CN106750205A - A kind of preparation method of Graphene modified poly ester film - Google Patents
A kind of preparation method of Graphene modified poly ester film Download PDFInfo
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The present invention relates to a kind of preparation method of Graphene modified poly ester film, the graphene dispersing solution of 0.18wt%~1.76wt% is obtained first, the pre-dispersed liquid of Graphene is introduced in the synthesis of Graphene modified poly ester, Graphene modified poly ester is prepared using situ aggregation method, the Graphene modified poly ester that will be prepared is used as component A, normal polyester is used as B component, component A and B component go out to be compounded to form AB bilayers or ABA three-deckers by T-shaped mould coextrusion head, through slab, biaxial tension, thermal finalization and winding are obtained Graphene modified poly ester film of the thickness at 20 μm~400 μm.The present invention has excellent mechanical property and UVResistant effect because of component A, there is good lasting tensile strength and uvioresistant performance so as to assign film, simultaneously can be by the mechanics and uvioresistant performance that change the addition of Graphene in Graphene modified poly ester to regulate and control polyester film, and with preferable thermodynamic compatibility.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene modified poly ester film, more particularly to a kind of in-situ polymerization function
The preparation method of polyester, belongs to polyester film technical field.
Background technology
Polyethylene terephthalate (PET) is one of currently the most important ones synthetic material, and PET film is strong with its machinery
Degree is high, cold-resistant heat-resist, shrinkage is stable and excellent electrical insulation capability and optical property, is widely used in packaging, work
The field such as industry, electric, electronics, magnetic, photosensitive.
Though the country has produced polyester film for many years, still suffered from terms of product quality stability, multi items, multipurpose
Problems, therefore so far, many features polyester films still need to rely on external import.Ground in high-performance polyester film
Study carefully aspect, domestic and international experts and scholars have done many work, it was also proposed that many new methods and thinking, study on the modification is concentrated mainly on
Improve several aspects such as the crystalline rate of PET, heat distortion temperature, water vapor barrier property, mechanical property, weather resistance.At present with
The continuous expansion of PET film product application, especially as vibrating membrane, horn diaphragm field etc. will to the mechanical property of PET film product
Ask and increasingly lifted, and it is two kinds of important channels for obtaining high-strength thin-film to improve drawing process and reasonable employment additive.
CN101293413A is disclosed《A kind of preparation method of high-strength reduction polyester film》, sophistication (especially indulges
To double stretching), optimizing raw material, proportioning, technique etc., realize at a high speed (up to 380 ms/min), wide cut is (up to 8.2 meters of width
It is wide), the record of production of rate of film build (not rupture of membranes) high substantially increases production capacity, reduces production cost.
In terms of uvioresistant polyester thin film study and product development, primarily form to be introduced in the polyester synthesis stage at present and received
The resistance organic light stabilizer of amine side base and inorganic nanometer functional powder, assign polyester film UVResistant effect.CN1552765A is disclosed
's《The method of preparing uvioresistant polyester by nanometer titania generated in situ》, abandoned the additional ultraviolet screener in polyester monocase
Agent carries out polymerization and prepares the method for uvioresistant polyester, but has synthesized a kind of dibasic alkoxide of the controllable titanium of hydrolysis rate, makes it
The polyester with anti-ultraviolet function is prepared in the method in-situ polymerization of polyester polymerization process situ generation nano-titanium oxide.
Disclosed in CN105085887A《A kind of uvioresistant polyester film》A kind of the anti-of new polyester copolymer containing hindered amine side base is provided
Ultraviolet polyester film, not only shows the outstanding ultraviolet light stability of hindered amine compound, and it is good to have polyester film concurrently
Mechanical property and ultraviolet light stability, additionally, also have that hydrolytic resistance is good, volatility is low, low smell, resistance to migration and resistance to extraction etc.
Advantage.
Grapheme material is high temperature resistant, the high-tenacity composite high-molecular material developed in recent years.The height of grapheme material
Specific surface area, electric conductivity, performance of watertightness, UV absorption, high elastic modulus and other still not well known particularity
A revolution of field of new can be triggered, while also causing that Graphene modified function complex fiber material turns into research heat
Point.
In terms of reinforced polyester thin film mechanical performance and uvioresistant performance, although there is the document report of correlation both at home and abroad,
But how to realize that polyester film high intensity and the multi-functional compound method of modifying of uvioresistant are rarely reported.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Graphene modified poly ester film, introduced in the polyester synthesis stage
The pre-dispersed liquid of graphene oxide, so as to prepare Graphene modified poly ester and machine-shaping into film, by graphite
The control of the addition of alkene modified poly ester reaches effective with uvioresistant performance to the polyester film mechanical property finally prepared
Regulation and control.
The present invention is that the technical scheme for reaching above-mentioned purpose is:A kind of preparation method of Graphene modified poly ester film, its
It is characterised by:The preparation including graphene dispersing solution, the synthesis of Graphene modified poly ester, Graphene modified poly ester are processed into successively
Type is concretely comprised the following steps into film:
(1), the preparation of graphene dispersing solution:
Add the concentrated sulfuric acid of 90mL to the reaction bulb that is placed in ice-water bath, stirring is lower to add 2g graphite powders and 4g sodium nitrate
Solid mixture, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, stirring reaction 30min
Afterwards, by heating water bath to 35 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, by heating water bath to 98 DEG C, after
Add hydrogen peroxide after continuous stirring 30min, solution is changed into glassy yellow, reaction is emerged end to without gas, is filtered while hot, uses watery hydrochloric acid
With deionized water washed product, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is fully dried, obtained graphite oxide and preserve standby
With;
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, is warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after 24h is reacted under the conditions of this, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, then in 60 DEG C of vacuum
Fully dried in drying box, obtain Graphene and save backup;Graphene is dispersed in ethylene glycol using probe sonication, the profit after 2h
With observation by light microscope it is well dispersed after, be obtained 0.18wt%~1.76wt% graphene dispersing solution;
(2), the synthesis of Graphene modified poly ester:
By the graphene dispersing solution of prepared 0.18wt%~1.76wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio
Mashing, added the mixing of catalyst, heat stabilizer and antioxidant before esterification starts, after all materials are well mixed
It is added in polyester synthesis reactor, is esterified and polycondensation reaction, wherein, catalyst charge is terephthalic acid (TPA) quality
100~500ppm, heat stabilizer addition is the 0.001~0.02% of terephthalic acid (TPA) quality, and antioxidant addition is right
The 0.001~0.03% of phthalic acid quality;Esterification temperature during esterification is maintained at 240~260 DEG C, Stress control exists
100~300kPa, esterification continues 3~5h, and when esterification water yield reaches theoretical more than 98%, esterification terminates, then
30~80pa of vacuum pressure control carries out polycondensation reaction, and temperature is maintained at 255~285 DEG C, and the reaction time, in 2~4h, is obtained stone
Black alkene modified poly ester;
(3)), the machine-shaping of Graphene modified poly ester is into film:
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form AB bilayers or ABA three-deckers, thickness is obtained through slab, biaxial tension, thermal finalization and winding
Spend the Graphene modified poly ester film at 20 μm~400 μm.
The present invention is had the characteristics that using above-mentioned technical proposal.
(1) present invention is combined to realize polyester film high intensity with uvioresistant performance, is introduced in the polyester synthesis stage and aoxidized
The pre-dispersed liquid of Graphene, and the addition of pre-dispersed liquid can be set according to final products performance requirement.Pre-dispersed liquid
The monomer ethylene glycol used by polyester synthesis is chosen as dispersion, it is ensured that good compatibility between graphene oxide and polyester.
(2) this most thin two-dimensional nano particle of graphene oxide is introduced as filler using situ aggregation method, it is ensured that
The good dispersive property in PET of graphene oxide, substantially reduces powder reuniting phenomenon, realizes the polymerization of Graphene modified poly ester
The stability of process.
(3), the present invention Graphene modified poly ester and normal polyester are gone out by T-shaped mould coextrusion head it is compound, by polyester film
Tri- layers of AB bilayers or ABA are designed to, A layer components are the modified copolyester for preparing, and B layer components are normal polyester, A in film
Matrix material is polyester in layer component, with B layer components without adhesive-layer, with thermodynamic compatibility.Film has because of A layer components
Excellent mechanical property and UVResistant effect, so that assigning film has good lasting tensile strength and uvioresistant performance, together
When can be by the mechanics and uvioresistant performance that change the addition of Graphene in Graphene modified poly ester to regulate and control polyester film.
The present invention prepares Graphene modified poly ester and machine-shaping is into film, realizes polyester film in mechanical property and ultraviolet-resistent property
Can be multi-functional compound.
Specific embodiment
A kind of preparation method of Graphene modified poly ester film of the invention, successively the preparation including graphene dispersing solution,
Synthesis, the Graphene modified poly ester machine-shaping of Graphene modified poly ester are comprised the following steps that into film.
(1), the preparation of graphene dispersing solution.
Add the concentrated sulfuric acid of 90mL to the reaction bulb that is placed in ice-water bath, stirring is lower to add 2g graphite powders and 4g sodium nitrate
Solid mixture, graphite Powder Particle Size is more than 95% less than 30 μm, content, carbon content 99.85%, then by 10g potassium permanganate point extremely
Few three additions, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min, and heating water bath to 35 DEG C continues to stir 5h
Afterwards, it is poured slowly into 180mL deionized waters, heating water bath to 98 DEG C continues to add hydrogen peroxide, solution to become after stirring 30min
It is glassy yellow, reaction is emerged end to without gas, is filtered while hot, with watery hydrochloric acid and deionized water washed product, finally by filter cake
It is placed in 60 DEG C of vacuum drying chamber and fully dries, obtains graphite oxide and save backup.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, is warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after 24h is reacted under the conditions of this, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, then in 60 DEG C of vacuum
Fully dried in drying box, obtain Graphene and save backup;Graphene is dispersed in ethylene glycol using probe sonication, can be used
The graphene dispersion of 0.18g~1.76g is divided after 2h in the ethylene glycol of 98.24g~99.82g using observation by light microscope
After dissipating well, the graphene dispersing solution of 0.18wt%~1.76wt% is obtained.
The concentrated sulfuric acid, potassium permanganate, sodium nitrate, hydrogen peroxide, hydrochloric acid that the present invention is used when prepared by graphene dispersing solution
And hydrazine hydrate is and analyzes pure, such as using the concentrated sulfuric acid of mass fraction 95%~98%, mass fraction is 36% hydrochloric acid, quality
Fraction be 30% hydrogen peroxide and mass fraction be 80% hydrazine hydrate.
(2), the synthesis of Graphene modified poly ester.
By the graphene dispersing solution of prepared 0.18wt%~1.76wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio
Mashing, before esterification starts, adds the mixing of catalyst, heat stabilizer and antioxidant, well mixed in all materials
After be added in polyester synthesis reactor, be esterified and polycondensation reaction, wherein, catalyst charge is terephthalic acid (TPA) quality
100~500ppm, the catalyst be butyl titanate, titanium ethylene glycolate, antimony oxide, antimony acetate or antimony glycol wherein
Plant or two or more mixtures;Heat stabilizer addition is the 0.001~0.02% of terephthalic acid (TPA) quality, and heat stabilizer is
The one of which or two or more mixtures of trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters, and antioxygen
Agent addition is the 0.001~0.03% of terephthalic acid (TPA) quality, and the antioxidant is antioxidant 1010, antioxidant
168 or antioxidant 616 wherein or two or more mixtures.
Esterification temperature during esterification be maintained at 240~260 DEG C, Stress control in 100~300kPa, esterification is held
Continuous 3~5h, reaction is terminated when esterification water yield reaches theoretical more than 98%, and esterification terminates, then controls 30 in vacuum pressure
~80pa carries out polycondensation reaction, and temperature is maintained at 255~285 DEG C, and the reaction time, in 2~4h, is obtained Graphene modified poly ester, stone
Graphene content in black alkene modified poly ester is in 0.05wt%~0.5wt%.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form that AB is double-deck or ABA three-deckers, through slab, biaxial tension, thermal finalization, the present invention can be
Slab is cooled down to diaphragm less than 30 DEG C of slab rollers of temperature, during biaxial tension, the temperature of longitudinal stretching is 70~110 DEG C, stretches
Than being 3~3.4, the temperature of cross directional stretch is 100~130 DEG C, draw ratio is 2.5~4.0, and thermal finalization control is 170~240
DEG C, winding is obtained Graphene modified poly ester film of the thickness at 20 μm~400 μm, and Graphene modified poly ester film A thickness
Degree is at 1 μm~20 μm.
Embodiment 1
A kind of preparation method of Graphene modified poly ester film of the invention, comprises the following steps that.
(1), the preparation of graphene dispersing solution.
The reaction bulb of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction bulb being placed in ice-water bath, stirred
The solid mixture of lower addition 2g graphite powders and 4g sodium nitrate is mixed, graphite Powder Particle Size is more than 95%, carbon content less than 30 μm, content
99.85%, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min,
By heating water bath to 35 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, heating water bath to 98 DEG C continues to stir
Add hydrogen peroxide, solution to be changed into glassy yellow after mixing 30min, when reaction terminates to without gas reaction of emerging, filter while hot, use dilute salt
, finally be placed in filter cake in 60 DEG C of vacuum drying chamber and fully dry by acid and deionized water washed product, obtains graphite oxide preservation
It is standby.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, when being warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after reaction 24h with this understanding, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, it is then true at 60 DEG C
Fully dried in empty drying box, obtain Graphene and save backup.
The Graphene of 0.18g is dispersed in 99.82g ethylene glycol using probe sonication, light microscope is utilized after 2h
After observation is well dispersed, the graphene dispersing solution of 0.18wt% is obtained.
(2), the synthesis of Graphene modified poly ester:
By the graphene dispersing solution of prepared 0.18wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten, in ester
Before change reaction starts, catalyst, heat stabilizer and antioxidant are added, being added to polyester after all materials are well mixed closes
Into in reactor, it is esterified and polycondensation reaction.Wherein, catalyst charge is the 100ppm of terephthalic acid (TPA) quality, and this is urged
Agent uses butyl titanate or titanium ethylene glycolate, and heat stabilizer addition is the 0.001% of terephthalic acid (TPA) quality, heat stabilizer
Trimethyl phosphate or alkyl phosphoric acid diester are used, and antioxidant addition is the 0.001% of terephthalic acid (TPA) quality, it is anti-oxidant
Agent uses antioxidant 1010.
Esterification temperature during esterification be maintained at 240 DEG C, Stress control in 200~300kPa, esterification is lasting
3.5h, when esterification water yield reaches theoretical more than 98%, esterification terminates, then controls 30~50pa to be contracted in vacuum pressure
Poly- reaction, temperature is maintained at 255~265 DEG C, and the reaction time, in 2h, is obtained Graphene modified poly ester, and Graphene modified poly ester
Middle Graphene content is in 0.05wt%.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form AB double-deckers, slab is cooled down to diaphragm in the slab roller less than 30 DEG C of temperature, longitudinal direction is drawn
The temperature stretched is 70~80 DEG C, draw ratio is 3.4, and the temperature of cross directional stretch is 100~110 DEG C, draw ratio is 4, again 220~
Thermal finalization at a temperature of 230 DEG C, is obtained Graphene modified poly ester film of the thickness at 20 μm, and wherein A thickness degree is at 1 μm.
Embodiment 2
A kind of preparation method of Graphene modified poly ester film of the invention, comprises the following steps that.
(1), the preparation of graphene dispersing solution.
The reaction bulb of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction bulb being placed in ice-water bath, stirred
The solid mixture of lower addition 2g graphite powders and 4g sodium nitrate is mixed, graphite Powder Particle Size is more than 95%, carbon content less than 30 μm, content
99.85%, then 10g potassium permanganate is added in four times, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min, by water
Bath is heated to 35 DEG C, after continuing to stir 5h, is poured slowly into 180mL deionized waters, and heating water bath to 98 DEG C continues to stir
Add hydrogen peroxide, solution to be changed into glassy yellow after 30min, when reaction terminates to without gas reaction of emerging, filter while hot, use watery hydrochloric acid
With deionized water washed product, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is fully dried, obtained graphite oxide and preserve standby
With.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, when being warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after reaction 24h with this understanding, the product that will be obtained is multiple with methyl alcohol and deionized water rinsing successively, then at 60 DEG C
Vacuum drying chamber in fully dry, obtain Graphene and save backup.
The Graphene of 0.5g is dispersed in 99.50g ethylene glycol using probe sonication, is seen using light microscope after 2h
Examine it is well dispersed after, be obtained 0.5wt% graphene dispersing solution.
(2), the synthesis of Graphene modified poly ester.
By the graphene dispersing solution of prepared 0.5wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten, in esterification
Before reaction starts, the mixing of catalyst, heat stabilizer and antioxidant is added, polyester is added to after all materials are well mixed
In synthesis reactor, it is esterified and polycondensation reaction.Wherein, catalyst charge is the 200ppm of terephthalic acid (TPA) quality, should
Catalyst uses antimony oxide or antimony acetate;Heat stabilizer addition is the 0.005% of terephthalic acid (TPA) quality, heat stabilizer
Using trimethyl phosphate and alkyl phosphoric acid diester, both do not limit ratio, and antioxidant addition is terephthalic acid (TPA) quality
0.005%, antioxidant uses anti-antioxidant 168 or antioxidant 616.
Esterification temperature during esterification be maintained at 250~255 DEG C, Stress control in 100~200kPa, esterification is held
Continuous 4h, when esterification water yield reaches theoretical more than 98%, esterification terminates, then controls 40~60pa to be contracted in vacuum pressure
Poly- reaction, temperature is maintained at 265~270 DEG C, and the reaction time, in 2.5h, is obtained Graphene modified poly ester, and Graphene is modified poly-
Graphene content is in 0.05wt% in ester.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form ABA three-deckers, slab, longitudinal direction are cooled down to diaphragm with the slab roller less than 30 DEG C of temperature
The temperature of stretching is 90~100 DEG C, draw ratio is 3, and the temperature of cross directional stretch is 120~130 DEG C, draw ratio is 3.2, again
Thermal finalization at a temperature of 170~200 DEG C, winding is obtained Graphene modified poly ester film of the thickness at 100 μm, and wherein A thickness degree is 5
μm。
Embodiment 3
A kind of preparation method of Graphene modified poly ester film of the invention, comprises the following steps that.
(1), the preparation of graphene dispersing solution.
The reaction bulb of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction bulb being placed in ice-water bath, stirred
The solid mixture of lower addition 2g graphite powders and 4g sodium nitrate is mixed, graphite Powder Particle Size is more than 95%, carbon content less than 30 μm, content
99.85%, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min,
By heating water bath to 37 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, heating water bath to 98 DEG C continues to stir
Add hydrogen peroxide, solution to be changed into glassy yellow after mixing 30min, when reaction terminates to without gas reaction of emerging, filter while hot, use dilute salt
, finally be placed in filter cake in 60 DEG C of vacuum drying chamber and fully dry by acid and deionized water washed product, obtains graphite oxide preservation
It is standby.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, when being warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after reaction 24h with this understanding, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, it is then true at 60 DEG C
Fully dried in empty drying box, obtain Graphene and save backup.
The Graphene of 0.88g is dispersed in 99.12g ethylene glycol using probe sonication, light microscope is utilized after 2h
After observation is well dispersed, the graphene dispersing solution of 0.88wt% is obtained.
(2), the synthesis of Graphene modified poly ester.
By the graphene dispersing solution of prepared 0.88wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten, in ester
Before change reaction starts, the mixing of catalyst, heat stabilizer and antioxidant is added, be added to after all materials are well mixed poly-
In ester synthesis reaction device, it is esterified and polycondensation reaction.Wherein, catalyst charge is the 300ppm of terephthalic acid (TPA) quality,
The catalyst uses antimony glycol;Heat stabilizer addition is the 0.01% of terephthalic acid (TPA) quality, and heat stabilizer uses phosphoric acid
Trimethyl and three (nonyl phenyl) phosphite esters, both do not limit ratio, and antioxidant addition is terephthalic acid (TPA) quality
0.01%, antioxidant is that both antioxidant 1010 and antioxidant 616 ratios are not limited.
Esterification temperature during esterification be maintained at 255~260 DEG C, Stress control in 150~250kPa, esterification is held
Continuous 5h, when esterification water yield reaches theoretical more than 98%, esterification terminates, then controls 70~80pa to be contracted in vacuum pressure
Poly- reaction, temperature is maintained at 275~285 DEG C, and the reaction time, in 4h, is obtained Graphene modified poly ester;And Graphene modified poly ester
Middle Graphene content is in 0.25wt%.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form ABA three-deckers, slab, longitudinal direction are cooled down to diaphragm with the slab roller less than 30 DEG C of temperature
The temperature of stretching is 100~110 DEG C, draw ratio is 3.2, and the temperature of cross directional stretch is 120~130 DEG C, draw ratio is 3, again
Thermal finalization at a temperature of 200~220 DEG C, winding is obtained Graphene modified poly ester film of the thickness at 100 μm, and wherein A thickness degree is 5
μm。
Embodiment 4
A kind of preparation method of Graphene modified poly ester film of the invention, comprises the following steps that.
(1), the preparation of graphene dispersing solution.
The reaction bulb of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction bulb being placed in ice-water bath, stirred
The solid mixture of lower addition 2g graphite powders and 4g sodium nitrate is mixed, graphite Powder Particle Size is more than 95%, carbon content less than 30 μm, content
99.85%, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min,
By heating water bath to 33 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, heating water bath to 98 DEG C continues to stir
Add hydrogen peroxide, solution to be changed into glassy yellow after mixing 30min, when reaction terminates to without gas reaction of emerging, filter while hot, use dilute salt
, finally be placed in filter cake in 60 DEG C of vacuum drying chamber and fully dry by acid and deionized water washed product, obtains graphite oxide preservation
It is standby.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, when being warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after reaction 24h with this understanding, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, it is then true at 60 DEG C
Fully dried in empty drying box, obtain Graphene and save backup.
The Graphene of 1.3g is dispersed in 98.70g ethylene glycol using probe sonication, is seen using light microscope after 2h
Examine it is well dispersed after, be obtained 1.3wt% graphene dispersing solution.
(2), the synthesis of Graphene modified poly ester.
By the graphene dispersing solution of prepared 1.3wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten, in esterification
Before reaction starts, the mixing of catalyst, heat stabilizer and antioxidant is added, polyester is added to after all materials are well mixed
In synthesis reactor, it is esterified and polycondensation reaction.Wherein, catalyst charge is the 400ppm of terephthalic acid (TPA) quality, should
Catalyst uses butyl titanate and titanium ethylene glycolate mixture, and both do not limit ratio;Heat stabilizer addition is terephthalic acid (TPA)
The 0.015% of quality, heat stabilizer uses trimethyl phosphate and alkyl phosphoric acid diester, and both do not limit ratio;Antioxidant is added
Amount is the 0.02% of terephthalic acid (TPA) quality, and antioxidant uses antioxidant 168 and antioxidant 616, and both do not limit ratio.
Esterification temperature during esterification be maintained at 245~255 DEG C, Stress control in 250~300kPa, esterification is held
Continuous 4h, when esterification water yield reaches theoretical more than 98%, esterification terminates, then controls 60~70pa to be contracted in vacuum pressure
Poly- reaction, temperature is maintained at 265~275 DEG C, and the reaction time, in 3.5h, is obtained Graphene modified poly ester;And Graphene is modified poly-
Graphene content is in 0.5wt% in ester.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form ABA three-deckers, slab, longitudinal direction are cooled down to diaphragm with the slab roller less than 30 DEG C of temperature
The temperature of stretching is 90~100 DEG C, draw ratio is 3.1, and the temperature of cross directional stretch is 115~125 DEG C, draw ratio is 3.5, again
Thermal finalization at a temperature of 230~240 DEG C, winding is obtained required thickness in 100 μm of Graphene modified poly ester films, wherein A thickness degree
At 5 μm.
Embodiment 5
A kind of preparation method of Graphene modified poly ester film of the invention, comprises the following steps that.
(1), the preparation of graphene dispersing solution.
The reaction bulb of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction bulb being placed in ice-water bath, stirred
The solid mixture of lower addition 2g graphite powders and 4g sodium nitrate is mixed, graphite Powder Particle Size is more than 95%, carbon content less than 30 μm, content
99.85%, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min,
By heating water bath to 35 ± 2 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, by heating water bath to 98 DEG C, after
Add hydrogen peroxide, solution to be changed into glassy yellow after continuous stirring 30min, when reaction terminates to without gas reaction of emerging, filter while hot, use
, finally be placed in filter cake in 60 DEG C of vacuum drying chamber and fully dry by watery hydrochloric acid and deionized water washed product, obtains graphite oxide
Save backup.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, when being warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after reaction 24h with this understanding, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, it is then true at 60 DEG C
Fully dried in empty drying box, obtain Graphene and save backup.
The Graphene of 1.76g is dispersed in 98.24g ethylene glycol using probe sonication, light microscope is utilized after 2h
After observation is well dispersed, the graphene dispersing solution of 1.76wt% is obtained.
(2), the synthesis of Graphene modified poly ester.
By the graphene dispersing solution of prepared 1.76wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten, in ester
Before change reaction starts, the mixing of catalyst, heat stabilizer and antioxidant is added, be added to after all materials are well mixed poly-
In ester synthesis reaction device, it is esterified and polycondensation reaction.Wherein, catalyst charge is the 350ppm of terephthalic acid (TPA) quality,
The catalyst uses butyl titanate and titanium ethylene glycolate mixture, and both do not limit ratio;Heat stabilizer addition is terephthaldehyde
The 0.015% of sour quality, heat stabilizer uses trimethyl phosphate and alkyl phosphoric acid diester, and both do not limit ratio;Antioxidant adds
Enter amount is terephthalic acid (TPA) quality 0.02%, antioxidant uses antioxidant 168 and antioxidant 616, and both ratios are not
Limit.
Esterification temperature during esterification be maintained at 240~250 DEG C, Stress control in 120~180kPa, esterification is held
Continuous 3h, when esterification water yield reaches theoretical more than 98%, esterification terminates, then controls 30~40pa to be contracted in vacuum pressure
Poly- reaction, temperature is maintained at 260~265 DEG C, and the reaction time, in 4h, is obtained Graphene modified poly ester;And Graphene modified poly ester
Middle Graphene content is in 0.35wt%.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form AB double-deckers, slab is cooled down to diaphragm with the slab roller less than 30 DEG C of temperature, longitudinal direction is drawn
The temperature stretched is 100~110 DEG C, draw ratio is 3, and the temperature of cross directional stretch is 120~130 DEG C, draw ratio is 2.8, again 215
Thermal finalization at a temperature of~225 DEG C, winding is obtained required thickness in 188 μm of Graphene modified poly ester films, and wherein A thickness degree exists
9.4μm。
Embodiment 6
A kind of preparation method of Graphene modified poly ester film of the invention, comprises the following steps that.
(1), the preparation of graphene dispersing solution.
The reaction bulb of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction bulb being placed in ice-water bath, stirred
The solid mixture of lower addition 2g graphite powders and 4g sodium nitrate is mixed, graphite Powder Particle Size is more than 95%, carbon content less than 30 μm, content
99.85%, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min,
By heating water bath to 36 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, heating water bath to 98 DEG C continues to stir
Add hydrogen peroxide, solution to be changed into glassy yellow after mixing 30min, when reaction terminates to without gas reaction of emerging, filter while hot, use dilute salt
, finally be placed in filter cake in 60 DEG C of vacuum drying chamber and fully dry by acid and deionized water washed product, obtains graphite oxide preservation
It is standby.
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then divide under ultrasound condition
Few 1h is dissipated to, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, when being warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
Filtered after reaction 24h with this understanding, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, it is then true at 60 DEG C
Fully dried in empty drying box, obtain Graphene and save backup.
The Graphene of 1.76g is dispersed in 98.24g ethylene glycol using probe sonication, light microscope is utilized after 2h
After observation is well dispersed, the graphene dispersing solution of 1.76wt% is obtained.
(2), the synthesis of Graphene modified poly ester.
By the graphene dispersing solution of prepared 1.76wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten, in ester
Before change reaction starts, the mixing of catalyst, heat stabilizer and antioxidant is added, be added to after all materials are well mixed poly-
In ester synthesis reaction device, it is esterified and polycondensation reaction.Wherein, catalyst charge is the 500ppm of terephthalic acid (TPA) quality,
The catalyst uses antimony oxide, antimony acetate and antimony glycol, and ratio is not limited.Heat stabilizer addition is terephthalic acid (TPA) matter
The 0.02% of amount, heat stabilizer uses trimethyl phosphate, alkyl phosphoric acid diester and three (nonyl phenyl) phosphite esters, and ratio is not limited.
And antioxidant addition is the 0.03% of terephthalic acid (TPA) quality, antioxidant uses antioxidant 168 and antioxidant
616, ratio is not limited.
Esterification temperature during esterification be maintained at 245~250 DEG C, Stress control in 180~250kPa, esterification is held
Continuous 4.5h, when esterification water yield reaches theoretical more than 98%, esterification terminates, then is carried out in 55~65pa of vacuum pressure control
Polycondensation reaction, temperature is maintained at 270~280 DEG C, and the reaction time, in 3.4h, is obtained Graphene modified poly ester, and Graphene is modified
Graphene content is in 0.5wt% in polyester.
(3)), the machine-shaping of Graphene modified poly ester is into film.
, used as component A, normal polyester is used as B component, and component A and B component are logical for the Graphene modified poly ester that will be prepared
Cross T-shaped mould coextrusion head and go out to be compounded to form ABA three-deckers, slab, longitudinal direction are cooled down to diaphragm with the slab roller less than 30 DEG C of temperature
The temperature of stretching is 90~100 DEG C, draw ratio is 3, and the temperature of cross directional stretch is 115~125 DEG C, draw ratio is 2.5, again
Thermal finalization at a temperature of 190~210 DEG C, winding is obtained required Graphene modified poly ester film of the thickness at 400 μm, wherein A thickness
Degree is at 20 μm.
Comparative example 1
A, B component use normal polyester, and A layers and B layers goes out compound AB double-deckers by T-shaped mould coextrusion head, is being less than
30 DEG C of slab rollers of temperature cool down slab to diaphragm, and the temperature of longitudinal stretching is 70~80 DEG C, draw ratio is 3.4, cross directional stretch
Temperature for 100~110 DEG C, draw ratio be 4, the thermal finalization at a temperature of 220~230 DEG C again, winding be obtained needed for thickness in 20 μ
M polyester films, wherein A thickness degree is at 1 μm.
Comparative example 2
A, B component use normal polyester, and A layer goes out compound ABA three-deckers with B layers by T-shaped mould coextrusion head, with being less than
30 DEG C of slab rollers of temperature cool down slab to diaphragm, and the temperature of longitudinal stretching is 90~100 DEG C, draw ratio is 3, cross directional stretch
Temperature is 120~130 DEG C, draw ratio is 3.2, the thermal finalization at a temperature of 170~200 DEG C again, and winding is obtained required thickness 100
μm polyester film, wherein A thickness degree is at 5 μm.
Comparative example 3
A, B component use normal polyester, and A layer goes out compound AB double-deckers with B layers by T-shaped mould coextrusion head, with being less than
30 DEG C of slab rollers of temperature cool down slab to diaphragm, and the temperature of longitudinal stretching is 100~110 DEG C, draw ratio is 3, cross directional stretch
Temperature for 120~130 DEG C, draw ratio be 2.8, the thermal finalization at a temperature of 215~225 DEG C again, winding be obtained needed for thickness exist
188 μm of polyester films, wherein A thickness degree is at 9.4 μm.
Comparative example 4
A, B component use normal polyester, and A layer goes out compound ABA three-deckers with B layers by T-shaped mould coextrusion head, with being less than
30 DEG C of slab rollers of temperature cool down slab to diaphragm, and the temperature of longitudinal stretching is 90~100 DEG C, draw ratio is 3, cross directional stretch
Temperature is 115~125 DEG C, draw ratio is 2.5, the thermal finalization at a temperature of 190~210 DEG C again, and winding is obtained required thickness 400
μm polyester film, wherein A thickness degree is at 20 μm.
The present invention is tested to the polyester film correlated performance in the various embodiments described above and comparative example, and performance data is detailed
Feelings are shown in Table 1.
The detection method of properties in table:
1st, thickness is tested by the prescriptive procedure of the chapters of GB/T 13542.2-2009 the 4th.
2., tensile strength is tested by the prescriptive procedure of GB/T 13542.2-2009 Chapter 11s.
3., yellowness index is tested by IEC 61215-2005 prescriptive procedures.
Table 1
By embodiment 1 and comparative example 1, embodiment 2,3,4 and comparative example 2, embodiment 5 and comparative example 3, embodiment 6 with
The contrast of comparative example 4, find A layer use Graphene modified poly ester after, can not only enhanced film tensile strength, moreover it is possible to effectively carry
Film uvioresistant performance high.By embodiment 2~4 as can be seen that film tensile strength not with Graphene addition into simple
Proportional relation, so the ratio range of the invention be optimum proportioning scope.
Claims (6)
1. a kind of preparation method of Graphene modified poly ester film, it is characterised in that:Successively including graphene dispersing solution preparation,
Synthesis, the Graphene modified poly ester machine-shaping of Graphene modified poly ester are concretely comprised the following steps into film:
(1), the preparation of graphene dispersing solution:
The solid of the concentrated sulfuric acid of 90mL, the lower addition 2g graphite powders of stirring and 4g sodium nitrate is added to the reaction bulb being placed in ice-water bath
Mixture, then by least three times additions of 10g potassium permanganate point, reaction temperature control is no more than 20 DEG C, after stirring reaction 30min,
By heating water bath to 35 DEG C, after continuing to stir 5h, it is poured slowly into 180mL deionized waters, heating water bath to 98 DEG C continues to stir
Mix and add after 30min hydrogen peroxide, solution is changed into glassy yellow, reaction is emerged ends to without gas, is filtered while hot, with watery hydrochloric acid with go
, finally be placed in filter cake in 60 DEG C of vacuum drying chamber and fully dry by ionized water washed product, obtains graphite oxide and saves backup;
The graphite oxide of 100mg is dispersed in the 100g aqueous solution, brown color suspension is obtained, then be dispersed under ultrasound condition
Few 1h, the dispersion liquid stablized;It is then transferred in four-hole boiling flask, is warmed up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise, at this
Filtered after 24h is reacted under part, the product that will be obtained successively with methyl alcohol and deionized water rinsing repeatedly, then in 60 DEG C of vacuum drying
Fully dried in case, obtain Graphene and save backup;Graphene is dispersed in ethylene glycol using probe sonication, light is utilized after 2h
Learn micro- sem observation it is well dispersed after, be obtained 0.18wt%~1.76wt% graphene dispersing solution;
(2), the synthesis of Graphene modified poly ester:
By the graphene dispersing solution of prepared 0.18wt%~1.76wt% and terephthalic acid (TPA) according to 1.2:1 mixed in molar ratio is beaten
Slurry, added the mixing of catalyst, heat stabilizer and antioxidant before esterification starts, and added after all materials are well mixed
Enter in polyester synthesis reactor, be esterified and polycondensation reaction, wherein, catalyst charge is terephthalic acid (TPA) quality
100~500ppm, heat stabilizer addition is the 0.001~0.02% of terephthalic acid (TPA) quality, and antioxidant addition is right
The 0.001~0.03% of phthalic acid quality;Esterification temperature during esterification is maintained at 240~260 DEG C, Stress control exists
100~300kPa, esterification continues 3~5h, and when esterification water yield reaches theoretical more than 98%, esterification terminates, then
30~80pa of vacuum pressure control carries out polycondensation reaction, and temperature is maintained at 255~285 DEG C, and the reaction time, in 2~4h, is obtained stone
Black alkene modified poly ester;
(3)), the machine-shaping of Graphene modified poly ester is into film:
, used as component A, used as B component, component A and B component are by T-shaped for normal polyester for the Graphene modified poly ester that will be prepared
Die head is coextruded and is compounded to form AB bilayers or ABA three-deckers, and thickness is obtained through slab, biaxial tension, thermal finalization and winding exists
20 μm~400 μm of Graphene modified poly ester film.
2. the preparation method of a kind of Graphene modified poly ester film according to claim 1, it is characterised in that:In the first step
In, the graphite Powder Particle Size is more than 95%, carbon content 99.85%, the described concentrated sulfuric acid, potassium permanganate, nitre less than 30 μm, content
It is pure that sour sodium, hydrogen peroxide, hydrochloric acid and hydrazine hydrate are analysis.
3. the preparation method of a kind of Graphene modified poly ester film according to claim 1, it is characterised in that:In second step
In, the Graphene content in the Graphene modified poly ester is in 0.05wt%~0.5wt%.
4. the preparation method of a kind of Graphene modified poly ester film according to claim 1, it is characterised in that:Described urges
Agent is the one of which or two or more mixed in butyl titanate, titanium ethylene glycolate, antimony oxide, antimony acetate or antimony glycol
Compound.
5. the preparation method of a kind of Graphene modified poly ester film according to claim 1, it is characterised in that the heat is fixed
Agent is one of which or two or more mixtures in trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters.
6. the preparation method of a kind of Graphene modified poly ester film according to claim 1, it is characterised in that:The antioxygen
Agent is one of which or two or more mixtures in antioxidant 1010, antioxidant 168 or antioxidant 616.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105778070A (en) * | 2016-03-24 | 2016-07-20 | 江苏裕兴薄膜科技股份有限公司 | Preparation method of anti-fog anti-ultraviolet polyester film |
CN105820519A (en) * | 2016-02-29 | 2016-08-03 | 洛阳尖端技术研究院 | PET-based graphene composite material, preparation method thereof, and aerostat |
-
2016
- 2016-11-30 CN CN201611077238.XA patent/CN106750205B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105820519A (en) * | 2016-02-29 | 2016-08-03 | 洛阳尖端技术研究院 | PET-based graphene composite material, preparation method thereof, and aerostat |
CN105778070A (en) * | 2016-03-24 | 2016-07-20 | 江苏裕兴薄膜科技股份有限公司 | Preparation method of anti-fog anti-ultraviolet polyester film |
Non-Patent Citations (1)
Title |
---|
马文石等: "石墨烯的制备与表征", 《高校化学工程学报》 * |
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