strong impact on its extensive application in field of compound material, in order to improve
The methods such as the dispersibility of Graphene and the interaction with matrix, ultrasound, surface treatment and chemical modification are by widely
For modified graphene, wherein, chemical modification is to improving Graphene dispersion in the base and the interaction effect with matrix
Fruit substantially, especially inorganic-graphene nano hybrid material existing uniform dispersibility in the base, and with fabulous compatible
Property and interface performance.Nano silicon have that specific surface area is big, density is little as the inorganic nano material of excellent performance and point
The characteristic such as scattered performance is good, and be present the hydroxyl of undersaturated double bond and different bond styles in surface, be often used as efficiently resistance to
Filler of ablator, adiabator, catalyst carrier and high-grade paint etc..Additionally, nano silicon is incorporated into matrix
It is central to improve wearability, increase toughness of material, improve tensile strength and impact strength and heat resistance, however it is existing
There is no report by modified graphene to improve the technology of phenolic resin PUR film properties in technology.
The content of the invention
It is an object of the invention to overcome the shortcoming of above-mentioned prior art, there is provided a kind of modified graphene oxide, MGO-
SiO2Nano-hybrid material and MGO-SiO2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film, phenolic resin prepared by the method
Hot melt adhesive film has excellent thermostability and moulding property, low cost, and can be applied to dry method prepreg moulding process.
For reaching above-mentioned purpose, the preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse after stirring obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
Stir after 3a) mixed silane coupler with ethanol B, obtain mixed solution B, then mixed solution B is added to into mixing
In solution A, and the stirring reaction at 25~75 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.1~0.5g:50~
250mL:0.05~0.65g:1.5~10g:10~65mL.
Step 1a) in time of stirring be 1~3h, time of ultrasonic disperse is 1~3h;
Step 3a) in silane coupler is mixed with ethanol B after stir 30min;
Step 3a) at 25~75 DEG C stirring reaction response time be 12~24h.
Catalyst is that dicyclohexylcarbodiimide, triphenylphosphine or dicyclohexylcarbodiimide and triphenylphosphine press quality
Compare 1-5:The mixture of 1 mixing.
The silane coupler is gamma-aminopropyl-triethoxy-silane, γ-(2,3- glycidoxies) propyl trimethoxy
Silane or gamma-aminopropyl-triethoxy-silane and γ-(2,3- glycidoxies) propyl trimethoxy silicane 1-5 in mass ratio:
The mixture of 1 mixing.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide weighed 1b), then by modified graphite oxide
Alkene is added to blend solvent, ultrasonic disperse after stirring, obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then stir at a temperature of 25~65 DEG C
Reaction, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.1~0.5g:100~
500mL:0.10~1mL:1~10g.
Step 1b) in time of stirring be 1-3h, time of ultrasonic disperse is 1-3h;
Step 3b) at a temperature of 25~65 DEG C stirring reaction response time be 12-24h.
Blend solvent is made up of ethanol C and water, wherein, in the blend solvent of 100~500mL the volume of water be 15~
150mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, ultrasonic disperse is then carried out again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2The ratio of nano-hybrid material and solvent is
0.1~1g:50~500mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 0.5~3% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 0.1~1% of thermosetting phenolic resin quality in solidity phenol resin solution;
4c) mixed solution E vacuum constant temperature stirring reaction is removed unnecessary molten in solution E at a temperature of 25~80 DEG C
Agent, when the viscosity of product is more than or equal to preset value, pours out product, obtains MGO-SiO2Phenol-formaldehyde resin modified PUR
Film.
Step 1c) in the concrete operations of ultrasonic disperse be:1~6h of ultrasonic disperse under conditions of 0 DEG C;
Step 4c) at a temperature of 25~80 DEG C the response time of vacuum constant temperature stirring reaction be 1~5h, mixing speed is
100~300rpm, vacuum are more than or equal to 0.09MPa;
Step 4c) in viscosity when product is at 60~90 DEG C when being 0.5~2.0Pa s, then pour out reaction and produce
Thing.
Thermosetting phenolic resin in thermosetting phenolic resin solution is ba phenolic resin, Mo-phenolic resin, tungsten phenolic aldehyde tree
One or more mixture for mixing in any proportion in fat, ammonia phenolic resin and phosphorous-containing phenolic resin;
The film former is PAUR, EU, aliphatic polyurethane, acroleic acid polyurethane, fragrance
Adoption urethane, end amido LNBR, hydroxyl terminated butyl nitrile (HTBN) rubber, epoxy terminated nitrile rubber, end carboxyl butyronitrile rubber
One or more in glue, polyether sulfone, polysulfones, poly ether imide, polyketone ether, polyphenylene oxide and PAEK mix in any proportion
Mixture;
The solvent is that deionized water, dehydrated alcohol, acetone, one or two in tetrahydrofuran mix in any proportion
Mixed solvent.
The invention has the advantages that:
Modified graphene oxide of the present invention, MGO-SiO2Nano-hybrid material and MGO-SiO2Phenol-formaldehyde resin modified
In concrete operations, the surface for being grafted to graphene oxide by silane coupler prepares modified oxygen to the preparation method of hot melt adhesive film
Graphite alkene, makes the modified graphene oxide for preparing have higher hydrophilic, while making modified graphene oxide mixed
Dispersibility in bonding solvent is largely increased.In addition, the present invention prepares MGO-SiO on the basis of modified graphene oxide2Receive
Rice hybrid material, in preparation process, by by modified graphene oxide and tetraethyl orthosilicate hybrid reaction, making modified oxidized stone
The silane coupler on black alkene surface is cogelled with tetraethyl orthosilicate, generates Nano-meter SiO_22And deposit it into modified graphene oxide
Surface, obtain MGO-SiO2Nano-hybrid material, makes MGO-SiO2Nano-hybrid material has equal in thermosetting phenolic resin
Even dispersibility, the fabulous compatibility and interface performance.Then by MGO-SiO2Nano-hybrid material is incorporated into thermosetting phenolic
Prepare in resin and there is graphene oxide and Nano-meter SiO_2 simultaneously2The MGO-SiO of characteristic2Phenol-formaldehyde resin modified hot melt adhesive film, so as to
Give full play to Nano-meter SiO_22The hot property and mechanical property of the performance such as excellent ablation resistance and wearability and graphene oxide
Can, greatly improve the thermostability and moulding property of phenolic resin PUR film, and low cost, and it is pre- to be applied to dry method
Leaching material moulding process.
Description of the drawings
Fig. 1 is the SEM figures that embodiment five prepares graphene oxide;
Fig. 2 is that embodiment five prepares MGO-SiO2The TEM figures of nano-hybrid material;
Fig. 3 is graphene oxide, modified graphene oxide and MGO-SiO prepared by embodiment five2Nano-hybrid material
Infrared spectrogram;
Fig. 4 is graphene oxide, modified graphene oxide and MGO-SiO prepared by embodiment five2Nano-hybrid material exists
TG curves under nitrogen atmosphere;
Fig. 5 contains 0.3%MGO-SiO for prepared by embodiment five2The thermostated viscosity of phenol-formaldehyde resin modified hot melt adhesive film is bent
Line;
Fig. 6 contains 0.3%MGO-SiO for prepared by embodiment five2Phenol-formaldehyde resin modified hot melt adhesive film and pure phenolic resin
TG curves after hot melt adhesive film solidification in air atmosphere;
Fig. 7 contains 0.3%MGO-SiO for prepared by embodiment five2Phenol-formaldehyde resin modified hot melt adhesive film and pure phenolic resin
DTG curves after hot melt adhesive film solidification in air atmosphere.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is described in further detail:
Embodiment one
The preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse 2h after stirring 1h obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
30min is stirred after 3a) mixed silane coupler with ethanol B, obtains mixed solution B, then mixed solution B is added to
In mixed solution A, and stirring reaction 12h at 75 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.1g:50mL:0.05g:
1.6g:20mL.
Catalyst is dicyclohexylcarbodiimide.
The silane coupler is gamma-aminopropyl-triethoxy-silane.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide are weighed 1b), wherein, then will be modified oxidized
Graphene is added to blend solvent, and ultrasonic disperse 2h after stirring 1h obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 25 DEG C
24h, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.1g:100mL:1mL:1g.
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 100mL, the volume of water is 150mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, then the ultrasonic disperse 3h under conditions of 0 DEG C again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material with
The ratio of solvent is 0.15g:100mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 2% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 0.15% of thermosetting phenolic resin quality in solidity phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction 3h is removed into the excess of solvent in solution E at a temperature of 70 DEG C 4c),
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film,
Wherein, the vacuum of vacuum is more than or equal to 0.09MPa, and mixing speed is 225rpm, and the viscosity when product is at 60 DEG C is
During 0.5Pa s, then product is poured out.
Thermosetting phenolic resin in thermosetting phenolic resin solution is ba phenolic resin;
The film former is PAUR;
The solvent is deionized water.
Embodiment two
The preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse 2h after stirring 1h obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
30min is stirred after 3a) mixed silane coupler with ethanol B, obtains mixed solution B, then mixed solution B is added to
In mixed solution A, and stirring reaction 12h at 75 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.1g:50mL:0.05g:
1.6g:65mL.
Catalyst is triphenylphosphine.
The silane coupler is γ-(2,3- glycidoxies) propyl trimethoxy silicane.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide are weighed 1b), wherein, then will be modified oxidized
Graphene is added to blend solvent, and ultrasonic disperse 2h after stirring 1h obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 25 DEG C
24h, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.1g:500mL:1mL:10g.
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 500mL, the volume of water is 15mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, then the ultrasonic disperse 3h under conditions of 0 DEG C again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material with
The ratio of solvent is 0.3g:100mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 2% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 0.3% of thermosetting phenolic resin quality in solidity phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction 5h is removed into the excess of solvent in solution E at a temperature of 70 DEG C 4c),
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film,
Wherein, the vacuum of vacuum is more than or equal to 0.09MPa, and mixing speed is 100rpm, and the viscosity when product is at 90 DEG C is
During 2.0Pa s, then product is poured out.
Thermosetting phenolic resin in thermosetting phenolic resin solution is Mo-phenolic resin;
The film former is EU;
The solvent is dehydrated alcohol.
Embodiment three
The preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse 3h after stirring 3h obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
30min is stirred after 3a) mixed silane coupler with ethanol B, obtains mixed solution B, then mixed solution B is added to
In mixed solution A, and stirring reaction 12h at 60 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.1g:50mL:0.05g:
1.5g:10mL.
Catalyst is dicyclohexylcarbodiimide and triphenylphosphine in mass ratio 1:The mixture of 1 mixing.
The silane coupler is gamma-aminopropyl-triethoxy-silane and γ-(2,3- glycidoxies) propyl group trimethoxy
Base silane in mass ratio 1:The mixture of 1 mixing.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide are weighed 1b), wherein, then will be modified oxidized
Graphene is added to blend solvent, and ultrasonic disperse 1h after stirring 3h obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 65 DEG C
12h, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.1g:100mL:1mL:1g.
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 200mL, the volume of water is 20mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, then the ultrasonic disperse 1h under conditions of 0 DEG C again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material with
The ratio of solvent is 0.3g:50mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 3% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 0.1% of thermosetting phenolic resin quality in solidity phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction 3h is removed into the excess of solvent in solution E at a temperature of 80 DEG C 4c),
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film,
Wherein, the vacuum of vacuum is more than or equal to 0.09MPa, and mixing speed is 300rpm, and the viscosity when product is at 80 DEG C is
During 1.8Pa s, then product is poured out.
Thermosetting phenolic resin in thermosetting phenolic resin solution is W-phenolic resin;
The film former is aliphatic polyurethane;
The solvent is acetone.
Example IV
The preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse 1h after stirring 2h obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
30min is stirred after 3a) mixed silane coupler with ethanol B, obtains mixed solution B, then mixed solution B is added to
In mixed solution A, and stirring reaction 15h at 25 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.1g:250mL:0.65g:
3.2g:20mL.
Catalyst is dicyclohexylcarbodiimide and triphenylphosphine in mass ratio 5:The mixture of 1 mixing.
The silane coupler is gamma-aminopropyl-triethoxy-silane and γ-(2,3- glycidoxies) propyl group trimethoxy
Base silane in mass ratio 5:The mixture of 1 mixing.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide are weighed 1b), wherein, then will be modified oxidized
Graphene is added to blend solvent, and ultrasonic disperse 2h after stirring 1.5h obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 50 DEG C
24h, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.1g:100mL:0.3mL:
1g。
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 300mL, the volume of water is 80mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, then the ultrasonic disperse 3h under conditions of 0 DEG C again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material with
The ratio of solvent is 0.1g:500mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 3% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 0.1% of thermosetting phenolic resin quality in solidity phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction 5h is removed into the excess of solvent in solution E at a temperature of 25 DEG C 4c),
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film,
Wherein, the vacuum of vacuum is more than or equal to 0.09MPa, and mixing speed is 100rpm, and the viscosity when product is at 65 DEG C is
During 1.8Pa s, then product is poured out.
Thermosetting phenolic resin in thermosetting phenolic resin solution is W-phenolic resin;
The film former is aliphatic polyurethane;
The solvent is tetrahydrofuran.
Embodiment five
The preparation process of graphite oxide is as follows:
The concentrated sulphuric acid of 115mL is added in 500mL beakers, and makes temperature maintain 0 DEG C or so, under mechanical agitation with frozen water
The mixture of 5g powderies crystalline flake graphite and 2.5g sodium nitrates is added, being stirred vigorously makes reaction temperature uniform;Add 15g again in batches
Potassium permanganate, by temperature control at 0 DEG C or so, charging stirs 2h after finishing, and removes ice-water bath afterwards;Temperature is raised to into 35 DEG C,
Continue stirring 2h;Distilled water is slowly added into, allowing temperature to rise to 98 DEG C or so carries out pyroreaction, stirs 1.5h;It is eventually adding
Deionized water, and the substantial amounts of hydrogen peroxide of Deca, after standing a period of time, outwell the supernatant, and the hydrochloric acid for being with concentration 15% is rushed
Wash, after pickling, then be washed twice with deionized water, neutrality is close to system;With the high speed centrifugation of 3500r/min or so rotating speeds
Machine, is centrifuged once every 5min, is constantly rinsed with ionized water, till value reaches neutrality;After vacuum drying 24h, obtain
Graphite oxide.
The preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse 2h after stirring 1h obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
30min is stirred after 3a) mixed silane coupler with ethanol B, obtains mixed solution B, then mixed solution B is added to
In mixed solution A, and stirring reaction 24h at 75 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.5g:50mL:0.05g:
3.2g:20mL.
Catalyst is dicyclohexylcarbodiimide and triphenylphosphine in mass ratio 3:The mixture of 1 mixing.
The silane coupler is gamma-aminopropyl-triethoxy-silane and γ-(2,3- glycidoxies) propyl group trimethoxy
Base silane in mass ratio 2:The mixture of 1 mixing.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide are weighed 1b), wherein, then will be modified oxidized
Graphene is added to blend solvent, and ultrasonic disperse 1h after stirring 3h obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 25 DEG C
20h, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.5g:100mL:0.35mL:
5g。
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 100mL, the volume of water is 85mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, then the ultrasonic disperse 3h under conditions of 0 DEG C again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material with
The ratio of solvent is 0.3g:50mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 1% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 0.7% of thermosetting phenolic resin quality in solidity phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction 3h is removed into the excess of solvent in solution E at a temperature of 70 DEG C 4c),
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film,
Wherein, the vacuum of vacuum is more than or equal to 0.09MPa, and mixing speed is 300rpm, and the viscosity when product is at 90 DEG C is
During 0.5Pa s, then product is poured out.
Thermosetting phenolic resin in thermosetting phenolic resin solution is ammonia phenolic resin;
The film former is acroleic acid polyurethane;
The solvent is tetrahydrofuran.
Embodiment six
The preparation method of modified graphene oxide of the present invention is comprised the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added to into ethanol
In A, ultrasonic disperse 2.5h after stirring 2.5h obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
30min is stirred after 3a) mixed silane coupler with ethanol B, obtains mixed solution B, then mixed solution B is added to
In mixed solution A, and stirring reaction 24h at 40 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.2g:100mL:0.1g:
10g:65mL.
Catalyst is dicyclohexylcarbodiimide and triphenylphosphine in mass ratio 2:The mixture of 1 mixing.
The silane coupler is gamma-aminopropyl-triethoxy-silane and γ-(2,3- glycidoxies) propyl group trimethoxy
Base silane in mass ratio 4:The mixture of 1 mixing.
MGO-SiO of the present invention2The preparation method of nano-hybrid material is comprised the following steps:
Blend solvent, strong aqua ammonia, tetraethyl orthosilicate and modified graphene oxide are weighed 1b), wherein, then will be modified oxidized
Graphene is added to blend solvent, and ultrasonic disperse 3h after stirring 1.2h obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, must mix after stirring
Solution C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 50 DEG C
15h, then carries out sucking filtration, washing and drying again successively, obtains MGO-SiO2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 1.2g:250mL:0.10mL:
4g。
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 250mL, the volume of water is 40mL;
MGO-SiO of the present invention2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film is comprised the following steps:
Solvent and MGO-SiO are weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano-hybrid material is added to solvent
In, then the ultrasonic disperse 6h under conditions of 0 DEG C again, obtains MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material with
The ratio of solvent is 1g:60mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added to into thermosetting phenolic resin solution
In, stirring makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is
The 0.5% of thermosetting phenolic resin quality in thermosetting phenolic resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes
MGO-SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is heat
The 1% of thermosetting phenolic resin quality in solidity phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction 1h is removed into the excess of solvent in solution E at a temperature of 70 DEG C 4c),
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film,
Wherein, the vacuum of vacuum is more than or equal to 0.09MPa, and mixing speed is 180rpm, and the viscosity when product is at 65 DEG C is
During 1Pa s, then product is poured out.
Thermosetting phenolic resin in thermosetting phenolic resin solution is ba phenolic resin, Mo-phenolic resin and tungsten phenolic aldehyde tree
The mixture that fat mixes in any proportion;
The film former is the mixture that PAUR and EU mix in any proportion;
The solvent is the mixed solvent that deionized water is mixed in any proportion with dehydrated alcohol.
It should be noted that thermosetting phenolic resin in thermosetting phenolic resin solution can also for phosphorous-containing phenolic resin,
Or in ba phenolic resin, Mo-phenolic resin, W-phenolic resin, ammonia phenolic resin and phosphorous-containing phenolic resin it is several in any proportion
The mixture of mixing, the concentration of strong aqua ammonia is 28wt%.
Film former can also be aromatic urethane, end amido LNBR, hydroxyl terminated butyl nitrile (HTBN) rubber, end ring
In epoxide nitrile rubber, nbr carboxyl terminal, polyether sulfone, polysulfones, poly ether imide, polyketone ether, polyphenylene oxide and PAEK
One kind or PAUR, EU, aliphatic polyurethane, acroleic acid polyurethane, aromatic urethane,
End amido LNBR, hydroxyl terminated butyl nitrile (HTBN) rubber, epoxy terminated nitrile rubber, nbr carboxyl terminal, polyether sulfone,
Several mixture for mixing in any proportion in polysulfones, poly ether imide, polyketone ether, polyphenylene oxide and PAEK.
Fig. 1 and Fig. 2 is respectively graphene oxide and MGO-SiO prepared by embodiment five2The SEM of nano-hybrid material and
TEM schemes, from figure 1 it appears that relatively thin graphene oxide is successfully prepared, and surface of graphene oxide is because of degree of oxidation
There is fold in difference.Fig. 2 is MGO-SiO2The TEM figures of nano-hybrid material, from figure 2 it can be seen that Nano-meter SiO_22Particle success
Deposit to surface of graphene oxide, and be evenly distributed, particle diameter is in 5nm or so.
Fig. 3 is graphene oxide, modified graphene oxide and MGO-SiO prepared by embodiment five2Nano-hybrid material
Infrared spectrogram, as can be seen that in 3412cm from the infrared spectrum of graphene oxide-1The absworption peak for nearby occurring, is oxidation
The stretching vibration peak of graphenic surface O-H;1725cm-1The absworption peak for nearby occurring, belongs to surface of graphene oxide carboxyl C=O
Stretching vibration peak;1626cm-1The absworption peak of appearance, belongs to the stretching vibration of surface of graphene oxide C=C;1053cm-1With
805cm-1Place belongs to the stretching vibration of surface of graphene oxide epoxy radicals C-O;The appearance of these groups proves graphite by oxygen
Chemical conversion graphite oxide, and the oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy radicals are contained on surface;From modified graphene oxide and MGO-
SiO2It is found that in 2800-3000cm in the infrared spectrogram of nano-hybrid material-1The absworption peak for nearby occurring is silane point
- CH in subchain2Stretching vibration peak;Meanwhile, 1090cm-1And 779cm-1Place's absworption peak is belonging respectively to Si-O-C/Si-O-Si not
To the stretching vibration into stretching vibration and Si-C;Additionally, 1725cm-1Place surface of graphene oxide carboxyl C=O peaks and
1053cm-1And 805cm-1The disappearance at place epoxy radicals C-O peak, the carboxyl and epoxy radicals for illustrating surface of graphene oxide are reacted
And successfully ATPES is connected.
Fig. 4 is graphene oxide, modified graphene oxide and MGO-SiO prepared by embodiment five2Nano-hybrid material exists
TG curves under nitrogen atmosphere.It can be seen from figure 4 that graphene oxide is maximum in 150 DEG C or so weight loss rates, this be due to
The a large amount of oxygen-containing functional groups of surface of graphene oxide decompose and cause.For graphene oxide, modified graphene oxide and
MGO-SiO2The heat stability of nano-hybrid material has lifting by a relatively large margin, and this is that the carboxyl on their surfaces and epoxy radicals are taken
For caused.In pyrolytic process, the Nano-meter SiO_2 of surface deposition2Granule defines the SiO of densification2Resistance to ablation layer, protects oxidation
Graphene, MGO-SiO2Nano-hybrid material weightlessness is relatively low, improves the heat stability of graphene oxide.
Fig. 5 contains 0.3%MGO-SiO for prepared by embodiment five2The phenolic resin PUR film of nano-hybrid material
Constant temperature viscosity curve.It can be seen that when temperature is 70 DEG C, MGO-SiO2Phenol-formaldehyde resin modified hot melt adhesive film is at 90 points
Viscosity in clock between 0.7~2.5Pa s, with relatively low viscosity and wider work platformses.Meet Resin Film Infusion work
The requirement of skill and prepreg dipping.When temperature is 80 DEG C, MGO-SiO2Phenol-formaldehyde resin modified hot melt adhesive film is in 105 minutes
Viscosity between 0.4~2.5Pa s, with relatively low viscosity and wider work platformses.Meet Resin film infusion and pre-
The requirement of leaching material dipping.
Prepared by Fig. 6 and Fig. 7 respectively embodiments five contains 0.3%MGO-SiO2Phenol-formaldehyde resin modified hot melt adhesive film and pure
TG and DTG curves after the solidification of phenolic resin PUR film in air atmosphere.From fig. 6 it can be seen that at 470 DEG C afterwards,
Unmodified phenolic resin PUR film weight loss rate is significantly greater than MGO-SiO2Phenol-formaldehyde resin modified hot melt adhesive film.Additionally, from
DTG curves can be seen that unmodified phenolic resin PUR film weight loss rate is larger 500 DEG C~570 DEG C periods, and MGO-
SiO2The not significantly weightlessness behavior of phenol-formaldehyde resin modified hot melt adhesive film.Meanwhile, MGO-SiO2Phenol-formaldehyde resin modified hot melt adhesive film
Big weightless interval has been postponed till between 600 DEG C~670 DEG C, and weight loss rate is also significantly less than unmodified system, shows
MGO-SiO2The addition of nano-hybrid material improves the heat stability of phenolic resin, embodies MGO-SiO2Nano-hybrid material
Contribution to phenolic resin thermostability.
Claims (10)
1. a kind of preparation method of modified graphene oxide, it is characterised in that comprise the following steps:
Graphite oxide, ethanol A, catalyst, silane coupler and ethanol B 1a) is weighed, then graphite oxide is added in ethanol A,
Ultrasonic disperse after stirring, obtains graphene oxide dispersion;
Catalyst is added to into step 1a 2a)) in the graphene oxide dispersion that obtains, obtain mixed solution A;
Stir after 3a) mixed silane coupler with ethanol B, obtain mixed solution B, then mixed solution B is added to into mixed solution A
In, and the stirring reaction at 25~75 DEG C, sucking filtration drying is then carried out again, obtains modified graphene oxide;
Wherein, the ratio of graphite oxide, ethanol A, catalyst, silane coupler and ethanol B is 0.1~0.5g:50~250mL:
0.05~0.65g:1.5~10g:10~65mL.
2. the preparation method of modified graphene oxide according to claim 1, it is characterised in that step 1a) in stirring
Time is 1~3h, and the time of ultrasonic disperse is 1~3h;
Step 3a) in silane coupler is mixed with ethanol B after stir 30min;
Step 3a) at 25~75 DEG C stirring reaction response time be 12~24h.
3. the preparation method of modified graphene oxide according to claim 1, it is characterised in that catalyst is dicyclohexyl
Carbodiimide, triphenylphosphine or dicyclohexylcarbodiimide and triphenylphosphine 1-5 in mass ratio:The mixture of 1 mixing.
4. the preparation method of modified graphene oxide according to claim 1, it is characterised in that the silane coupler is
Gamma-aminopropyl-triethoxy-silane, γ-(2,3- glycidoxies) propyl trimethoxy silicane or gamma-aminopropyl-triethoxy
Silane and γ-(2,3- glycidoxies) propyl trimethoxy silicane 1-5 in mass ratio:The mixture of 1 mixing.
5. a kind of MGO-SiO2The preparation method of nano-hybrid material, it is characterised in that comprise the following steps:
Modified graphene oxide prepared by blend solvent, strong aqua ammonia, tetraethyl orthosilicate and claim 1 1b) is weighed, then will be changed
Property graphene oxide is added to blend solvent, and ultrasonic disperse after stirring obtains modified graphene oxide dispersion liquid;
Strong aqua ammonia is added to into step 1b 2b)) in the modified graphene oxide dispersion liquid that obtains, after stirring mixed solution
C;
Tetraethyl orthosilicate is added drop-wise to into step 2b 3b)) in the mixed solution C that obtains, then the stirring reaction at a temperature of 25~65 DEG C,
Then sucking filtration, washing and drying are carried out again successively, MGO-SiO is obtained2Nano-hybrid material;
The ratio of modified graphene oxide, blend solvent, strong aqua ammonia and tetraethyl orthosilicate is 0.1~0.5g:100~500mL:
0.10~1mL:1~10g.
6. MGO-SiO according to claim 52The preparation method of nano-hybrid material, it is characterised in that
Step 1b) in time of stirring be 1-3h, time of ultrasonic disperse is 1-3h;
Step 3b) at a temperature of 25~65 DEG C stirring reaction response time be 12-24h.
7. MGO-SiO according to claim 52The preparation method of nano-hybrid material, it is characterised in that
Blend solvent is made up of ethanol C and water, and wherein, in the blend solvent of 100~500mL, the volume of water is 15~150mL.
8. a kind of MGO-SiO2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film, it is characterised in that comprise the following steps:
The MGO-SiO that solvent and claim 5 are prepared is weighed 1c)2Nano-hybrid material, then by MGO-SiO2Nano hybridization
Material is added in solvent, is then carried out ultrasonic disperse again, is obtained MGO-SiO2Dispersion liquid, wherein, MGO-SiO2Nano-hybrid material
Ratio with solvent is 0.1~1g:50~500mL;
Film former and thermosetting phenolic resin solution 2c) is weighed, then film former is added in thermosetting phenolic resin solution, stirred
Mixing makes film former dispersing and dissolving in thermosetting phenolic resin solution, obtains mixed solution D, and wherein, the quality of film former is thermosetting
The 0.5~3% of thermosetting phenolic resin quality in property phenol resin solution;
3c) by step 1c) MGO-SiO that obtains2Dispersion liquid is added to step 2c) in the mixed solution D that obtains, stirring makes MGO-
SiO2Homogeneous dispersion is distributed in mixed solution D, obtains mixed solution E, wherein, MGO-SiO2The quality of dispersion liquid is thermosetting
The 0.1~1% of thermosetting phenolic resin quality in phenol resin solution;
Mixed solution E vacuum constant temperature stirring reaction is removed into the excess of solvent in solution E at a temperature of 25~80 DEG C 4c), when
When the viscosity of product is more than or equal to preset value, product is poured out, MGO-SiO is obtained2Phenol-formaldehyde resin modified hot melt adhesive film.
9. MGO-SiO according to claim 82The preparation method of phenol-formaldehyde resin modified hot melt adhesive film, it is characterised in that
Step 1c) in the concrete operations of ultrasonic disperse be:1~6h of ultrasonic disperse under conditions of 0 DEG C;
Step 4c) at a temperature of 25~80 DEG C vacuum constant temperature stirring reaction response time be 1~5h, mixing speed is 100
~300rpm, vacuum are more than or equal to 0.09MPa;
Step 4c) in viscosity when product is at 60~90 DEG C when being 0.5~2.0Pa s, then pour out product.
10. MGO-SiO according to claim 82The preparation method of phenol-formaldehyde resin modified hot melt adhesive film, it is characterised in that
Thermosetting phenolic resin in thermosetting phenolic resin solution is ba phenolic resin, Mo-phenolic resin, W-phenolic resin, ammonia
One or more mixture for mixing in any proportion in phenolic resin and phosphorous-containing phenolic resin;
The film former is PAUR, EU, aliphatic polyurethane, acroleic acid polyurethane, fragrant adoption
It is urethane, end amido LNBR, hydroxyl terminated butyl nitrile (HTBN) rubber, epoxy terminated nitrile rubber, nbr carboxyl terminal, poly-
It is mixed that one or more in ether sulfone, polysulfones, poly ether imide, polyketone ether, polyphenylene oxide and PAEK mix in any proportion
Compound;
The solvent be deionized water, dehydrated alcohol, acetone, one or two in tetrahydrofuran mix in any proportion it is mixed
Bonding solvent.
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