CN109468843A - A method of hydroxy-end capped dissaving polymer is grafted in carbon fiber surface - Google Patents
A method of hydroxy-end capped dissaving polymer is grafted in carbon fiber surface Download PDFInfo
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- CN109468843A CN109468843A CN201811260450.9A CN201811260450A CN109468843A CN 109468843 A CN109468843 A CN 109468843A CN 201811260450 A CN201811260450 A CN 201811260450A CN 109468843 A CN109468843 A CN 109468843A
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
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Abstract
A method of it being grafted hydroxy-end capped dissaving polymer in carbon fiber surface, it is related to a kind of method of modifying of carbon fiber surface.The problem of the invention aims to solve the synthesis technology of carbon fiber and the weak and hydroxy-end capped dissaving polymer of resin matrix interface cohesion complexity, synthesis material is toxic, restricts its modified carbon fiber.Method: one, hydroxy-end capped dissaving polymer is prepared；Two, the extracting processing of carbon fiber；Three, it aoxidizes；Four, it is grafted, obtains the carbon fiber of the hydroxy-end capped dissaving polymer of surface grafting.The present invention has a large amount of polar hydroxyl groups and hole configurations due to hydroxy-end capped dissaving polymer, after being grafted to carbon fiber surface, wellability and caking property between carbon fiber and resin are significantly increased, this will substantially improve the interface performance of composite material, and then improve the mechanical property and thermal stability of composite material.The present invention can get a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface.
Description
Technical field
The present invention relates to a kind of method of modifying of carbon fiber surface.
Background technique
In recent years, carbon fiber (CF) is widely used as the ideal of advanced composite material and increases due to its high-intensitive, high-modulus
The performance of Qiang Ti, carbon fiber reinforced polymer (CFRP) composite material are largely dependent upon interface performance, high quality interface
It is the guarantee that load is uniformly transferred to carbon fiber from resin.But since the smooth presentation chemical inertness of carbon fiber surface, surface energy are low,
With the wellability and bad adhesion of resin matrix, the interface performance of composite material and the performance of other performance, institute are finally affected
Most important with development of the surface treatment of carbon fibers to its reinforcing material, current unmodified carbon fiber and resin matrix interface are tied
Close weak, the interface shear strength of unmodified carbon fibre composite is about 49MPa, it is therefore desirable to which the surface of carbon fiber is carried out
It is modified, it mainly include at present surface oxidation technology, chemical vapour deposition technique and surface to the process for modifying surface of carbon fiber
Coating technology etc., these methods can improve the wellability of carbon fiber and resin substantially, but there are production technology complexity, it is at high cost
With the reaction time it is longer the problems such as.Therefore, we are dedicated to finding a kind of mild condition, environmentally protective, efficient carbon fiber at present
Dimension table surface modification process, it is intended to while avoiding monfil bulk strength from declining, more active sites are formed on its surface,
To improve the interface bond strength of carbon fiber and resin.
The graft polymers technology research direction emerging as one, is that macromolecular is grafted on carbon fiber surface, with
Improve carbon fiber surface activity and roughness, and then improves its interfacial combined function.Hydroxy-end capped dissaving polymer (HTHBP)
Due to widely being paid close attention to a large amount of terminal polar hydroxyl, hole configurations and high resin compatibility, it is not only provided
The a large amount of active sites that can be reacted with carbon fiber and resin matrix, and the reaction of curing agent and epoxy resin can be promoted, because
This can become functionalized carbon fiber ideal material, but there are hydroxy-end capped dissaving polymer synthesis technology it is complex and close
The problems such as toxic at raw material.
Summary of the invention
The invention aims to solve carbon fiber and the weak and hydroxy-end capped dissaving polymer of resin matrix interface cohesion
Synthesis technology it is complicated, synthesis material is toxic, the problem of restricting its modified carbon fiber, and provides and a kind of be grafted in carbon fiber surface
The method of hydroxy-end capped dissaving polymer.
A method of it being grafted hydroxy-end capped dissaving polymer in carbon fiber surface, is completed by the following steps:
One, hydroxy-end capped dissaving polymer is prepared:
1., isophorone diisocyanate and n,N-dimethylacetamide be added in glass container, obtain different Fo Er
Ketone diisocyanate solution；Glass container equipped with isophorone diisocyanate solution is placed in 0 DEG C~5 DEG C of ice-water bath again
In；
Step 1 1. described in the quality of isophorone diisocyanate and the volume ratio of DMAC N,N' dimethyl acetamide be
(6g~12g): 50mL；
2., trishydroxymethylaminomethane is added in n,N-dimethylacetamide, then ultrasonic mixing 10min~20min,
Obtain tris solution；
Step 1 2. described in trishydroxymethylaminomethane quality and DMAC N,N' dimethyl acetamide volume ratio be (3g
~6g): 50mL；
3., by step 1 1. in be placed in 0 DEG C~5 DEG C ice-water bath glass container in isophorone diisocyanate it is molten
Liquid is stirred, mixing speed be 300r/min~400r/min, then by tris solution with 10 drops/min~
15 drops/min rate of addition is added drop-wise to the isophorone that temperature is 0 DEG C~5 DEG C, mixing speed is 300r/min~400r/min
In diisocyanate solution, reaction solution I is obtained；
Step 1 3. described in isophorone diisocyanate solution and tris solution volume ratio
For 1:1；
4., the temperature of reaction solution I is warming up to 5 DEG C~10 DEG C, then be stirred to react at being 5 DEG C~10 DEG C in temperature 5h~
6h, then the temperature of reaction solution I is warming up to 35 DEG C~40 DEG C, then two fourth of tin dilaurate is added into 35 DEG C~40 DEG C reaction solutions I
Ji Xi is finally stirred to react 10h~15h in the case where temperature is 35 DEG C~40 DEG C and mixing speed is 300r/min~400r/min,
Obtain reaction solution II；
Step 1 4. described in dibutyl tin dilaurate quality and reaction solution I volume ratio be (0.08g~
0.12g):100mL；
5., reaction solution II is add to deionized water to precipitation precipitating, then stand 25min~30min, then in centrifugal speed
To be centrifuged under 6000r/min~8000r/min, solid reaction product is obtained；
6., using deionized water solid reaction product is cleaned 3 times~5 times, then the solid after deionized water is cleaned is anti-
It answers product to be put into freeze drier, then is freeze-dried 36h~48h at being -10 DEG C~-5 DEG C in temperature, obtain dry white
Solid matter, as hydroxy-end capped dissaving polymer；
Two, the extracting processing of carbon fiber:
1., carbon fiber is put into the Soxhlet extractor equipped with acetone, then acetone is heated to 75 DEG C~85 DEG C, acetone is not
It is disconnected to steam and condensed in Soxhlet extractor, so that the impurity of carbon fiber surface is continuously available cleaning in the acetone of distillation, cleans
Time is 48h~72h, then carbon fiber is taken out, and obtains the carbon fiber of removal surface impurity；The carbon fiber of surface impurity will be removed
It takes out, then being placed in temperature is dry 2h~4h in 70 DEG C~80 DEG C of baking oven, obtains extracting treated carbon fiber；
Three, it aoxidizes:
1., will extracting treated that carbon fiber is immersed in potassium peroxydisulfate/silver nitrate mixed aqueous solution, be heated to 60 DEG C~
80 DEG C, then constant temperature 1h~2h under conditions of temperature is 60 DEG C~80 DEG C, the carbon fiber after being aoxidized；The persulfuric acid
The concentration of potassium peroxydisulfate is 0.1mol/L~0.2mol/L in potassium/silver nitrate mixed aqueous solution；Potassium peroxydisulfate/the silver nitrate
The concentration of silver nitrate is 0.0001mol/L~0.05mol/L in mixed aqueous solution；
Step 3 1. described in extracting treated carbon fiber quality and potassium peroxydisulfate/silver nitrate mixed aqueous solution
Volume ratio is (0.3g~1.5g): (300mL~500mL)；
2., the carbon fiber after the oxidation that under room temperature 1. obtains step 3 5min~10min is impregnated in distilled water,
Carbon fiber after impregnating in distilled water is taken out, reject distilled water；
Step 3 2. described in oxidation after carbon fiber quality and distilled water volume ratio be (0.3g~1.5g):
(300mL~500mL)；
3., repeat step 3 2. 3 times~5 times, obtain distilled water cleaning after carbon oxide fiber；
4., the carbon oxide fiber after the distilled water cleaning that 3. obtains step 3 is under conditions of temperature is 70 DEG C~80 DEG C
Dry 2h~4h, the carbon oxide fiber after being dried；
5., the carbon oxide fiber after 4. drying that step 3 obtains is placed in the Soxhlet extractor equipped with dehydrated alcohol,
Washes of absolute alcohol carbon oxide fiber is used under conditions of temperature is 90 DEG C~100 DEG C, scavenging period is 2h~4h, obtains nothing
The carbon fiber of the oxidation of water-ethanol cleaning；
6., the carbon fiber of the oxidation of washes of absolute alcohol that 5. obtains step 3 be 70 DEG C~80 DEG C in temperature condition
Lower dry 2h~4h, obtains dry carbon oxide fiber；
Four, it is grafted:
1., hydroxy-end capped dissaving polymer is added in n,N-dimethylacetamide, re-ultrasonic dispersion 15min~
Then dry carbon oxide fiber, 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 4- is added in 30min
Dimethylamino naphthyridine finally stirs under conditions of temperature is 100 DEG C~150 DEG C and mixing speed is 300r/min~400r/min
Reflux 12h~for 24 hours is mixed, the carbon fiber that obtains that treated；
Step 4 1. described in hydroxy-end capped dissaving polymer quality and DMAC N,N' dimethyl acetamide volume ratio
For (1g~1.5g): (30mL~60mL)；
Step 4 1. described in drying the quality of carbon oxide fiber and the volume ratio of DMAC N,N' dimethyl acetamide be
(1.0~2.0g): (30mL~60mL)；
Step 4 1. described in 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate quality and N, N-
The volume ratio of dimethyl acetamide is (0.5g~1.0g): (30mL~60mL)；
Step 4 1. described in 4-dimethylaminopyridine quality and DMAC N,N' dimethyl acetamide volume ratio be (0.05
~0.1g): (30mL~60mL)；
2., will treated carbon fiber take out after be immersed in 10min~15min in distilled water；
3., circulation step four 3. 3 times~5 times, obtain distilled water cleaning treated carbon fiber；
4., by distilled water cleaning, treated that carbon fiber is placed in the Soxhlet extractor equipped with dehydrated alcohol, in temperature
Washes of absolute alcohol distilled water clean that treated carbon fiber, scavenging period 2h is used under conditions of being 90 DEG C~100 DEG C
~4h obtains washes of absolute alcohol treated carbon fiber；
5., dry 3h in the baking oven that is 75 DEG C~80 DEG C by washes of absolute alcohol treated carbon fiber is placed in temperature~
5h obtains the carbon fiber of the hydroxy-end capped dissaving polymer of surface grafting.
The principle of the present invention and advantage:
One, present invention uses nontoxic and high activity trishydroxymethylaminomethanes (TOAM) to be used as synthesis material, largely
Generated time is shortened, environmental pollution is reduced；
Two, hydroxy-end capped grafted by super branched polymer to carbon fiber surface is prepared for by the present invention using covalence graft method
A kind of not only surface contains a large amount of polar terminals hydroxyls and be easy to be formed the carbon fiber of covalent bond with matrix；
Three, since hydroxy-end capped dissaving polymer has a large amount of polar hydroxyl groups and hole configurations, when being grafted to
After carbon fiber surface, wellability and caking property between carbon fiber and resin are significantly increased, this will substantially improve composite material
Interface performance, and then improve composite material mechanical property and thermal stability；
Four, the interface shear strength of the carbon fiber of the hydroxy-end capped dissaving polymer of surface grafting prepared by the present invention
(IFSS) 60.9MPa~87.8MP is increased to by the 48.8MPa of precursor (non-grafted carbon fiber), improve 25%~
79.9%；Interlaminar shear strength (ILSS) by the 58.6MPa of precursor (non-grafted carbon fiber) be increased to 69.7MPa~
81.8MPa improves 19%~39.6%.
The present invention can get a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface.
Detailed description of the invention
Fig. 1 is the XPS spectrum figure of 3. extracting treated carbon fiber that one step 2 of embodiment obtains；
Fig. 2 is the swarming spectrogram of Fig. 1, and 1 is C1s (1) in figure, and 2 be C1s (2), and 3 be C1s (3)；
Fig. 3 is the XPS of the carbon fiber of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains
Spectrogram；
Fig. 4 is the swarming spectrogram of Fig. 3, and 4 be C-N in figure, and 5 be C-O, and 6 be C=O, and 7 be NCOO；
Fig. 5 is the SEM figure of 3. extracting treated carbon fiber that one step 2 of embodiment obtains；
Fig. 6 is the SEM of the carbon fiber of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains
Figure；
Fig. 7 is interface shear strength histogram, 1 extracting 3. obtained for one step 2 of embodiment treated carbon fiber in figure
The interface shear strength of dimension, the carbon fiber of the 2 hydroxy-end capped dissaving polymers of surface grafting 5. obtained for one step 4 of embodiment
The interface shear strength of dimension；
Fig. 8 is interlaminar shear strength histogram, 1 extracting 3. obtained for one step 2 of embodiment treated carbon fiber in figure
The interlaminar shear strength of dimension, the carbon fiber of the 2 hydroxy-end capped dissaving polymers of surface grafting 5. obtained for one step 4 of embodiment
The interlaminar shear strength of dimension.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of to be grafted hydroxy-end capped dissaving polymer in carbon fiber surface
Method is completed by the following steps:
One, hydroxy-end capped dissaving polymer is prepared:
1., isophorone diisocyanate and n,N-dimethylacetamide be added in glass container, obtain different Fo Er
Ketone diisocyanate solution；Glass container equipped with isophorone diisocyanate solution is placed in 0 DEG C~5 DEG C of ice-water bath again
In；
Step 1 1. described in the quality of isophorone diisocyanate and the volume ratio of DMAC N,N' dimethyl acetamide be
(6g~12g): 50mL；
2., trishydroxymethylaminomethane is added in n,N-dimethylacetamide, then ultrasonic mixing 10min~20min,
Obtain tris solution；
Step 1 2. described in trishydroxymethylaminomethane quality and DMAC N,N' dimethyl acetamide volume ratio be (3g
~6g): 50mL；
3., by step 1 1. in be placed in 0 DEG C~5 DEG C ice-water bath glass container in isophorone diisocyanate it is molten
Liquid is stirred, mixing speed be 300r/min~400r/min, then by tris solution with 10 drops/min~
15 drops/min rate of addition is added drop-wise to the isophorone that temperature is 0 DEG C~5 DEG C, mixing speed is 300r/min~400r/min
In diisocyanate solution, reaction solution I is obtained；
Step 1 3. described in isophorone diisocyanate solution and tris solution volume ratio
For 1:1；
4., the temperature of reaction solution I is warming up to 5 DEG C~10 DEG C, then be stirred to react at being 5 DEG C~10 DEG C in temperature 5h~
6h, then the temperature of reaction solution I is warming up to 35 DEG C~40 DEG C, then two fourth of tin dilaurate is added into 35 DEG C~40 DEG C reaction solutions I
Ji Xi is finally stirred to react 10h~15h in the case where temperature is 35 DEG C~40 DEG C and mixing speed is 300r/min~400r/min,
Obtain reaction solution II；
Step 1 4. described in dibutyl tin dilaurate quality and reaction solution I volume ratio be (0.08g~
0.12g):100mL；
5., reaction solution II is add to deionized water to precipitation precipitating, then stand 25min~30min, then in centrifugal speed
To be centrifuged under 6000r/min~8000r/min, solid reaction product is obtained；
6., using deionized water solid reaction product is cleaned 3 times~5 times, then the solid after deionized water is cleaned is anti-
It answers product to be put into freeze drier, then is freeze-dried 36h~48h at being -10 DEG C~-5 DEG C in temperature, obtain dry white
Solid matter, as hydroxy-end capped dissaving polymer；
Two, the extracting processing of carbon fiber:
1., carbon fiber is put into the Soxhlet extractor equipped with acetone, then acetone is heated to 75 DEG C~85 DEG C, acetone is not
It is disconnected to steam and condensed in Soxhlet extractor, so that the impurity of carbon fiber surface is continuously available cleaning in the acetone of distillation, cleans
Time is 48h~72h, then carbon fiber is taken out, and obtains the carbon fiber of removal surface impurity；The carbon fiber of surface impurity will be removed
It takes out, then being placed in temperature is dry 2h~4h in 70 DEG C~80 DEG C of baking oven, obtains extracting treated carbon fiber；
Three, it aoxidizes:
1., will extracting treated that carbon fiber is immersed in potassium peroxydisulfate/silver nitrate mixed aqueous solution, be heated to 60 DEG C~
80 DEG C, then constant temperature 1h~2h under conditions of temperature is 60 DEG C~80 DEG C, the carbon fiber after being aoxidized；The persulfuric acid
The concentration of potassium peroxydisulfate is 0.1mol/L~0.2mol/L in potassium/silver nitrate mixed aqueous solution；Potassium peroxydisulfate/the silver nitrate
The concentration of silver nitrate is 0.0001mol/L~0.05mol/L in mixed aqueous solution；
Step 3 1. described in extracting treated carbon fiber quality and potassium peroxydisulfate/silver nitrate mixed aqueous solution
Volume ratio is (0.3g~1.5g): (300mL~500mL)；
2., the carbon fiber after the oxidation that under room temperature 1. obtains step 3 5min~10min is impregnated in distilled water,
Carbon fiber after impregnating in distilled water is taken out, reject distilled water；
Step 3 2. described in oxidation after carbon fiber quality and distilled water volume ratio be (0.3g~1.5g):
(300mL~500mL)；
3., repeat step 3 2. 3 times~5 times, obtain distilled water cleaning after carbon oxide fiber；
4., the carbon oxide fiber after the distilled water cleaning that 3. obtains step 3 is under conditions of temperature is 70 DEG C~80 DEG C
Dry 2h~4h, the carbon oxide fiber after being dried；
5., the carbon oxide fiber after 4. drying that step 3 obtains is placed in the Soxhlet extractor equipped with dehydrated alcohol,
Washes of absolute alcohol carbon oxide fiber is used under conditions of temperature is 90 DEG C~100 DEG C, scavenging period is 2h~4h, obtains nothing
The carbon fiber of the oxidation of water-ethanol cleaning；
6., the carbon fiber of the oxidation of washes of absolute alcohol that 5. obtains step 3 be 70 DEG C~80 DEG C in temperature condition
Lower dry 2h~4h, obtains dry carbon oxide fiber；
Four, it is grafted:
1., hydroxy-end capped dissaving polymer is added in n,N-dimethylacetamide, re-ultrasonic dispersion 15min~
Then dry carbon oxide fiber, 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 4- is added in 30min
Dimethylamino naphthyridine finally stirs under conditions of temperature is 100 DEG C~150 DEG C and mixing speed is 300r/min~400r/min
Reflux 12h~for 24 hours is mixed, the carbon fiber that obtains that treated；
Step 4 1. described in hydroxy-end capped dissaving polymer quality and DMAC N,N' dimethyl acetamide volume ratio
For (1g~1.5g): (30mL~60mL)；
Step 4 1. described in drying the quality of carbon oxide fiber and the volume ratio of DMAC N,N' dimethyl acetamide be
(1.0~2.0g): (30mL~60mL)；
Step 4 1. described in 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate quality and N, N-
The volume ratio of dimethyl acetamide is (0.5g~1.0g): (30mL~60mL)；
Step 4 1. described in 4-dimethylaminopyridine quality and DMAC N,N' dimethyl acetamide volume ratio be (0.05
~0.1g): (30mL~60mL)；
2., will treated carbon fiber take out after be immersed in 10min~15min in distilled water；
3., circulation step four 3. 3 times~5 times, obtain distilled water cleaning treated carbon fiber；
4., by distilled water cleaning, treated that carbon fiber is placed in the Soxhlet extractor equipped with dehydrated alcohol, in temperature
Washes of absolute alcohol distilled water clean that treated carbon fiber, scavenging period 2h is used under conditions of being 90 DEG C~100 DEG C
~4h obtains washes of absolute alcohol treated carbon fiber；
5., dry 3h in the baking oven that is 75 DEG C~80 DEG C by washes of absolute alcohol treated carbon fiber is placed in temperature~
5h obtains the carbon fiber of the hydroxy-end capped dissaving polymer of surface grafting.
The principle and advantage of present embodiment:
One, present embodiment has used nontoxic and high activity trishydroxymethylaminomethane (TOAM) as synthesis material,
Generated time largely is shortened, reduces environmental pollution；
Two, present embodiment uses covalence graft method, by hydroxy-end capped grafted by super branched polymer to carbon fiber surface, system
Contain a large amount of polar terminals hydroxyls for a kind of not only surface and is easy to be formed the carbon fiber of covalent bond with matrix；
Three, since hydroxy-end capped dissaving polymer has a large amount of polar hydroxyl groups and hole configurations, when being grafted to
After carbon fiber surface, wellability and caking property between carbon fiber and resin are significantly increased, this will substantially improve composite material
Interface performance, and then improve composite material mechanical property and thermal stability；
Four, the interface shear strength of the carbon fiber of the hydroxy-end capped dissaving polymer of surface grafting of present embodiment preparation
(IFSS) 60.9MPa~87.8MP is increased to by the 48.8MPa of precursor (non-grafted carbon fiber), improve 25%~
79.9%；Interlaminar shear strength (ILSS) by the 58.6MPa of precursor (non-grafted carbon fiber) be increased to 69.7MPa~
81.8MPa improves 19%~39.6%.
Present embodiment can get a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: step 1 1. described in it is different
The quality of isophorone diisocyanate and the volume ratio of DMAC N,N' dimethyl acetamide are (10g~12g): 50mL.Other steps with
Specific embodiment one is identical.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: step 1 2. in
The quality of the trishydroxymethylaminomethane and the volume ratio of DMAC N,N' dimethyl acetamide are (5g~6g): 50mL.Other steps
It is rapid the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: step 1 4. in
The quality of the dibutyl tin dilaurate and the volume ratio of reaction solution I are (0.1g~0.12g): 100mL.Other steps with
Specific embodiment one to three is identical.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: step 4 1. in
The quality of the hydroxy-end capped dissaving polymer and the volume ratio of DMAC N,N' dimethyl acetamide are (1.2g~1.5g):
(45mL~60mL).Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: step 1 2. in
The ultrasonic power is 343W~346.5W.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: step 4 1. in
The quality of the carbon oxide fiber of the drying and the volume ratio of DMAC N,N' dimethyl acetamide are (1.5~2.0g): (30mL~
60mL).Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: step 4 1. in
The quality of described 1- ethyl-(3- dimethylaminopropyl) the phosphinylidyne diimmonium salt hydrochlorate and the volume of DMAC N,N' dimethyl acetamide
Than for (0.5g~0.67g): (50mL~60mL).Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: step 4 1. in
The ultrasonic power is 343W~346.5W.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: step 4 1. in
The quality of the 4-dimethylaminopyridine and the volume ratio of DMAC N,N' dimethyl acetamide are (0.05~0.067g): (50mL~
60mL).Other steps are identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of method being grafted hydroxy-end capped dissaving polymer in carbon fiber surface is complete according to the following steps
At:
One, hydroxy-end capped dissaving polymer is prepared:
1., 12g isophorone diisocyanate and 50mL n,N-dimethylacetamide be added in three-necked flask, obtain
To isophorone diisocyanate solution；Glass container equipped with isophorone diisocyanate solution is placed in 0 DEG C of ice again
In water-bath；
2., 6g trishydroxymethylaminomethane is added in 50mL n,N-dimethylacetamide, then be in ultrasonic power
Ultrasonic mixing 20min under 346.5W, obtains tris solution；
3., by step 1 1. in be placed in 0 DEG C ice-water bath glass container in isophorone diisocyanate solution into
Row stirring, mixing speed 400r/min, then by step 1 2. obtained in tris solution with 15 drops/min
Rate of addition be added drop-wise in the isophorone diisocyanate solution that temperature is 0 DEG C, mixing speed is 400r/min, obtain anti-
Answer liquid I；
4., the temperature of reaction solution I is warming up to 5 DEG C, then 6h is stirred to react at being 5 DEG C in temperature, then by the temperature of reaction solution I
Degree is warming up to 40 DEG C, then 0.1g dibutyl tin dilaurate is added into 40 DEG C of reaction solutions I, is finally 40 DEG C and stirring in temperature
Speed is to be stirred to react 15h under 400r/min, obtains reaction solution II；
5., by step 1 4. obtained in reaction solution II be added to be precipitated in 500mL deionized water and precipitate, then stand
30min, then be centrifuged in the case where centrifugal speed is 8000r/min, obtain solid reaction product；
6., using deionized water solid reaction product is cleaned 5 times, then the solid reaction product after deionized water is cleaned
It is put into freeze drier, then is freeze-dried 48h at being -10 DEG C in temperature, obtain dry white solid matter, as hydroxyl
Terminated hyperbranched polymer；
Two, the extracting processing of carbon fiber:
1., carbon fiber is put into the Soxhlet extractor equipped with acetone, then acetone is heated to 82 DEG C, acetone constantly steams
And condensed in Soxhlet extractor, so that the impurity of carbon fiber surface is continuously available cleaning in the acetone of distillation, scavenging period is
72h, then carbon fiber is taken out, obtain the carbon fiber of removal surface impurity；The carbon fiber for removing surface impurity is taken out, then is placed in
Temperature is dry 4h in 70 DEG C of baking oven, obtains extracting treated carbon fiber；
Three, it aoxidizes:
1., will extracting treated that carbon fiber is immersed in potassium peroxydisulfate/silver nitrate mixed aqueous solution, be heated to 70 DEG C,
Constant temperature 1h under conditions of temperature is 70 DEG C again, the carbon fiber after being aoxidized；The potassium peroxydisulfate/silver nitrate mixing is water-soluble
The concentration of potassium peroxydisulfate is 0.1mol/L in liquid；The concentration of silver nitrate is in the potassium peroxydisulfate/silver nitrate mixed aqueous solution
0.01mol/L；
Step 3 1. described in extracting treated carbon fiber quality and potassium peroxydisulfate/silver nitrate mixed aqueous solution
Volume ratio is 1.5g:500mL；
2., the carbon fiber after 1. oxidation that step 3 obtains impregnated into 10min in distilled water under room temperature, will be through steaming
Carbon fiber after impregnating in distilled water takes out, reject distilled water；
Step 3 2. described in oxidation after carbon fiber quality and distilled water volume ratio be 1.5g:500mL；
3., repeat step 3 2. 5 times, obtain distilled water cleaning after carbon oxide fiber；
4., the carbon oxide fiber after the distilled water cleaning that 3. obtains step 3 it is dry under conditions of temperature is 70 DEG C
4h, the carbon oxide fiber after being dried；
5., the carbon oxide fiber after 4. drying that step 3 obtains is placed in the Soxhlet extractor equipped with dehydrated alcohol,
Washes of absolute alcohol carbon oxide fiber is used under the conditions of at a temperature of 90 °C, scavenging period 2h obtains washes of absolute alcohol
Oxidation carbon fiber；
6., the carbon fiber of the oxidation of washes of absolute alcohol that 5. obtains step 3 it is dry under conditions of temperature is 70 DEG C
4h obtains dry carbon oxide fiber；
Four, it is grafted:
1., the hydroxy-end capped dissaving polymer of 1.5g is added in 60mL n,N-dimethylacetamide, then in ultrasonic function
Rate is ultrasound 30min under 346.5W, and the dry carbon oxide fiber of 1.5g, 0.67g 1- ethyl-(3- dimethylamino is then added
Propyl) phosphinylidyne diimmonium salt hydrochlorate and 0.067g 4-dimethylaminopyridine are finally 100 DEG C in temperature and mixing speed is
It is stirred at reflux under conditions of 400r/min for 24 hours, the carbon fiber that obtains that treated；
2., will treated carbon fiber take out after be immersed in 15min in distilled water；
3., circulation step four 3. 5 times, obtain distilled water cleaning treated carbon fiber；
4., by distilled water cleaning, treated that carbon fiber is placed in the Soxhlet extractor equipped with dehydrated alcohol, in temperature
Using the washes of absolute alcohol distilled water carbon fiber that cleans that treated under conditions of being 90 DEG C, scavenging period 2h obtains nothing
Water-ethanol cleaning treated carbon fiber；
5., dry 4h in the baking oven that is 80 DEG C by washes of absolute alcohol treated carbon fiber is placed in temperature, obtain table
Face is grafted the carbon fiber of hydroxy-end capped dissaving polymer, is expressed as CF-HTHBP.
Fig. 1 is the XPS spectrum figure of 3. extracting treated carbon fiber that one step 2 of embodiment obtains；
Fig. 2 is the swarming spectrogram of Fig. 1, and 1 is C1s (1) in figure, and 2 be C1s (2), and 3 be C1s (3)；
Fig. 3 is the XPS of the carbon fiber of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains
Spectrogram；
Fig. 4 is the swarming spectrogram of Fig. 3, and 4 be C-N in figure, and 5 be C-O, and 6 be C=O, and 7 be NCOO；
Table 1 is constituent content variation before and after carbon fiber modifying.Carbon fiber surface is grafted hydroxy-end capped dissaving polymer
(HTHBP) after, O content is dramatically increased, and is increased to 20.19% by untreated 3.32%.It can from the swarming figure of CF-HTHBP
It can be NCOO new peak occur at 289eV in combination, these are the result shows that hydroxy-end capped dissaving polymer to find out
(HTHBP) to carbon fiber surface, i.e. the carboxyl in hydroxyl and carbon oxide fiber in HTHBP reacts generation covalence graft
Ester bond, the relative amount of the key are 4.67%.
Table 1
Note: CF is the extracting that 3. obtains of one step 2 of embodiment treated carbon fiber, and CF-HTHBP is one step of embodiment
The carbon fiber of the rapid four hydroxy-end capped dissaving polymers of surface grafting 5. obtained.
Fig. 5 is the SEM figure of 3. extracting treated carbon fiber that one step 2 of embodiment obtains；
Fig. 6 is the SEM of the carbon fiber of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains
Figure；
Can be seen that non-grafted carbon fiber from Fig. 5~Fig. 6, (treated for 3. extracting that one step 2 of embodiment obtains
Carbon fiber) surface is relatively smooth.And the carbon of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains
The surface fiber (CF-HTHBP) forms one layer of covering, this is because hydroxy-end capped dissaving polymer (HTHBP) is uniform
For covalence graft in carbon fiber surface, this will improve fiber surface roughness and specific surface area, be conducive to increased fiber and resin it
Between mechanical interlock and physical entanglement density, to form the bigger interface cohesion of adhesion strength.
Table 2 is 5. the extracting that 3. obtains of one step 2 of embodiment treated carbon fiber (CF) and one step 4 of embodiment must
The variation of the contact angle of the carbon fiber (CF-HTHBP) of the hydroxy-end capped dissaving polymer of the surface grafting arrived and surface energy, by table
2 it can be concluded that, carbon fiber be grafted HTHBP after, contact angle in water and diiodomethane all significantly reduces, polar component,
Dispersive component and surface can be correspondingly improved, and surface can be increased to 61.19mN/m by 29.97mN/m and improve 104.2%.
This illustrates that HTHBP is grafted to carbon fiber surface and fiber surface polar group and roughness is made to have raising by a relatively large margin, thus carbon
The wetability of fiber surface and resin improves significantly.
Table 2
Interface shear strength tests (one):
(1) this experiment uses FA620 type composite material interface evaluating apparatus (Japanese Dong Rong Co., Ltd.).First by carbon
Fibre single thread is pasted on metallic support securely with double-sided adhesive, then weighs epoxy resin E-51 and consolidate that mass ratio is 100:32
Agent H-256 is simultaneously uniformly mixed, and dips a dropping point on carbon mono-filaments surface with steel needle, and epoxy resin can be made because of surface tension
With resin droplet is formed, then constant temperature keeps 2h, 2h and 3h to be solidified respectively at 90 DEG C, 120 DEG C and 150 DEG C, to make
Obtain carbon fiber/epoxy resin droplet composite material.During the test, 80 μm of diameter or so of resin droplet is chosen as test
Object, resin bulb diameter too greatly be easy by break of CFRP and resin balls not with fiber be detached from, if resin balls are too small, the equipment edge of a knife
It can't clip, the effect edge of a knife that test process does not test power is just slipped over from resin balls, and load loading velocity is 0.5 μm of s-1,
Every group of sample measures 50 valid data and calculates its average value, and the carbon fiber is 3. pumping that one step 2 of embodiment obtains
The carbon fiber (CF) that mentions that treated.Interface shear strength (IFSS) can be obtained according to formula (1):
F in formulamax--- the load peaks (N) when fiber pull-out；
D --- fiber filament diameter (m)；
L --- epoxy resin droplet embeds length (m).
The interface shearing of the extracting according to the method described above 3. one step 2 of embodiment obtained treated carbon fiber (CF)
Intensity is tested；
Interface shear strength test (two): the difference of this test and interface shear strength test (one) is: the carbon
Fiber is the carbon fiber (CF-HTHBP) of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains.Its
His step and test method are identical as interface shear strength test (one).
Test results are shown in figure 7 for interface shear strength test (one) and interface shear strength test (two)；
Fig. 7 is interface shear strength histogram, 1 extracting 3. obtained for one step 2 of embodiment treated carbon fiber in figure
The interface shear strength of dimension, the carbon fiber of the 2 hydroxy-end capped dissaving polymers of surface grafting 5. obtained for one step 4 of embodiment
The interface shear strength of dimension；
From figure 7 it can be seen that the interface shear strength (IFSS) after carbon fiber grafting HTHBP is mentioned by the 48.8MPa of precursor
Height arrives 87.8MPa, improves 79.9%.
Interlaminar shear strength tests (one):
(1) this experiment uses three-point bending method test carbon on electronic universal tester GT-7000-A2X (TaiWan, China)
The ILSS of fibrous composite.The carbon fiber of 20 circle of winding first on the frame of 20cm long, then weighing mass ratio is 100:32
Epoxy resin E-51 and curing agent H-256 and be uniformly mixed, so that matrix resin is sufficiently infiltrated carbon fiber, then set
In mold, mold is put into vacuum oven and carries out froth in vacuum, then mold is put on hot press by following technique
Solidification, constant temperature keeps 2h, 2h and 3h to be solidified respectively at 90 DEG C, 120 DEG C and 150 DEG C, so that carbon fiber/asphalt mixtures modified by epoxy resin be made
Resin composite material.During the test, specimen size is 20mm × 6mm × 2mm, and sample span and thickness ratio are 5, load load
Speed is 2mmmin-1, test and carry out at room temperature, every group of sample measures 50 valid data and calculate its average value, described
Carbon fiber be the extracting that 3. obtains of one step 2 of embodiment treated carbon fiber (CF).Interlaminar shear strength (ILSS) can root
It is obtained according to formula (2):
F in formula --- maximum load (N) when tomography；
B --- sample cross width (mm)；
H --- sample cross thickness (mm).
The interlayer shear of the extracting according to the method described above 3. one step 2 of embodiment obtained treated carbon fiber (CF)
Intensity is tested；
Interlaminar shear strength test (two): the difference of this test and interlaminar shear strength test (one) is: the carbon
Fiber is the carbon fiber (CF-HTHBP) of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains.Its
His step and test method are identical as interlaminar shear strength test (one).
Test results are shown in figure 8 for interlaminar shear strength test (one) and interlaminar shear strength test (two)；
Fig. 8 is interlaminar shear strength histogram, 1 extracting 3. obtained for one step 2 of embodiment treated carbon fiber in figure
The interlaminar shear strength of dimension, the carbon fiber of the 2 hydroxy-end capped dissaving polymers of surface grafting 5. obtained for one step 4 of embodiment
The interlaminar shear strength of dimension.
From figure 8, it is seen that 58.6MPa of the carbon fiber grafting HTHBP later interlaminar shear strength (ILSS) by precursor
It is increased to 81.8MPa, improves 39.6%.
The interface shearing of the carbon fiber of the 5. hydroxy-end capped dissaving polymer of surface grafting that one step 4 of embodiment obtains
Intensity and interlaminar shear strength improve very much, this is because carbon fiber surface contains a large amount of polar hydroxyl groups after being grafted HTHBP,
Chemical reaction can be participated in resin group.At the same time, fiber and resin can be enhanced in the increase of carbon fiber surface surface roughness
Mechanical interlock and physical entanglement density, so that carbon fibre reinforced composite be made to have better interface cohesion, this will be helped
In the raising of the interface performance of final composite material.
Embodiment two: a kind of method being grafted hydroxy-end capped dissaving polymer in carbon fiber surface is complete according to the following steps
At:
One, hydroxy-end capped dissaving polymer is prepared:
1., 6g isophorone diisocyanate and 50mL n,N-dimethylacetamide be added in three-necked flask, obtain
Isophorone diisocyanate solution；Glass container equipped with isophorone diisocyanate solution is placed in 5 DEG C of ice water again
In bath；
2., 3g trishydroxymethylaminomethane is added in 50mL n,N-dimethylacetamide, then be in ultrasonic power
Ultrasonic mixing 10min under 343W, obtains tris solution；
3., by step 1 1. in be placed in 5 DEG C ice-water bath glass container in isophorone diisocyanate solution into
Row stirring, mixing speed 300r/min, then by step 1 2. obtained in tris solution with 15 drops/min
Rate of addition be added drop-wise in the isophorone diisocyanate solution that temperature is 5 DEG C, mixing speed is 300r/min, obtain anti-
Answer liquid I；
4., the temperature of reaction solution I is warming up to 10 DEG C, then 5h is stirred to react at being 10 DEG C in temperature, then by reaction solution I
Temperature is warming up to 35 DEG C, then 0.1g dibutyl tin dilaurate is added into 35 DEG C of reaction solutions I, finally for 35 DEG C and stirs in temperature
Mixing speed is to be stirred to react 10h under 300r/min, obtains reaction solution II；
5., by step 1 4. obtained in reaction solution II be added to be precipitated in 500mL deionized water and precipitate, then stand
25min, then be centrifuged in the case where centrifugal speed is 7000r/min, obtain solid reaction product；
6., using deionized water solid reaction product is cleaned 5 times, then the solid reaction product after deionized water is cleaned
It is put into freeze drier, then is freeze-dried 36h at being -10 DEG C in temperature, obtain dry white solid matter, as hydroxyl
Terminated hyperbranched polymer；
Two, the extracting processing of carbon fiber:
1., carbon fiber is put into the Soxhlet extractor equipped with acetone, then acetone is heated to 82 DEG C, acetone constantly steams
And condensed in Soxhlet extractor, so that the impurity of carbon fiber surface is continuously available cleaning in the acetone of distillation, scavenging period is
48h, then carbon fiber is taken out, obtain the carbon fiber of removal surface impurity；The carbon fiber for removing surface impurity is taken out, then is placed in
Temperature is dry 2h in 80 DEG C of baking oven, obtains extracting treated carbon fiber；
Three, it aoxidizes:
1., will extracting treated that carbon fiber is immersed in potassium peroxydisulfate/silver nitrate mixed aqueous solution, be heated to 60 DEG C,
Constant temperature 2h under conditions of temperature is 60 DEG C again, the carbon fiber after being aoxidized；The potassium peroxydisulfate/silver nitrate mixing is water-soluble
The concentration of potassium peroxydisulfate is 0.2mol/L in liquid；The concentration of silver nitrate is in the potassium peroxydisulfate/silver nitrate mixed aqueous solution
0.005mol/L；
Step 3 1. described in extracting treated carbon fiber quality and potassium peroxydisulfate/silver nitrate mixed aqueous solution
Volume ratio is 1.5g:300mL；
2., the carbon fiber after 1. oxidation that step 3 obtains impregnated into 5min in distilled water under room temperature, will be through steaming
Carbon fiber after impregnating in distilled water takes out, reject distilled water；
Step 3 2. described in oxidation after carbon fiber quality and distilled water volume ratio be 1.5g:500mL；
3., repeat step 3 2. 3 times, obtain distilled water cleaning after carbon oxide fiber；
4., the carbon oxide fiber after the distilled water cleaning that 3. obtains step 3 it is dry under conditions of temperature is 80 DEG C
2h, the carbon oxide fiber after being dried；
5., the carbon oxide fiber after 4. drying that step 3 obtains is placed in the Soxhlet extractor equipped with dehydrated alcohol,
Washes of absolute alcohol carbon oxide fiber is used under the conditions of at a temperature of 90 °C, scavenging period 2h obtains washes of absolute alcohol
Oxidation carbon fiber；
6., the carbon fiber of the oxidation of washes of absolute alcohol that 5. obtains step 3 it is dry under conditions of temperature is 80 DEG C
2h obtains dry carbon oxide fiber；
Four, it is grafted:
1., the hydroxy-end capped dissaving polymer of 1g is added in 30mL n,N-dimethylacetamide, then in ultrasonic power
For ultrasound 30min under 343W, the dry carbon oxide fiber of 1.5g, 0.5g 1- ethyl-(3- dimethylaminopropyl) is then added
Phosphinylidyne diimmonium salt hydrochlorate and 0.05g 4-dimethylaminopyridine, are finally 150 DEG C in temperature and mixing speed is 400r/min
Under conditions of be stirred at reflux 12h, the carbon fiber that obtains that treated；
2., will treated carbon fiber take out after be immersed in 10min in distilled water；
3., circulation step four 3. 4 times, obtain distilled water cleaning treated carbon fiber；
4., by distilled water cleaning, treated that carbon fiber is placed in the Soxhlet extractor equipped with dehydrated alcohol, in temperature
Using the washes of absolute alcohol distilled water carbon fiber that cleans that treated under conditions of being 90 DEG C, scavenging period 2h obtains nothing
Water-ethanol cleaning treated carbon fiber；
5., dry 4h in the baking oven that is 80 DEG C by washes of absolute alcohol treated carbon fiber is placed in temperature, obtain table
Face is grafted the carbon fiber of hydroxy-end capped dissaving polymer, is expressed as CF-HTHBP.
The experimental result of embodiment two is as follows:
Element variation before and after carbon fiber modifying: CF-HTHBP is compared with CF, and surface is increased to containing oxygen element
14.36%, become 0.18 from the ratio between original oxygen element/carbon 0.034.
Microscopic appearance variation before and after carbon fiber modifying: fiber oxidation rear surface defect is more, causes to fiber bodies intensity
Damage.
Contact angle and surface energy before and after carbon fiber modifying: contact angle in water and diiodomethane is larger, so as to cause
The wetability of carbon fiber and resin is poor.
Carbon fiber interface shear strength and interlaminar shear strength analysis: interface shear strength (IFSS) is by precursor
48.8MPa is increased to 60.9MPa, improves 25%.Interlaminar shear strength (ILSS) is increased to by the 58.6MPa of precursor
69.7MPa improves 19%.
By analyzing it is found that more preferable using the effect of embodiment one.
Claims (10)
1. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface, it is characterised in that one kind is in carbon fiber surface
The method that face is grafted hydroxy-end capped dissaving polymer is completed by the following steps:
One, hydroxy-end capped dissaving polymer is prepared:
1., isophorone diisocyanate and n,N-dimethylacetamide be added in glass container, obtain isophorone two
Isocyanate solution；The glass container equipped with isophorone diisocyanate solution is placed in 0 DEG C~5 DEG C of ice-water bath again；
Step 1 1. described in isophorone diisocyanate quality and DMAC N,N' dimethyl acetamide volume ratio be (6g~
12g):50mL；
2., trishydroxymethylaminomethane is added in n,N-dimethylacetamide, then ultrasonic mixing 10min~20min is obtained
Tris solution；
Step 1 2. described in trishydroxymethylaminomethane quality and DMAC N,N' dimethyl acetamide volume ratio be (3g~
6g):50mL；
3., by step 1 1. in be placed in 0 DEG C~5 DEG C ice-water bath glass container in isophorone diisocyanate solution into
Row stirring, mixing speed be 300r/min~400r/min, then by tris solution with 10 drops/min~15 drop/
It is different that the rate of addition of min is added drop-wise to the isophorone two that temperature is 0 DEG C~5 DEG C, mixing speed is 300r/min~400r/min
In cyanic acid ester solution, reaction solution I is obtained；
Step 1 3. described in isophorone diisocyanate solution and tris solution volume ratio be 1:
1；
4., the temperature of reaction solution I is warming up to 5 DEG C~10 DEG C, then be stirred to react 5h~6h at being 5 DEG C~10 DEG C in temperature, then
The temperature of reaction solution I is warming up to 35 DEG C~40 DEG C, then dibutyl tin dilaurate is added into 35 DEG C~40 DEG C reaction solutions I,
It finally is stirred to react 10h~15h in the case where temperature is 35 DEG C~40 DEG C and mixing speed is 300r/min~400r/min, is obtained anti-
Answer liquid II；
Step 1 4. described in dibutyl tin dilaurate quality and reaction solution I volume ratio be (0.08g~0.12g):
100mL；
5., reaction solution II is add to deionized water to precipitation precipitating, then stand 25min~30min, then be in centrifugal speed
It is centrifuged under 6000r/min~8000r/min, obtains solid reaction product；
6., using deionized water solid reaction product is cleaned 3 times~5 times, then the solid reaction after deionized water is cleaned produces
Object is put into freeze drier, then is freeze-dried 36h~48h at being -10 DEG C~-5 DEG C in temperature, obtains dry white solid
Substance, as hydroxy-end capped dissaving polymer；
Two, the extracting processing of carbon fiber:
1., carbon fiber is put into the Soxhlet extractor equipped with acetone, then acetone is heated to 75 DEG C~85 DEG C, acetone constantly steams
It condenses out and in Soxhlet extractor, the impurity of carbon fiber surface is made to be continuously available cleaning, scavenging period in the acetone of distillation
For 48h~72h, then carbon fiber taken out, obtains the carbon fiber of removal surface impurity；The carbon fiber for removing surface impurity is taken
Out, then to be placed in temperature be dry 2h~4h in 70 DEG C~80 DEG C of baking oven, obtains extracting treated carbon fiber；
Three, it aoxidizes:
1., will extracting treated that carbon fiber is immersed in potassium peroxydisulfate/silver nitrate mixed aqueous solution, be heated to 60 DEG C~80
DEG C, then constant temperature 1h~2h under conditions of temperature is 60 DEG C~80 DEG C, the carbon fiber after being aoxidized；The potassium peroxydisulfate/
The concentration of potassium peroxydisulfate is 0.1mol/L~0.2mol/L in silver nitrate mixed aqueous solution；Potassium peroxydisulfate/the silver nitrate is mixed
The concentration of silver nitrate is 0.0001mol/L~0.05mol/L in Heshui solution；
Step 3 1. described in extracting treated carbon fiber quality and potassium peroxydisulfate/silver nitrate mixed aqueous solution volume
Than for (0.3g~1.5g): (300mL~500mL)；
2., the carbon fiber after the oxidation that under room temperature 1. obtains step 3 5min~10min is impregnated in distilled water, will be through
Carbon fiber after impregnating in distilled water takes out, reject distilled water；
Step 3 2. described in oxidation after carbon fiber quality and distilled water volume ratio be (0.3g~1.5g): (300mL
~500mL)；
3., repeat step 3 2. 3 times~5 times, obtain distilled water cleaning after carbon oxide fiber；
4., the carbon oxide fiber after the distilled water cleaning that 3. obtains step 3 it is dry under conditions of temperature is 70 DEG C~80 DEG C
2h~4h, the carbon oxide fiber after being dried；
5., the carbon oxide fiber after 4. drying that step 3 obtains is placed in the Soxhlet extractor equipped with dehydrated alcohol, in temperature
Degree uses washes of absolute alcohol carbon oxide fiber under conditions of being 90 DEG C~100 DEG C, scavenging period is 2h~4h, obtains anhydrous second
The carbon fiber of the oxidation of alcohol cleaning；
6., the carbon fiber of the oxidation of washes of absolute alcohol that 5. obtains step 3 it is dry under conditions of temperature is 70 DEG C~80 DEG C
Dry 2h~4h obtains dry carbon oxide fiber；
Four, it is grafted:
1., hydroxy-end capped dissaving polymer is added in n,N-dimethylacetamide, re-ultrasonic dispersion 15min~30min,
Then dry carbon oxide fiber, 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and 4- diformazan ammonia is added
Yl pyridines are finally stirred at reflux under conditions of temperature is 100 DEG C~150 DEG C and mixing speed is 300r/min~400r/min
12h~for 24 hours, the carbon fiber that obtains that treated；
Step 4 1. described in hydroxy-end capped dissaving polymer quality and DMAC N,N' dimethyl acetamide volume ratio be (1g
~1.5g): (30mL~60mL)；
Step 4 1. described in drying carbon oxide fiber quality and DMAC N,N' dimethyl acetamide volume ratio be (1.0~
2.0g): (30mL~60mL)；
Step 4 1. described in 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate quality and N, N- diformazan
The volume ratio of yl acetamide is (0.5g~1.0g): (30mL~60mL)；
Step 4 1. described in 4-dimethylaminopyridine quality and DMAC N,N' dimethyl acetamide volume ratio be (0.05~
0.1g): (30mL~60mL)；
2., will treated carbon fiber take out after be immersed in 10min~15min in distilled water；
3., circulation step four 3. 3 times~5 times, obtain distilled water cleaning treated carbon fiber；
4., by distilled water cleaning, treated that carbon fiber is placed in the Soxhlet extractor equipped with dehydrated alcohol, be 90 in temperature
DEG C~100 DEG C under conditions of using the washes of absolute alcohol distilled water carbon fiber that cleans that treated, scavenging period is 2h~4h,
Obtain washes of absolute alcohol treated carbon fiber；
5., dry 3h~5h in the baking oven that is 75 DEG C~80 DEG C by washes of absolute alcohol treated carbon fiber is placed in temperature,
Obtain the carbon fiber of the hydroxy-end capped dissaving polymer of surface grafting.
2. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Levying the quality of isophorone diisocyanate and the volume ratio of DMAC N,N' dimethyl acetamide described in being step 1 1. is
(10g~12g): 50mL.
3. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Sign be step 1 2. described in trishydroxymethylaminomethane quality and DMAC N,N' dimethyl acetamide volume ratio be (5g~
6g):50mL。
4. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
The volume ratio of the quality and reaction solution I of levying the dibutyl tin dilaurate described in being step 1 4. is (0.1g~0.12g):
100mL。
5. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Levying the quality of hydroxy-end capped dissaving polymer and the volume ratio of DMAC N,N' dimethyl acetamide described in being step 4 1. is
(1.2g~1.5g): (45mL~60mL).
6. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Levying the ultrasonic power described in being step 1 2. is 343W~346.5W.
7. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
The volume ratio of the quality and DMAC N,N' dimethyl acetamide of levying the carbon oxide fiber of the drying described in being step 4 1. is (1.5
~2.0g): (30mL~60mL).
8. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Levy the quality and N of 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate described in being step 4 1., N- bis-
The volume ratio of methylacetamide is (0.5g~0.67g): (50mL~60mL).
9. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Levying the ultrasonic power described in being step 4 1. is 343W~346.5W.
10. a kind of method for being grafted hydroxy-end capped dissaving polymer in carbon fiber surface according to claim 1, special
Sign be step 4 1. described in 4-dimethylaminopyridine quality and DMAC N,N' dimethyl acetamide volume ratio be (0.05~
0.067g): (50mL~60mL).
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| CN110435185A (en) * | 2019-08-20 | 2019-11-12 | 大同新成新材料股份有限公司 | A kind of fibre reinforced thermoplastic resin based composite material preparation method and preparation facilities |
| CN113388230A (en) * | 2021-06-30 | 2021-09-14 | 南京晓庄学院 | Glass fiber reinforced plastic composite material 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 |
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