CN106750205B - 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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- 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
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Abstract
The present invention relates to a kind of preparation methods of graphene modified poly ester film, the graphene dispersing solution of 0.18wt%~1.76wt% is made 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, using the graphene modified poly ester being prepared as component A, normal polyester is as B component, component A and B component are coextruded by T-die is compounded to form AB bilayer or ABA three-decker, through slab, biaxial tension, graphene modified poly ester film of the thickness at 20 μm~400 μm is made in thermal finalization and winding.The present invention has excellent mechanical property and UVResistant effect because of component A, there is good lasting tensile strength and uvioresistant performance to assign film, the mechanics and uvioresistant performance of polyester film can be regulated and controled by changing the additive amount of graphene in graphene modified poly ester simultaneously, and there is preferable thermodynamic compatibility.
Description
Technical field
The present invention relates to a kind of preparation methods 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 technique
Polyethylene terephthalate (PET) is one of currently the most important ones synthetic material, and PET film is mechanical strong with it
Degree is high, resist cold electrical insulation capability and optical property heat-resist, that shrinkage is stable and excellent, is widely used in packaging, work
The fields such as industry, electrical, electronics, magnetism, photosensitive.
Though the country produced polyester film for many years, in terms of stable product quality, multi items, multipurpose there are still
Problems, therefore so far, many features polyester films still need to rely on external import.It is 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 are concentrated mainly on
Improve the crystalline rate of PET, heat distortion temperature, water vapor barrier property, mechanical property, several aspects such as weather resistance.At present with
The continuous expansion of PET film product application, especially as the mechanical property of PET film product is wanted in vibrating membrane, horn diaphragm field etc.
Ask and increasingly promoted, and improve drawing process and reasonable employment additive be obtain high-strength thin-film two kinds of important channels.
CN101293413A is disclosed " a kind of preparation method of high-strength reduction polyester film ", and sophistication is (especially vertical
To stretching twice in succession), optimizing raw material, proportion, technique etc., realize 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 height (not rupture of membranes) substantially increases production capacity, reduces production cost.
In terms of uvioresistant polyester thin film study and product development, primarily formed at present the polyester synthesis stage introduce by
The organic light stabilizer of amine side group and inorganic nanometer functional powder are hindered, polyester film UVResistant effect is assigned.CN1552765A is disclosed
" method of preparing uvioresistant polyester by nanometer titania generated in situ ", abandoned in polyester monocase outer plus ultraviolet screener
Agent carries out the method that polymerization prepares uvioresistant polyester, but has synthesized a kind of dibasic alkoxide of titanium that hydrolysis rate is controllable, makes it
The method in-situ polymerization of in-situ preparation nano-titanium oxide is prepared for the polyester with anti-ultraviolet function in polyester polymerization process.
" a kind of uvioresistant polyester film " disclosed in CN105085887A provides a kind of the anti-of the polyester copolymer of novel side group containing hindered amine
Ultraviolet polyester film not only shows the outstanding ultraviolet light stability of hindered amine compound, but also it is good to have polyester film concurrently
Mechanical property and ultraviolet light stability, in addition, also have hydrolytic resistance is good, volatility is low, low smell, it is resistance to migration and it is resistance to extraction etc.
Advantage.
Grapheme material is the high temperature resistant developed in recent years, high-tenacity composite polymer material.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 materials can be caused, while but also graphene modified function complex fiber material becomes research heat
Point.
In terms of reinforced polyester thin film mechanical performance and uvioresistant performance, although having relevant document report both at home and abroad,
But how to realize that polyester film is high-intensitive and the multi-functional compound method of modifying of uvioresistant is rarely reported.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of graphene modified poly ester film, introduce in the polyester synthesis stage
The pre-dispersed liquid of graphene oxide, so that graphene modified poly ester and machine-shaping be prepared at film, by graphite
The control of the additive amount of alkene modified poly ester reaches to the effective of the polyester film mechanical property and uvioresistant performance finally prepared
Regulation.
The technical solution of the present invention in order to achieve the above objectives is: a kind of preparation method of graphene modified poly ester film,
It is characterized in that: being successively processed into including the preparation of graphene dispersing solution, the synthesis of graphene modified poly ester, graphene modified poly ester
Type is at film, specific steps are as follows:
(1), the preparation of graphene dispersing solution:
The concentrated sulfuric acid of 90mL is added to the reaction flask that is placed in ice-water bath, is added with stirring 2g graphite powder and 4g sodium nitrate
Solid mixture, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, is stirred to react 30min
Afterwards, by heating water bath to 35 DEG C, continue after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, after
It is added hydrogen peroxide after continuous stirring 30min, solution becomes glassy yellow, and reaction to no gas is emerged end, filters while hot, uses dilute hydrochloric acid
With deionized water washed product, finally filter cake is placed in 60 DEG C of vacuum oven and is sufficiently dried, it is standby to obtain graphite oxide preservation
With；
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, is warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours under this condition, successively use methanol and deionized water to rinse repeatedly, then in 60 DEG C of vacuum obtained product
It is sufficiently dry in drying box, it obtains graphene and saves backup；Graphene is dispersed in ethylene glycol using probe sonication, it is sharp after 2h
With optical microscopy observation it is well dispersed after, be made 0.18wt%~1.76wt% graphene dispersing solution；
(2), the synthesis of graphene modified poly ester:
The graphene dispersing solution of obtained 0.18wt%~1.76wt% is mixed with terephthalic acid (TPA) according to 1.2:1 molar ratio
Mashing, before esterification starts be added catalyst, heat stabilizer and antioxidant mixing, all materials after mixing
It is added in polyester synthesis reactor, carries out esterification and polycondensation reaction, wherein catalyst charge is terephthalic acid (TPA) quality
100~500ppm, heat stabilizer additional amount are the 0.001~0.02% of terephthalic acid (TPA) quality, and antioxidant additional amount is pair
The 0.001~0.03% of phthalic acid quality；Esterification temperature when esterification be maintained at 240~260 DEG C, pressure control exist
100~300kPa, esterification continue 3~5h, and when esterification water yield reaches 98% or more theory, esterification terminates, then
Vacuum pressure controls 30~80pa and carries out polycondensation reaction, and temperature is maintained at 255~285 DEG C, and in 2~4h, stone is made in the reaction time
Black alkene modified poly ester；
(3)), the machine-shaping of graphene modified poly ester is at film:
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form AB bilayer or ABA three-decker, thickness is made through slab, biaxial tension, thermal finalization and winding
Spend the graphene modified poly ester film at 20 μm~400 μm.
The present invention has the characteristics that by adopting the above technical scheme.
(1) present invention is compound to realize polyester film high intensity and uvioresistant performance, introduces and aoxidizes in the polyester synthesis stage
The pre-dispersed liquid of graphene, and the additive amount of pre-dispersed liquid can be set according to final products performance requirement.Pre-dispersed liquid
Monomer ethylene glycol used in polyester synthesis is chosen as dispersion, ensure 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, ensure that
Graphene oxide good dispersion performance in PET, substantially reduces powder reuniting phenomenon, realizes the polymerization of graphene modified poly ester
The stability of process.
(3), graphene modified poly ester and normal polyester are coextruded compound by the present invention by T-die, by polyester film
It is designed to that AB bilayer or tri- layers of ABA, A layer component are the modified copolyester being prepared, B layer component is normal polyester, A in film
Basis material is polyester in layer component, is not necessarily to adhesive-layer with B layer component, has thermodynamic compatibility.Film has because of A layer component
Excellent mechanical property and UVResistant effect, so that assigning film has good lasting tensile strength and uvioresistant performance, together
When can regulate and control the mechanics and uvioresistant performance of polyester film by changing the additive amount of graphene in graphene modified poly ester.
Graphene modified poly ester is prepared in the present invention and machine-shaping is at film, realizes polyester film in mechanical property and ultraviolet-resistent property
It can be multi-functional compound.
Specific embodiment
A kind of preparation method of graphene modified poly ester film of the invention, successively including graphene dispersing solution preparation,
The synthesis of graphene modified poly ester, the machine-shaping of graphene modified poly ester are at film, and specific step is as follows.
(1), the preparation of graphene dispersing solution.
The concentrated sulfuric acid of 90mL is added to the reaction flask that is placed in ice-water bath, is added with stirring 2g graphite powder and 4g sodium nitrate
Solid mixture, graphite Powder Particle Size are greater than 95% less than 30 μm, content, carbon content 99.85%, then point extremely by 10g potassium permanganate
Few to be added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min, by heating water bath to 35 DEG C, continues to stir 5h
Afterwards, it is poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continues that hydrogen peroxide is added after stirring 30min, solution becomes
For glassy yellow, reaction to no gas is emerged end, is filtered while hot, with dilute hydrochloric acid and deionized water washed product, finally by filter cake
It is placed in 60 DEG C of vacuum oven and sufficiently dries, obtain graphite oxide and save backup.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, is warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours under this condition, successively use methanol and deionized water to rinse repeatedly, then in 60 DEG C of vacuum obtained product
It is sufficiently dry in drying box, it obtains graphene and saves backup；Graphene is dispersed in ethylene glycol using probe sonication, can be used
The graphene dispersion of 0.18g~1.76g utilizes optical microphotograph sem observation point in the ethylene glycol of 98.24g~99.82g after 2h
After dissipating well, the graphene dispersing solution of 0.18wt%~1.76wt% is made.
The present invention used concentrated sulfuric acid, potassium permanganate, sodium nitrate, hydrogen peroxide, hydrochloric acid when prepared by graphene dispersing solution
And hydrazine hydrate is that analysis is pure, such as uses the concentrated sulfuric acid of mass fraction 95%~98%, the hydrochloric acid that mass fraction is 36%, quality
The hydrazine hydrate hydrogen peroxide that score is 30% and that mass fraction is 80%.
(2), the synthesis of graphene modified poly ester.
The graphene dispersing solution of obtained 0.18wt%~1.76wt% is mixed with terephthalic acid (TPA) according to 1.2:1 molar ratio
Mashing is added catalyst, heat stabilizer and antioxidant mixing, is uniformly mixed in all materials before esterification starts
After be added in polyester synthesis reactor, carry out esterification and polycondensation reaction, wherein catalyst charge is terephthalic acid (TPA) quality
100~500ppm, which is butyl titanate, titanium ethylene glycolate, antimony oxide, antimony acetate or antimony glycol wherein one
Kind or two or more mixtures；Heat stabilizer additional amount is the 0.001~0.02% of terephthalic acid (TPA) quality, and heat stabilizer is
One of or two or more mixture of trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters, and antioxygen
Agent additional amount is the 0.001~0.03% of terephthalic acid (TPA) quality, which is antioxidant 1010, antioxidant
168 or antioxidant 616 wherein or two or more mixtures.
Esterification temperature when esterification be maintained at 240~260 DEG C, pressure control in 100~300kPa, esterification is held
Continuous 3~5h, when esterification water yield reaches 98% or more theory, reaction was completed, and esterification terminates, then controls 30 in vacuum pressure
~80pa carries out polycondensation reaction, and temperature is maintained at 255~285 DEG C, and in 2~4h, graphene modified poly ester, stone is made in the reaction time
Graphene content in black alkene modified poly ester is in 0.05wt%~0.5wt%.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form that AB is double-deck or ABA three-decker, through slab, biaxial tension, thermal finalization, the present invention can be
Lower than the slab roller of 30 DEG C of temperature to the cooling slab of diaphragm, when biaxial tension, the temperature of longitudinal stretching is 70~110 DEG C, stretches
Than being 3~3.4, temperature stretching in the transverse direction is 100~130 DEG C, draw ratio is 2.5~4.0, and thermal finalization control is 170~240
DEG C, it winds and graphene modified poly ester film of the thickness at 20 μm~400 μm is made, and the A thickness of graphene modified poly ester film
Degree is at 1 μm~20 μm.
Embodiment 1
A kind of preparation method of graphene modified poly ester film of the invention, specific step is as follows.
(1), the preparation of graphene dispersing solution.
The reaction flask of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, stirs
The lower solid mixture that 2g graphite powder and 4g sodium nitrate is added is mixed, graphite Powder Particle Size is greater than 95% less than 30 μm, content, carbon content
99.85%, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min,
By heating water bath to 35 DEG C, continues after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continue to stir
Hydrogen peroxide is added after mixing 30min, solution becomes glassy yellow, when reaction to no gas reaction of emerging terminates, filters while hot, with dilute salt
Filter cake is finally placed in 60 DEG C of vacuum oven and sufficiently dries by acid and deionized water washed product, obtains graphite oxide preservation
It is spare.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, when being warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours with this condition, successively use methanol and deionized water to rinse repeatedly obtained product, then is at 60 DEG C true
It is sufficiently dry in empty drying box, it obtains graphene and saves backup.
The graphene of 0.18g is dispersed in 99.82g ethylene glycol using probe sonication, optical microscopy is utilized after 2h
Observe it is well dispersed after, be made 0.18wt% graphene dispersing solution.
(2), the synthesis of graphene modified poly ester:
The graphene dispersing solution of obtained 0.18wt% and terephthalic acid (TPA) are mixed with beating according to 1.2:1 molar ratio, in ester
Before change reaction starts, catalyst, heat stabilizer and antioxidant is added, is added to polyester after mixing in all materials and closes
At in reactor, carry out esterification and polycondensation reaction.Wherein, catalyst charge is the 100ppm of terephthalic acid (TPA) quality, this is urged
Agent uses butyl titanate or titanium ethylene glycolate, and heat stabilizer additional amount is the 0.001% of terephthalic acid (TPA) quality, heat stabilizer
Trimethyl phosphate or alkyl phosphoric acid diester are used, and antioxidant additional amount is the 0.001% of terephthalic acid (TPA) quality, it is anti-oxidant
Agent uses antioxidant 1010.
Esterification temperature when esterification be maintained at 240 DEG C, pressure control in 200~300kPa, esterification is lasting
3.5h, when esterification water yield reaches 98% or more theory, esterification terminates, then controls 30~50pa in vacuum pressure and contract
Poly- reaction, temperature are maintained at 255~265 DEG C, and in 2h, graphene modified poly ester, and graphene modified poly ester is made in the reaction time
Middle graphene content is in 0.05wt%.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form AB double-layer structure, in the slab roller lower than 30 DEG C of temperature to the cooling slab of diaphragm, Zong Xiangla
The temperature stretched is 70~80 DEG C, draw ratio 3.4, and temperature stretching in the transverse direction is 100~110 DEG C, draw ratio 4, again 220~
Thickness is made in 20 μm of graphene modified poly ester film in thermal finalization at a temperature of 230 DEG C, 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, specific step is as follows.
(1), the preparation of graphene dispersing solution.
The reaction flask of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, stirs
The lower solid mixture that 2g graphite powder and 4g sodium nitrate is added is mixed, graphite Powder Particle Size is greater than 95% less than 30 μm, content, carbon content
99.85%, then 10g potassium permanganate is added in four times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min, by water
Bath is heated to 35 DEG C, continues after stirring 5h, is poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continues to stir
Hydrogen peroxide is added after 30min, solution becomes glassy yellow, when reaction to no gas reaction of emerging terminates, filters while hot, uses dilute hydrochloric acid
With deionized water washed product, finally filter cake is placed in 60 DEG C of vacuum oven and is sufficiently dried, it is standby to obtain graphite oxide preservation
With.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, when being warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and is filtered afterwards for 24 hours with this condition, successively use methanol and deionized water to rinse repeatedly, then at 60 DEG C obtained product
Vacuum oven in it is sufficiently dry, obtain graphene and save backup.
The graphene of 0.5g is dispersed in 99.50g ethylene glycol using probe sonication, is seen after 2h using optical microscopy
Examine it is well dispersed after, be made 0.5wt% graphene dispersing solution.
(2), the synthesis of graphene modified poly ester.
The graphene dispersing solution of obtained 0.5wt% and terephthalic acid (TPA) are mixed with beating according to 1.2:1 molar ratio, are being esterified
Before reaction starts, catalyst, heat stabilizer and antioxidant mixing is added, is added to polyester after mixing in all materials
In synthesis reactor, esterification and polycondensation reaction are carried out.Wherein, catalyst charge is the 200ppm of terephthalic acid (TPA) quality, should
Catalyst uses antimony oxide or antimony acetate；Heat stabilizer additional amount is the 0.005% of terephthalic acid (TPA) quality, heat stabilizer
Using trimethyl phosphate and alkyl phosphoric acid diester, the two ratio is unlimited, and antioxidant additional amount is terephthalic acid (TPA) quality
0.005%, antioxidant uses anti-antioxidant 168 or antioxidant 616.
Esterification temperature when esterification be maintained at 250~255 DEG C, pressure control in 100~200kPa, esterification is held
Continuous 4h, when esterification water yield reaches 98% or more theory, esterification terminates, then controls 40~60pa in vacuum pressure and contract
Poly- reaction, temperature are maintained at 265~270 DEG C, and in 2.5h, graphene modified poly ester is made in the reaction time, and graphene is modified poly-
Graphene content is in 0.05wt% in ester.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form ABA three-decker, it is longitudinal with the slab roller lower than 30 DEG C of temperature to the cooling slab of diaphragm
The temperature of stretching is 90~100 DEG C, draw ratio 3, and temperature stretching in the transverse direction is 120~130 DEG C, draw ratio 3.2, again
Thermal finalization at a temperature of 170~200 DEG C winds and thickness is made in 100 μm of graphene modified poly ester film, and wherein A thickness degree is 5
μm。
Embodiment 3
A kind of preparation method of graphene modified poly ester film of the invention, specific step is as follows.
(1), the preparation of graphene dispersing solution.
The reaction flask of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, stirs
The lower solid mixture that 2g graphite powder and 4g sodium nitrate is added is mixed, graphite Powder Particle Size is greater than 95% less than 30 μm, content, carbon content
99.85%, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min,
By heating water bath to 37 DEG C, continues after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continue to stir
Hydrogen peroxide is added after mixing 30min, solution becomes glassy yellow, when reaction to no gas reaction of emerging terminates, filters while hot, with dilute salt
Filter cake is finally placed in 60 DEG C of vacuum oven and sufficiently dries by acid and deionized water washed product, obtains graphite oxide preservation
It is spare.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, when being warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours with this condition, successively use methanol and deionized water to rinse repeatedly obtained product, then is at 60 DEG C true
It is sufficiently dry in empty drying box, it obtains graphene and saves backup.
The graphene of 0.88g is dispersed in 99.12g ethylene glycol using probe sonication, optical microscopy is utilized after 2h
Observe it is well dispersed after, be made 0.88wt% graphene dispersing solution.
(2), the synthesis of graphene modified poly ester.
The graphene dispersing solution of obtained 0.88wt% and terephthalic acid (TPA) are mixed with beating according to 1.2:1 molar ratio, in ester
Before change reaction starts, catalyst, heat stabilizer and antioxidant mixing is added, is added to after mixing in all materials poly-
In ester synthesis reaction device, esterification and polycondensation reaction are carried out.Wherein, catalyst charge is the 300ppm of terephthalic acid (TPA) quality,
The catalyst uses antimony glycol；Heat stabilizer additional amount is the 0.01% of terephthalic acid (TPA) quality, and heat stabilizer uses phosphoric acid
Trimethyl and three (nonyl phenyl) phosphite esters, the two ratio is unlimited, and antioxidant additional amount is terephthalic acid (TPA) quality
0.01%, antioxidant is that both antioxidant 1010 and antioxidant 616 ratio are unlimited.
Esterification temperature when esterification be maintained at 255~260 DEG C, pressure control in 150~250kPa, esterification is held
Continuous 5h, when esterification water yield reaches 98% or more theory, esterification terminates, then controls 70~80pa in vacuum pressure and contract
Poly- reaction, temperature are maintained at 275~285 DEG C, and in 4h, graphene modified poly ester is made in the reaction time；And graphene modified poly ester
Middle graphene content is in 0.25wt%.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form ABA three-decker, it is longitudinal with the slab roller lower than 30 DEG C of temperature to the cooling slab of diaphragm
The temperature of stretching is 100~110 DEG C, draw ratio 3.2, and temperature stretching in the transverse direction is 120~130 DEG C, draw ratio 3, again
Thermal finalization at a temperature of 200~220 DEG C winds and thickness is made in 100 μm of graphene modified poly ester film, and wherein A thickness degree is 5
μm。
Embodiment 4
A kind of preparation method of graphene modified poly ester film of the invention, specific step is as follows.
(1), the preparation of graphene dispersing solution.
The reaction flask of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, stirs
The lower solid mixture that 2g graphite powder and 4g sodium nitrate is added is mixed, graphite Powder Particle Size is greater than 95% less than 30 μm, content, carbon content
99.85%, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min,
By heating water bath to 33 DEG C, continues after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continue to stir
Hydrogen peroxide is added after mixing 30min, solution becomes glassy yellow, when reaction to no gas reaction of emerging terminates, filters while hot, with dilute salt
Filter cake is finally placed in 60 DEG C of vacuum oven and sufficiently dries by acid and deionized water washed product, obtains graphite oxide preservation
It is spare.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, when being warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours with this condition, successively use methanol and deionized water to rinse repeatedly obtained product, then is at 60 DEG C true
It is sufficiently dry in empty drying box, it obtains graphene and saves backup.
The graphene of 1.3g is dispersed in 98.70g ethylene glycol using probe sonication, is seen after 2h using optical microscopy
Examine it is well dispersed after, be made 1.3wt% graphene dispersing solution.
(2), the synthesis of graphene modified poly ester.
The graphene dispersing solution of obtained 1.3wt% and terephthalic acid (TPA) are mixed with beating according to 1.2:1 molar ratio, are being esterified
Before reaction starts, catalyst, heat stabilizer and antioxidant mixing is added, is added to polyester after mixing in all materials
In synthesis reactor, esterification and polycondensation reaction are carried out.Wherein, catalyst charge is the 400ppm of terephthalic acid (TPA) quality, should
Catalyst uses butyl titanate and titanium ethylene glycolate mixture, and the two ratio is unlimited；Heat stabilizer additional amount is terephthalic acid (TPA)
The 0.015% of quality, heat stabilizer use trimethyl phosphate and alkyl phosphoric acid diester, and the two ratio is unlimited；Antioxidant is added
Amount is the 0.02% of terephthalic acid (TPA) quality, and antioxidant uses antioxidant 168 and antioxidant 616, and the two ratio is unlimited.
Esterification temperature when esterification be maintained at 245~255 DEG C, pressure control in 250~300kPa, esterification is held
Continuous 4h, when esterification water yield reaches 98% or more theory, esterification terminates, then controls 60~70pa in vacuum pressure and contract
Poly- reaction, temperature are maintained at 265~275 DEG C, and in 3.5h, graphene modified poly ester is made in the reaction time；And graphene is modified poly-
Graphene content is in 0.5wt% in ester.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form ABA three-decker, it is longitudinal with the slab roller lower than 30 DEG C of temperature to the cooling slab of diaphragm
The temperature of stretching is 90~100 DEG C, draw ratio 3.1, and temperature stretching in the transverse direction is 115~125 DEG C, draw ratio 3.5, again
Thermal finalization at a temperature of 230~240 DEG C winds and required thickness is made 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, specific step is as follows.
(1), the preparation of graphene dispersing solution.
The reaction flask of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, stirs
The lower solid mixture that 2g graphite powder and 4g sodium nitrate is added is mixed, graphite Powder Particle Size is greater than 95% less than 30 μm, content, carbon content
99.85%, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min,
By heating water bath to 35 ± 2 DEG C, continues after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, after
Hydrogen peroxide is added after continuous stirring 30min, solution becomes glassy yellow, when reaction to no gas reaction of emerging terminates, filters while hot, use
Filter cake is finally placed in 60 DEG C of vacuum oven and sufficiently dries, obtains graphite oxide by dilute hydrochloric acid and deionized water washed product
It saves backup.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, when being warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours with this condition, successively use methanol and deionized water to rinse repeatedly obtained product, then is at 60 DEG C true
It is sufficiently dry in empty drying box, it obtains graphene and saves backup.
The graphene of 1.76g is dispersed in 98.24g ethylene glycol using probe sonication, optical microscopy is utilized after 2h
Observe it is well dispersed after, be made 1.76wt% graphene dispersing solution.
(2), the synthesis of graphene modified poly ester.
The graphene dispersing solution of obtained 1.76wt% and terephthalic acid (TPA) are mixed with beating according to 1.2:1 molar ratio, in ester
Before change reaction starts, catalyst, heat stabilizer and antioxidant mixing is added, is added to after mixing in all materials poly-
In ester synthesis reaction device, esterification and polycondensation reaction are carried out.Wherein, catalyst charge is the 350ppm of terephthalic acid (TPA) quality,
The catalyst uses butyl titanate and titanium ethylene glycolate mixture, and the two ratio is unlimited；Heat stabilizer additional amount is terephthaldehyde
The 0.015% of sour quality, heat stabilizer use trimethyl phosphate and alkyl phosphoric acid diester, and the two ratio is unlimited；Antioxidant adds
Enter amount is terephthalic acid (TPA) quality 0.02%, antioxidant uses antioxidant 168 and antioxidant 616, and the two ratio is not
Limit.
Esterification temperature when esterification be maintained at 240~250 DEG C, pressure control in 120~180kPa, esterification is held
Continuous 3h, when esterification water yield reaches 98% or more theory, esterification terminates, then controls 30~40pa in vacuum pressure and contract
Poly- reaction, temperature are maintained at 260~265 DEG C, and in 4h, graphene modified poly ester is made in the reaction time；And graphene modified poly ester
Middle graphene content is in 0.35wt%.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form AB double-layer structure, with the slab roller lower than 30 DEG C of temperature to the cooling slab of diaphragm, Zong Xiangla
The temperature stretched is 100~110 DEG C, draw ratio 3, and temperature stretching in the transverse direction is 120~130 DEG C, draw ratio 2.8, again 215
Thermal finalization at a temperature of~225 DEG C winds and required thickness is made 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, specific step is as follows.
(1), the preparation of graphene dispersing solution.
The reaction flask of 250mL is placed in ice-water bath, the concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, stirs
The lower solid mixture that 2g graphite powder and 4g sodium nitrate is added is mixed, graphite Powder Particle Size is greater than 95% less than 30 μm, content, carbon content
99.85%, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min,
By heating water bath to 36 DEG C, continues after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continue to stir
Hydrogen peroxide is added after mixing 30min, solution becomes glassy yellow, when reaction to no gas reaction of emerging terminates, filters while hot, with dilute salt
Filter cake is finally placed in 60 DEG C of vacuum oven and sufficiently dries by acid and deionized water washed product, obtains graphite oxide preservation
It is spare.
The graphite oxide of 100mg is dispersed in 100g aqueous solution, brown color suspension is obtained, then is divided under ultrasound condition
It is dissipated to few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, when being warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise,
It reacts and filters afterwards for 24 hours with this condition, successively use methanol and deionized water to rinse repeatedly obtained product, then is at 60 DEG C true
It is sufficiently dry in empty drying box, it obtains graphene and saves backup.
The graphene of 1.76g is dispersed in 98.24g ethylene glycol using probe sonication, optical microscopy is utilized after 2h
Observe it is well dispersed after, be made 1.76wt% graphene dispersing solution.
(2), the synthesis of graphene modified poly ester.
The graphene dispersing solution of obtained 1.76wt% and terephthalic acid (TPA) are mixed with beating according to 1.2:1 molar ratio, in ester
Before change reaction starts, catalyst, heat stabilizer and antioxidant mixing is added, is added to after mixing in all materials poly-
In ester synthesis reaction device, esterification and polycondensation reaction are carried out.Wherein, catalyst charge is the 500ppm of terephthalic acid (TPA) quality,
The catalyst uses antimony oxide, antimony acetate and antimony glycol, and ratio is unlimited.Heat stabilizer additional amount is terephthalic acid (TPA) matter
The 0.02% of amount, heat stabilizer are unlimited using trimethyl phosphate, alkyl phosphoric acid diester and three (nonyl phenyl) phosphite esters, ratio.
And antioxidant additional amount is the 0.03% of terephthalic acid (TPA) quality, antioxidant uses antioxidant 168 and antioxidant
616, ratio is unlimited.
Esterification temperature when esterification be maintained at 245~250 DEG C, pressure control in 180~250kPa, esterification is held
Continuous 4.5h, when esterification water yield reaches 98% or more theory, esterification terminates, then controls 55~65pa in vacuum pressure and carry out
Polycondensation reaction, temperature are maintained at 270~280 DEG C, and in 3.4h, graphene modified poly ester is made in the reaction time, and graphene is modified
Graphene content is in 0.5wt% in polyester.
(3)), the machine-shaping of graphene modified poly ester is at film.
Using the graphene modified poly ester being prepared as component A, for normal polyester as B component, component A and B component are logical
It crosses T-die coextrusion and is compounded to form ABA three-decker, it is longitudinal with the slab roller lower than 30 DEG C of temperature to the cooling slab of diaphragm
The temperature of stretching is 90~100 DEG C, draw ratio 3, and temperature stretching in the transverse direction is 115~125 DEG C, draw ratio 2.5, again
Thermal finalization at a temperature of 190~210 DEG C winds and required thickness is made in 400 μm of graphene modified poly ester film, wherein A thickness
Degree is at 20 μm.
Comparative example 1
A, B component is all made of normal polyester, and A layers and B layers are coextruded compound AB double-layer structure by T-die, is being lower than
The slab roller of 30 DEG C of temperature is to the cooling slab of diaphragm, and the temperature of longitudinal stretching is 70~80 DEG C, draw ratio 3.4, cross directional stretch
Temperature be 100~110 DEG C, draw ratio 4, thermal finalization at a temperature of 220~230 DEG C again, wind be made required thickness in 20 μ
M polyester film, wherein A thickness degree is at 1 μm.
Comparative example 2
A, B component is all made of normal polyester, and A layers and B layers are coextruded compound ABA three-decker by T-die, with being lower than
For the slab roller of 30 DEG C of temperature to the cooling slab of diaphragm, the temperature of longitudinal stretching is 90~100 DEG C, draw ratio 3, stretching in the transverse direction
Temperature is 120~130 DEG C, draw ratio 3.2, thermal finalization at a temperature of 170~200 DEG C again, winds and required thickness is made 100
μm polyester film, wherein A thickness degree is at 5 μm.
Comparative example 3
A, B component is all made of normal polyester, and A layers and B layers are coextruded compound AB double-layer structure by T-die, with being lower than
The slab roller of 30 DEG C of temperature is to the cooling slab of diaphragm, and the temperature of longitudinal stretching is 100~110 DEG C, draw ratio 3, cross directional stretch
Temperature be 120~130 DEG C, draw ratio 2.8, thermal finalization at a temperature of 215~225 DEG C again, wind be made required thickness exist
188 μm of polyester films, wherein A thickness degree is at 9.4 μm.
Comparative example 4
A, B component is all made of normal polyester, and A layers and B layers are coextruded compound ABA three-decker by T-die, with being lower than
For the slab roller of 30 DEG C of temperature to the cooling slab of diaphragm, the temperature of longitudinal stretching is 90~100 DEG C, draw ratio 3, stretching in the transverse direction
Temperature is 115~125 DEG C, draw ratio 2.5, thermal finalization at a temperature of 190~210 DEG C again, winds and required thickness is made 400
μm polyester film, wherein A thickness degree is at 20 μm.
The present invention is tested 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:
1, thickness is tested by the prescriptive procedure of the 4th chapter of GB/T 13542.2-2009.
2., tensile strength tested by the prescriptive procedure of GB/T 13542.2-2009 Chapter 11.
3., yellowness index tested by IEC 61215-2005 prescriptive procedure.
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 comparison of comparative example 4, discovery A layer use graphene modified poly ester after, can not only enhanced film tensile strength, moreover it is possible to effectively mention
High film uvioresistant performance.By embodiment 2~4 as can be seen that film tensile strength is not with graphene additive amount at simple
Proportional relation, so the ratio range of the invention be optimum proportioning range.
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,
The synthesis of graphene modified poly ester, the machine-shaping of graphene modified poly ester are at film, specific steps are as follows:
(1), the preparation of graphene dispersing solution:
The concentrated sulfuric acid of 90mL is added to the reaction flask being placed in ice-water bath, is added with stirring the solid of 2g graphite powder and 4g sodium nitrate
Mixture, then 10g potassium permanganate point is at least added three times, reaction temperature control is no more than 20 DEG C, after being stirred to react 30min,
By heating water bath to 35 DEG C, continues after stirring 5h, be poured slowly into 180mL deionized water, by heating water bath to 98 DEG C, continue to stir
Mix and hydrogen peroxide be added after 30min, solution becomes glassy yellow, and reaction to no gas is emerged end, filter while hot, with dilute hydrochloric acid with go
Filter cake is finally placed in 60 DEG C of vacuum oven and sufficiently dries, obtains graphite oxide and save backup by ionized water washed product；
The graphite oxide of 100mg is dispersed in 100g aqueous solution, obtains brown color suspension, then be dispersed under ultrasound condition
Few 1h, obtains stable dispersion liquid；It is then transferred in four-hole boiling flask, is warming up to 80 DEG C, the hydrazine hydrate of 2mL is added dropwise, at this
It reacts under part and filters afterwards for 24 hours, successively use methanol and deionized water to rinse repeatedly, then in 60 DEG C of vacuum drying obtained product
It is sufficiently dry in case, it obtains graphene and saves 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 made 0.18wt%~1.76wt% graphene dispersing solution；
(2), the synthesis of graphene modified poly ester:
The graphene dispersing solution of obtained 0.18wt%~1.76wt% is mixed with terephthalic acid (TPA) according to 1.2:1 molar ratio and is beaten
Catalyst, heat stabilizer and antioxidant mixing are added before esterification starts, adds after mixing in all materials for slurry
Enter into polyester synthesis reactor, carries out esterification and polycondensation reaction, wherein catalyst charge is terephthalic acid (TPA) quality
100~500ppm, heat stabilizer additional amount are the 0.001~0.02% of terephthalic acid (TPA) quality, and antioxidant additional amount is pair
The 0.001~0.03% of phthalic acid quality；Esterification temperature when esterification be maintained at 240~260 DEG C, pressure control exist
100~300K Pa, esterification continue 3~5h, and when esterification water yield reaches 98% or more theory, esterification terminates, then
Vacuum pressure controls 30~80P a and carries out polycondensation reaction, and temperature is maintained at 255~285 DEG C, and in 2~4h, stone is made in the reaction time
Black alkene modified poly ester；
(3), the machine-shaping of graphene modified poly ester is at film:
Using the graphene modified poly ester being prepared as component A, normal polyester passes through T-type as B component, component A and B component
Die head coextrusion is compounded to form AB bilayer or ABA three-decker, and thickness is made through slab, biaxial tension, thermal finalization and winding and exists
20 μm~400 μm of graphene modified poly ester film.
2. a kind of preparation method 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 less than 30 μm, content be greater than 95%, carbon content 99.85%, the concentrated sulfuric acid, potassium permanganate, nitre
Sour sodium, hydrogen peroxide, hydrochloric acid and hydrazine hydrate are that analysis is pure.
3. a kind of preparation method 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. a kind of preparation method of graphene modified poly ester film according to claim 1, it is characterised in that: described urges
Agent is one of or two or more mixed in butyl titanate, titanium ethylene glycolate, antimony oxide, antimony acetate or antimony glycol
Close object.
5. a kind of preparation method of graphene modified poly ester film according to claim 1, which is characterized in that the heat is steady
Determining agent is one of or two or more mixing in trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters
Object.
6. a kind of preparation method of graphene modified poly ester film according to claim 1, it is characterised in that: the antioxygen
Agent is one of or two or more mixture in antioxidant 1010, antioxidant 168 or antioxidant 616.
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| CN110229477A (en) * | 2019-06-11 | 2019-09-13 | 义乌海源塑料制品有限公司 | A kind of graphene situ-formed graft polyester film and preparation method thereof |
| CN110628052B (en) * | 2019-09-25 | 2022-06-14 | 宁波石墨烯创新中心有限公司 | Graphene dispersion liquid, graphene/polymer composite material and preparation method thereof |
| CN110712412A (en) * | 2019-10-14 | 2020-01-21 | 合肥乐凯科技产业有限公司 | Weather-resistant barrier polyester film and manufacturing method thereof |
| CN111393618B (en) * | 2020-04-09 | 2022-10-04 | 海宁海利得纤维科技有限公司 | Preparation method of graphene modified polyester chip, modified polyester fiber and application |
| CN111592640A (en) * | 2020-05-12 | 2020-08-28 | 浙江恒澜科技有限公司 | Preparation method of graphene modified polyester composite material based on liquid phase stripping |
| CN116217876A (en) * | 2023-03-27 | 2023-06-06 | 南通高盟新材料有限公司 | High-barrier heat-resistant solvent-free polyurethane composite material and preparation method thereof |
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