CN110128634A - A kind of preparation method of graphene Modified polyester chips - Google Patents
A kind of preparation method of graphene Modified polyester chips Download PDFInfo
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- CN110128634A CN110128634A CN201910358358.4A CN201910358358A CN110128634A CN 110128634 A CN110128634 A CN 110128634A CN 201910358358 A CN201910358358 A CN 201910358358A CN 110128634 A CN110128634 A CN 110128634A
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- graphene
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- polyester chips
- modified polyester
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
Abstract
The present invention relates to synthetic fiber modified fields, and in particular to a kind of preparation method of graphene Modified polyester chips.The present invention is modified Hummers method graphene oxide using α-alkenyl silanes coupling agent, again with 3- sulfydryl -1,2- propylene glycol carries out the modified graphene oxide that sulfydryl-alkene clicking chemistry reaction preparation surface modification has polyhydroxy, and the modified graphene of surface modification polyhydroxy is obtained after reduction；Modified graphene is added to progress polycondensation reaction in p-phthalic acid and ethylene glycol and obtains graphene Modified polyester chips.Modified polyester chips of the invention have preferable electric conductivity by the fabric that the fiber that spinning obtains is worked out, and improve the antistatic effect of fabric, and antistatic effect is lasting.
Description
Technical field
The present invention relates to synthetic fiber modified fields, and in particular to a kind of preparation method of graphene Modified polyester chips.
Background technique
Polyester fiber (polyester fibre), is commonly called as " terylene ", abbreviation PET fiber, it is by organic dibasic acid and two
Polyester made of first alcohol polycondensation is through the resulting synthetic fibers of spinning.Polyester fiber biggest advantage be wrinkle resistance and conformality very
It is good, intensity with higher and elastic recovery capability, strong durable, wash and wear, not adhesive hair.
With the continuous development of science and technology and continuous improvement of people's living standards, people are more next to the functionality of clothes
More pay attention to.Clothes be no longer only have the function of hushing up a scandal, cold-proof, the functional textiles such as antibacterial, health care, UV resistance, antistatic
Increasingly receive an acclaim.
Graphene is a kind of Two-dimensional Carbon nanometer material for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom
Material, was found in 2004.Graphene has excellent optics, electricity, mechanical characteristic, in new energy, material, biomedical tool
There is important application prospect.
Nanoscale graphene is introduced into polymer fiber matrix, graphene/fibrous composite can be developed, it can
To improve the performances such as the intensity of fiber, heat resistance, weatherability, antistatic, the application field of fiber is improved.
Graphene can with the cellulose fibres such as pure cotton, viscose glue, terylene, polyamide fibre, acrylic fibers, spandex, aramid fiber, polyvinyl alcohol,
The synthetic fibers such as sodium alginate, polypropylene prepare composite fibre.Complex method include direct padding method, spray coating method, compositional liquor method,
Finishing method and cross-linking modified method etc..
The Chinese invention of publication number CN106350894A, which is applied for a patent, discloses a kind of graphene polyester monofilament, by graphite
Alkene, the pasty slurry of modified compatilizer and silane coupling agent KH-560 composition and polyester slice are obtained using double-screw melt blending
Graphene functional agglomerate, graphene functional agglomerate are prepared with terylene chips melt-spinning again.
The Chinese invention of publication number CN107119342A, which is applied for a patent, discloses a kind of superelevation conductive graphene polyester fiber,
Silicic acid gel burden graphene particles are first prepared, then are prepared with polyester slice melt blending extrusion.
But above method is all the graphene that will be modified and polyester slice by melt blending, belongs to physical blending
One kind, there are problems that graphene is reunited in polyester slice, reunite on the one hand be cannot complete body the effect of making graphene
Existing, the position that another aspect graphene is reunited is the mechanical property weak spot of polyester fiber, be easy to cause polyester fiber in external force
The lower fracture of effect.
Therefore, the reunion of graphene in the polyester how is reduced, improving dispersibility of the graphene in polyester fiber is to fill
The key factor of graphite olefinic functionality is waved in distribution.
Summary of the invention
(1) the technical issues of solving used
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparation sides of graphene Modified polyester chips
Method fundamentally solves the problems, such as the preparation of the polyester slice containing graphene.
(2) technical solution
To achieve the goals above, the present invention uses following scheme:
A kind of preparation method of graphene Modified polyester chips, includes the following steps,
S1: being added p-phthalic acid, polyhydroxy modified graphene and ethylene glycol in a reservoir, at 250~275 DEG C into
Row esterification, reaction process persistently remove the water of generation, reaction to esterification yield at least 92%, and cooling obtains esterification intermediate；
S2: by the esterification intermediate in step S1, in catalyst, the negative pressure of < 6000Pa, at 265~280 DEG C into
Row polycondensation reaction 1~1.5 hour, then negative pressure is adjusted to 80Pa is lower than, it is reacted 2~4 hours at 270~285 DEG C, cooling, casting
Band, cooling, pelletizing, obtain graphene Modified polyester chips.
Preferably, the mass ratio of p-phthalic acid described in step S1, polyhydroxy modified graphene and ethylene glycol are
100:0.3~2:100~120.
Preferably, the preparation method of polyhydroxy modified graphene described in step S1, includes the following steps,
S3: dehydrated alcohol and Hummers graphene oxide are added in a reservoir, ultrasonic disperse 30 minutes, α-alkenyl is added
Silane coupling agent is warming up to the micro- reflux of reaction system under stirring, continue to be stirred to react 0.5~2 hour, filter while hot, filters out solid
Body three times, is put into 60~80 DEG C of vacuum ovens and is dried to constant weight, obtain the modified oxidized stone of α-alkenyl with washes of absolute alcohol
Black alkene；
S4: α-alkenyl modified graphene oxide, ethyl acetate, 3- sulfydryl -1,2- propylene glycol and styrax in step S3
Double methyl ether anabolic reaction systems, under stirring, at dominant wavelength 365nm, the ultraviolet light of 20~180W/cm of luminous intensity irradiate 3~
90min removes ultraviolet light, is warming up to the micro- reflux of system, and reducing agent is added, and reacts 3~5 hours, filters while hot, filters out solid use
Washes of absolute alcohol three times, is put into 60~80 DEG C of vacuum ovens and dries to constant weight, obtain polyhydroxy modified graphene.
It is furthermore preferred that α described in step S3-alkenyl silanes coupling agent is selected from 1- cyclobutenyl trimethoxy silane, 1- butylene
Ethyl triethoxy silicane alkane, allyltrimethoxysilanis, allyl methyl dimethoxysilane, allyltriethoxysilane,
Allyl methyl diethoxy silane, vinyltrimethoxysilane, vinyl methyl dimethoxysilane, three ethoxy of vinyl
Base silane, vinyl methyl diethoxy silane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl
Base hydroxypropyl methyl dimethoxysilane, 3- methacryloxypropyl, 3- methacryloxypropyl
Methyldiethoxysilane, 3- acryloyloxypropyltrimethoxysilane, 3- acryloxypropyl dimethoxy silicon
One of alkane, 3- acryloxypropyl triethoxysilane and 3- acryloyloxy propyl methyl diethoxysilane are several
Kind.
It is furthermore preferred that dehydrated alcohol, Hummers oxidizing process graphene and α-alkenyl silanes coupling agent quality in step S3
Than for 100~1000:1:0.2~1.
It is furthermore preferred that α described in step S4-alkenyl modified graphene oxide, ethyl acetate, 3- sulfydryl-1,2-PD
Mass ratio with benzoin dimethylether is 1:100~1000:0.2~0.5:0.02~0.03.
It is furthermore preferred that reducing agent described in step S4 be selected from hydrazine hydrate, sodium borohydride, vitamin C, Dimethylhydrazine, to benzene two
One or more of phenol and phenylhydrazine are 1~3 times of α-alkenyl modified graphene oxide weight in step S4 using weight.
Preferably, the catalyst is antimony trioxide, and the usage amount of antimony trioxide is the reason for the polyester that polycondensation reaction obtains
By 300~400ppm of yield.
The graphite that a kind of preparation method of graphene Modified polyester chips described in any of the above-described embodiment is prepared
Alkene Modified polyester chips.
The modification that a kind of preparation method of graphene Modified polyester chips described in any of the above-described embodiment is prepared
Polyester slice is used to prepare polyester fiber and polyester complex fiber.
The present invention makes graphene oxide table using α-alkenyl silanes coupling agent treatment Hummers method graphene oxide is first used
Face chemical modification α-alkenyl-functional groups, α-alkenyl-functional groups are under ultraviolet light and sulfydryl-occurs for 3- sulfydryl -1,2-PD
Alkene clicking chemistry reaction, obtain the graphene oxide that surface modification has polyhydroxy functional groups, obtained after reduction surface modification have it is more
The graphene of hydroxy functional group.Organo-functional group and terephthalic acid (TPA) of the graphene due to surface with polyhydroxy after modification
And the compatibility of ethylene glycol is preferable, is easier in the reaction raw materials for being dispersed in terephthalic acid (TPA) and ethylene glycol composition, and
The hydroxyl of graphene surface participates in the esterification of terephthalic acid (TPA) and ethylene glycol, with the progress of esterification, reaction system
Concentration it is higher and higher, but graphene has gradually been grafted on the side chain of polyester macromolecule chain, therefore graphene is cut in polyester
Dispersibility in piece is preferably.
(3) beneficial effect
Compared to the prior art, the invention has the benefit that (1) graphene is scattered in polyester slice；(2) graphite
Alkene is grafted on polyester macromolecule chain by chemical bond, so that graphene is washable in the fiber made of Modified polyester chips
Property is good, and effect is lasting；(3) Modified polyester chips obtained both can individually carry out spinning, can also carry out with other polymers
Co-spun yarn；(4) fabric that the fiber that spinning obtains is prepared has preferable antistatic property.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, by embodiment to the present invention carry out into
One step elaborates, but is not intended to limit the present invention.
If not specified, the number in embodiment below is all parts by weight.
Prepare polyhydroxy modified graphene
150 parts of dehydrated alcohols and 1 part of Hummers are added in the container with stirring rod, thermometer and reflux condensing tube
Ultrasonic disperse 30 minutes, 0.2 part of vinyltrimethoxysilane was added in graphene oxide, and it is micro- to be warming up to reaction system under stirring
Reflux, continues to be stirred to react 2 hours, filters while hot, filter out solid washes of absolute alcohol three times, be put into 60 DEG C of vacuum ovens
Middle drying obtains vinyl modified graphene oxide to constant weight.FT-IR analysis, product is in 1409cm-1And 1613cm-1It is each to exist
One sharp strong absworption peak is the characteristic absorption peak of vinyl, in 1020~1130cm-1The strong peak divided there are one is
The absorption peak of Si-O-Si.
With stirring rod, thermometer and reflux condensing tube container in be added 1 part of vinyl modified graphene oxide,
120 parts of ethyl acetates, 0.2 part of 3- sulfydryl -1,2-PD and 0.02 part of benzoin dimethylether, under stirring, in dominant wavelength
365nm irradiates 3min under the ultraviolet light of luminous intensity 180W/cm, removes ultraviolet light, be warming up to the micro- reflux of system, 1 part of hydration is added
Hydrazine reacts 5 hours, filters while hot, filter out solid washes of absolute alcohol three times, is put into 80 DEG C of vacuum ovens and dries to perseverance
Weight, obtains polyhydroxy modified graphene 1.FT-IR analysis, product is in 3643cm-1There are the broad peaks of a moderate strength, are hydroxyl
Absorption peak, 1610cm-1There is no absorption peak nearby, illustrates that there is no carbon carbon unsaturated double-bonds in product, in 2560cm-1Near
There is no absorption peak, illustrates that there is no sulfydryls in product, in 1221cm-1There are a sharp weak peaks, are the absorption peak of C-S-C.
580 parts of dehydrated alcohols and 1 part of Hummers are added in the container with stirring rod, thermometer and reflux condensing tube
Ultrasonic disperse 30 minutes, 0.6 part of allyltrimethoxysilanis was added in graphene oxide, and it is micro- to be warming up to reaction system under stirring
Reflux, continues to be stirred to react 1 hour, filters while hot, filter out solid washes of absolute alcohol three times, be put into 80 DEG C of vacuum ovens
Middle drying obtains allyl modified graphene oxide to constant weight.
With stirring rod, thermometer and reflux condensing tube container in be added 1 part of allyl modified graphene oxide,
500 parts of ethyl acetates, 0.35 part of 3- sulfydryl -1,2-PD and 0.02 part of benzoin dimethylether, under stirring, in dominant wavelength
365nm irradiates 20min under the ultraviolet light of luminous intensity 120W/cm, removes ultraviolet light, be warming up to the micro- reflux of system, 2 parts of boron are added
Sodium hydride reacts 3.5 hours, filters while hot, filter out solid washes of absolute alcohol three times, is put into 60 DEG C of vacuum ovens and does
It is dry to constant weight, obtain polyhydroxy modified graphene 2.
1000 parts of dehydrated alcohols and 1 part of Hummers are added in the container with stirring rod, thermometer and reflux condensing tube
Graphene oxide ultrasonic disperse 30 minutes, is added 1 part of 1- cyclobutenyl trimethoxy silane, it is micro- to be warming up to reaction system under stirring
Reflux, continues to be stirred to react 0.5 hour, filters while hot, filter out solid washes of absolute alcohol three times, be put into 60 DEG C of vacuum drying
It dries in case to constant weight, obtains 1- cyclobutenyl modified graphene oxide.
With stirring rod, thermometer and reflux condensing tube container in be added 1 part of 1- cyclobutenyl modified graphene oxide,
1000 parts of ethyl acetates, 0.5 part of 3- sulfydryl -1,2-PD and 0.03 part of benzoin dimethylether, under stirring, in dominant wavelength
365nm irradiates 90min under the ultraviolet light of luminous intensity 20W/cm, removes ultraviolet light, be warming up to the micro- reflux of system, and 3 parts of dimensions lifes are added
Plain C reacts 3 hours, filters while hot, filter out solid washes of absolute alcohol three times, is put into 70 DEG C of vacuum ovens and dries extremely
Constant weight obtains polyhydroxy modified graphene 3.
Embodiment 1
100 parts of p-phthalic acids, 0.3 part of polyhydroxy are added in the container with stirring rod, thermometer and current divider
Modified graphene 1 and 120 part ethylene glycol carries out esterification at 250-255 DEG C, and reaction process persistently removes the water of generation,
The esterification yield of the viscosity monitoring reaction of reaction intermediates is measured, reaction to esterification yield reaches 92% or more, and cooling obtains in esterification
Mesosome 1.
Intermediates 1 and 320ppm are esterified being added 100 parts with stirring rod, thermometer and in the container for connecting vacuum pump
Antimony trioxide carries out polycondensation reaction 1.5 hours at the negative pressure of < 6000Pa, 267 DEG C, then adjusts negative pressure to 70Pa, at 270 DEG C
Lower reaction 4 hours, cooling, Cast Strip, cooling, pelletizing obtain graphene Modified polyester chips 1.
Embodiment 2
100 parts of p-phthalic acids, 0.7 part of polyhydroxy are added in the container with stirring rod, thermometer and current divider
Modified graphene 2 and 110 part ethylene glycol carries out esterification at 255-260 DEG C, and reaction process persistently removes the water of generation,
The esterification yield of the viscosity monitoring reaction of reaction intermediates, reaction to esterification yield at least 92% are measured, cooling obtains esterification intermediate
2。
Intermediates 2 and 350ppm are esterified being added 100 parts with stirring rod, thermometer and in the container for connecting vacuum pump
Antimony trioxide, the negative pressure of < 6000Pa carry out polycondensation reaction 1.5 hours at 270 DEG C, then adjust negative pressure to 66Pa, at 275 DEG C
Reaction 3 hours, cooling, Cast Strip, cooling, pelletizing obtain graphene Modified polyester chips 2.
Embodiment 3
100 parts of p-phthalic acids, 1.1 parts of polyhydroxy are added in the container with stirring rod, thermometer and current divider
Modified graphene 3 and 108 part ethylene glycol carries out esterification at 270-275 DEG C, and reaction process persistently removes the water of generation,
The esterification yield of the viscosity monitoring reaction of reaction intermediates, reaction to esterification yield at least 92% are measured, cooling obtains esterification intermediate
3。
It is having stirring rod, thermometer and 100 parts of esterification intermediates 3 and 380ppm tri- is added in the container for connecting vacuum pump
Antimony oxide, the negative pressure of < 6000Pa carry out polycondensation reaction 1 hour at 280 DEG C, then adjust negative pressure to 60Pa, react at 285 DEG C
2 hours, cooling, Cast Strip, cooling, pelletizing obtained graphene Modified polyester chips 3.
Embodiment 4
100 parts of p-phthalic acids, 1.5 parts of polyhydroxy are added in the container with stirring rod, thermometer and current divider
Modified graphene 2 and 103 part ethylene glycol carries out esterification at 275 DEG C, and reaction process persistently removes the water of generation, measurement
The esterification yield of the viscosity monitoring reaction of reaction intermediates, reaction to esterification yield at least 92%, cooling obtain esterification intermediate 4.
It is having stirring rod, thermometer and 100 parts of esterification intermediates 4 and 350ppm tri- is added in the container for connecting vacuum pump
Antimony oxide, the negative pressure of < 6000Pa carry out polycondensation reaction 1.5 hours at 275 DEG C, then adjust negative pressure to 65Pa, anti-at 285 DEG C
It answers 2 hours, cooling, Cast Strip, cooling, pelletizing obtain graphene Modified polyester chips 4.
Embodiment 5
100 parts of p-phthalic acids are added in the container with stirring rod, thermometer and current divider, 2 parts of polyhydroxy change
Property graphene 1 and 100 part ethylene glycol, carry out esterification at 275 DEG C, reaction process persistently removes the water of generation, and measurement is anti-
The viscosity of intermediary is answered to monitor the esterification yield of reaction, reaction to esterification yield at least 92%, cooling obtains esterification intermediate 5.
It is having stirring rod, thermometer and 100 parts of esterification intermediates and 350ppm tri- is added in the container for connecting vacuum pump
Antimony oxide, the negative pressure of < 6000Pa carry out polycondensation reaction 1.2 hours at 275 DEG C, then adjust negative pressure to 65Pa, anti-at 285 DEG C
It answers 2 hours, cooling, Cast Strip, cooling, pelletizing obtain graphene Modified polyester chips 5.
Embodiment 6
100 parts of p-phthalic acids, 2.3 parts of polyhydroxy are added in the container with stirring rod, thermometer and current divider
Modified graphene 1 and 100 part ethylene glycol carries out esterification at 275 DEG C, and reaction process persistently removes the water of generation, measurement
The esterification yield of the viscosity monitoring reaction of reaction intermediates, reaction to esterification yield at least 92%, cooling obtain esterification intermediate 6.
It is having stirring rod, thermometer and 100 parts of esterification intermediates and 350ppm tri- is added in the container for connecting vacuum pump
Antimony oxide, the negative pressure of < 6000Pa carry out polycondensation reaction 1.2 hours at 275 DEG C, then adjust negative pressure to 65Pa, anti-at 285 DEG C
It answers 2 hours, cooling, Cast Strip, cooling, pelletizing obtain graphene Modified polyester chips 6.
Performance test
Using the intrinsic viscosity of the graphene Modified polyester chips in solwution method difference testing example 1-6.As a result such as table 1
It is shown.
The Modified polyester chips in embodiment 1-6 are subjected to melt spinning respectively, observe the situation of melt spinning process.Knot
Fruit is as shown in table 1.
Amplify the surface appearance of sem observation fiber.The results are shown in Table 1.
Specific resistance test: molten using the Modified polyester chips in Gy321 fiber type specific resistance tester testing example 1-6
Melt the mass specific resistance of the fiber obtained after spinning.The results are shown in Table 1.
1 the performance test results of table
From the results shown in Table 1, the present invention adds polyhydroxy modified graphene in the preparation of polyester slice, can be with
The Modified polyester chips with preferable spinning effect are obtained, but polyhydroxy modified graphene cannot be added, and add will affect
The spinning effect of polyester slice.The mass specific resistance of the fiber obtained by Modified polyester chips melt spinning is with graphene content
Increase and reduce, antistatic property is preferable.
It should be noted that embodiment disclosed above only embodies and illustrates technical solution of the present invention, rather than it is used to limit this
The protection scope of invention, although explaining in detail referring to preferred embodiment to the present invention, any those skilled in the art is answered
Work as understanding, modify within the scope of technical solution of the present invention or various change, equivalent replacement not departing from, this all should belong to
The protection scope of invention.
Claims (10)
1. a kind of preparation method of graphene Modified polyester chips, it is characterised in that: include the following steps,
S1: p-phthalic acid, polyhydroxy modified graphene and ethylene glycol are added in a reservoir, ester is carried out at 250~275 DEG C
Change reaction, reaction process persistently removes the water of generation, reaction to esterification yield at least 92%, and cooling obtains esterification intermediate；
S2: by the esterification intermediate in step S1, in catalyst, the negative pressure of < 6000Pa contracts at 265~280 DEG C
Poly- reaction 1~1.5 hour, then adjust negative pressure to 80Pa is lower than, reacts 2~4 hours at 270~285 DEG C, cooling, Cast Strip, cold
But, pelletizing obtains graphene Modified polyester chips.
2. the preparation method of graphene Modified polyester chips according to claim 1, it is characterised in that: described in step S1
The mass ratio of p-phthalic acid, polyhydroxy modified graphene and ethylene glycol are 100:0.3~2:100~120.
3. the preparation method of graphene Modified polyester chips according to claim 1, it is characterised in that: described in step S1
The preparation method of polyhydroxy modified graphene, includes the following steps,
S3: dehydrated alcohol and Hummers graphene oxide are added in a reservoir, ultrasonic disperse 30 minutes, α-alkenyl silanes are added
Coupling agent is warming up to the micro- reflux of reaction system under stirring, continue to be stirred to react 0.5~2 hour, filter while hot, filters out solid use
Washes of absolute alcohol three times, is put into 60~80 DEG C of vacuum ovens and dries to constant weight, obtain α-alkenyl modified graphene oxide；
S4: the double first of α-alkenyl modified graphene oxide, ethyl acetate, 3- sulfydryl -1,2- propylene glycol and styrax in step S3
Ether anabolic reaction system under stirring, irradiates 3~90min at dominant wavelength 365nm, the ultraviolet light of 20~180W/cm of luminous intensity,
Ultraviolet light is removed, the micro- reflux of system is warming up to, reducing agent is added, is reacted 3~5 hours, is filtered while hot, filter out solid with anhydrous second
Alcohol cleans three times, is put into 60~80 DEG C of vacuum ovens and dries to constant weight, obtains polyhydroxy modified graphene.
4. the preparation method of graphene Modified polyester chips according to claim 3, it is characterised in that: described in step S3
α-alkenyl silanes coupling agent is selected from 1- cyclobutenyl trimethoxy silane, 1- cyclobutenyl triethoxysilane, allyl trimethoxy
Silane, allyl methyl dimethoxysilane, allyltriethoxysilane, allyl methyl diethoxy silane, vinyl
Trimethoxy silane, vinyl methyl dimethoxysilane, vinyltriethoxysilane, vinyl methyl diethoxy silicon
Alkane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropylmethyl dimethoxysilane, 3- first
Base acryloxypropyl triethoxysilane, 3- methacryloxypropyl methyl diethoxysilane, 3- acryloyl-oxy
Base propyl trimethoxy silicane, 3- acryloxypropyl dimethoxysilane, 3- acryloxypropyl triethoxy
One or more of silane and 3- acryloyloxy propyl methyl diethoxysilane.
5. the preparation method of graphene Modified polyester chips according to claim 3, it is characterised in that: anhydrous in step S3
Ethyl alcohol, Hummers oxidizing process graphene and α-alkenyl silanes coupling agent mass ratio are 100~1000:1:0.2~1.
6. the preparation method of graphene Modified polyester chips according to claim 3, it is characterised in that: described in step S4
α-alkenyl modified graphene oxide, ethyl acetate, 3- sulfydryl -1,2- propylene glycol and benzoin dimethylether mass ratio be 1:100
~1000:0.2~0.5:0.02~0.03.
7. the preparation method of graphene Modified polyester chips according to claim 3, it is characterised in that: described in step S4
Reducing agent is selected from one or more of hydrazine hydrate, sodium borohydride, vitamin C, Dimethylhydrazine, hydroquinone and phenylhydrazine, uses weight
Amount is 1~3 times of α-alkenyl modified graphene oxide weight in step S4.
8. the preparation method of graphene Modified polyester chips according to claim 1, it is characterised in that: the catalyst is
Antimony trioxide, the usage amount of antimony trioxide are 300~400ppm of the theoretical yield for the polyester that polycondensation reaction obtains.
9. a kind of graphene that the preparation method of the described in any item graphene Modified polyester chips of claim 1-8 is prepared changes
Property polyester slice.
10. a kind of modification that the preparation method of the described in any item graphene Modified polyester chips of claim 1-8 is prepared is poly-
Ester slice is used to prepare polyester fiber and polyester complex fiber.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112064171A (en) * | 2020-09-11 | 2020-12-11 | 涂一淼 | Antistatic fabric and preparation method thereof |
| CN113717436A (en) * | 2020-05-26 | 2021-11-30 | 远东新世纪股份有限公司 | Graphene dispersion liquid, preparation method thereof, composition for preparing polyurethane composite material and polyurethane composite material |
| WO2022189992A1 (en) * | 2021-03-11 | 2022-09-15 | Reliance Industries Limited | Graphene incorporated polymer fibre, corresponding fabric, process of preparation, and applications thereof |
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