CN110272550A - A kind of preparation method of organic-silicon-modified PET optical transparent film - Google Patents
A kind of preparation method of organic-silicon-modified PET optical transparent film Download PDFInfo
- Publication number
- CN110272550A CN110272550A CN201811392212.3A CN201811392212A CN110272550A CN 110272550 A CN110272550 A CN 110272550A CN 201811392212 A CN201811392212 A CN 201811392212A CN 110272550 A CN110272550 A CN 110272550A
- Authority
- CN
- China
- Prior art keywords
- silicon
- organic
- modified pet
- transparent film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to organosilicon technical fields, to solve the problems, such as that common PET film heat sealability is poor, the invention proposes a kind of preparation methods of organic-silicon-modified PET optical transparent film: being first esterified into the organic-silicon-modified polyethylene terephthalate of low polymerization degree, then final minification is polymerized to the organic-silicon-modified polyethylene terephthalate of final polyester product of high polymerization degree, is subsequently formed into the film of better heat stability.The organic-silicon-modified PET of preparation, while reducing the crystal property of PET, improves its ageing-resistant performance, simultaneously as having silicone segments in modified PET molecule, to improve the organosilicon of pet sheet face coating and the bonding force of PET film.
Description
Technical field
The present invention relates to organosilicon technical fields, and in particular to a kind of preparation of organic-silicon-modified PET optical transparent film
Method.
Background technique
General PET resin is crystal type high polymer, and one side crystallinity and grain size will affect the optical of PET film
Energy such as transparency, another aspect PET has biggish crystallization tendency after hot-stretch and thermal finalization, as sealed to it
Words, it will generate serious contraction distortion (shrinking deformation 2 ~ 2.5%).Therefore, common PET film does not have heat sealability.For
It solves the problems, such as this, usually carries out it with PE film or CPP film compound.PE or CPP and adhesive material must be increased in this way
Material and Compound Machining process lead to material of taking a lot of work, and increase cost, thus limit the application of PET film to a certain extent.
Modification by copolymerization is to improve one of the effective ways of PET heat sealability, and existing method is to add binary when preparing PET
Alcohol or binary acid, to reduce the crystallinity of PET.The characteristics of this unformed PET copolymer be it is transparent it is high, fusing point is low, high glaze,
Low haze, high convergency, heat sealable, application is wider.
In many factors for influencing PET material service life, photooxidation droping is concerned the destruction of its performance.It is ultraviolet
Radiation is to lead to the main reason of PET photooxidation droping.In general, the method for improving PET ultraviolet light resistant performance is that addition light is steady
Determine agent and coats anti-radiation coating in pet sheet face.(Wang Huayin, Hu Guoliang, Zhou Ying, Pan little Dan, ultraviolet radioactive is to polyester fiber
The influence of structure and performance, material science and technique, 2008,16(4): 582-588；Ma Chenghua, Chen Ying, Wu Peihua, PET's
Ultraviolet ageing performance and mechanism study, polyester industrial, 2015,28(3): 19-24；Chen Kang, Yi Zhiwen, Zhou Guiqiang, Yu Jian
It puts down, Wang Biao, Zhang Yumei, Wang Huaping, the preparation of anti-ultraviolet ageing high-strength polyester fibers and performance study, synthetic fibre maker
Industry, 2 017,40 (5): 1-6；Zhang Shiming, Luo Chunming, the research of anti-ultraviolet polyester film, insulating materials 2010,
43 (5): 3-6) addition antioxidant may will affect the light transmittance of PET material, and can then increase in pet sheet face coating uvioresistant coating
Add production stage and production cost.
Summary of the invention
To solve the problems, such as that common PET film heat sealability is poor, the invention proposes a kind of organic-silicon-modified PET optics
The preparation method of transparent membrane prepares organic-silicon-modified PET, while reducing the crystal property of PET, improves its resistance to ag(e)ing
Can, in addition, because having silicone segments in modified PET molecule, to improve the organosilicon and PET of pet sheet face coating
The bonding force of film.
Since organosilicon macromolecule has many advantages, such as that shrinking percentage is low, dimensionally stable, ultraviolet light resistant, therefore the present invention is logical
Cross following technical scheme realization: a kind of preparation method of organic-silicon-modified PET optical transparent film is following steps:
(1) organosilicon materials that both ends are hydroxyl are added into terephthalic acid (TPA) and ethylene glycol mixture, under catalyst,
133 ~ 180mmHg, the organic-silicon-modified polyethylene terephthalate of low polymerization degree is first esterified at 180 ~ 220 DEG C；
Preferably, the usage amount of terephthalic acid (TPA), ethylene glycol, the organosilicon materials that both ends are hydroxyl is rubbed according to carboxyl and hydroxyl
, than 1:1.05 ~ 1.3, both ends are that the organosilicon materials of hydroxyl are 0.5 ~ 15wt% of quality of glycol for you.
The both ends are that the organosilicon materials of hydroxyl are selected from α, ω-diphenyl dihydroxy silicone oil, α, alpha, omega-dihydroxy dimethyl
Silicone oil, α, alpha, omega-dihydroxy methyl phenyl silicone oil, α, alpha, omega-dihydroxy dimethyl fluorosilicon oil, α, alpha, omega-dihydroxy aminomethyl phenyl fluorine silicon
One or more of oil.Because of α, ω-diphenyl dihydroxy silicone oil anti-ultraviolet ageing performance is not so good as α, alpha, omega-dihydroxy dimethyl
Silicone oil, α, alpha, omega-dihydroxy methyl phenyl silicone oil, α, alpha, omega-dihydroxy dimethyl fluorosilicon oil, α, alpha, omega-dihydroxy aminomethyl phenyl fluorine silicon
Oil, and diphenyl silicon oxygen chain link may also crystallize, therefore preferably, the organosilicon materials that both ends are hydroxyl are α, ω-two
Hydroxyl dimethicone, α, alpha, omega-dihydroxy methyl phenyl silicone oil, α, alpha, omega-dihydroxy dimethyl fluorosilicon oil, α, alpha, omega-dihydroxy first
Base phenyl fluorosilicon oil, viscosity are 10 ~ 1000cp.Because both ends are that the organosilicon polymer viscosity of hydroxyl is higher, molecular weight is got over
Height, that is, molecule segment are longer, and the hydroxyl reactivity at both ends will be made lower；Moreover, its molecular weight is higher, Xiang Tongzhi
The both ends of amount are that the molecular number of the organosilicon polymer of hydroxyl is fewer, so that PET molecule segment, which is separated realization, reduces PET
The crystalline ability of copolymer is lower, so, more preferably, both ends are α in the organosilicon materials of hydroxyl, alpha, omega-dihydroxy
Dimethicone, α, alpha, omega-dihydroxy methyl phenyl silicone oil, α, alpha, omega-dihydroxy dimethyl fluorosilicon oil, α, alpha, omega-dihydroxy methylbenzene
Base fluorosilicon oil, viscosity are 10 ~ 400cp.
The catalyst usage amount is the 10 of the organosilicon materials gross mass that terephthalic acid (TPA), ethylene glycol and both ends are hydroxyl
~500ppm.Preferably, the catalyst be selected from germanium oxide, antimony oxide, antimony acetate, antimony glycol, butyl titanate,
One or more of potassium fluotitanate.
Preferably, the oligomeric degree is X=1 ~ 4, reaction time of esterification is 1 ~ 6h, since X=1 ~ 4 all can in polycondensation process
It generates, therefore low polymerization degree is the mixture of X=1 ~ 4.
(2) the organic-silicon-modified PET resin that then final minification is polymerized to high polymerization degree at 133 ~ 180mmHg, 280 ~ 300 DEG C is cut
Piece；
Preferably, the high polymerization degree is n=100 ~ 200, the poly- reaction time is 4 ~ 12h eventually.
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, is then squeezed out in an extruder in 260 ~ 300 DEG C,
Then it is quenched 2 ~ 8min in 20 ~ 40 DEG C of water, then through biaxial tension, obtains organic-silicon-modified PET optical transparent film.
The organic-silicon-modified PET resin is sliced first predrying, to prevent hydrolysis, then squeezes out in extruder through T shape mould
Unformed sheet, is quenched by cooler drum or coolant liquid, so that it is kept amorphous state, so as to stretch orientation.
Biaxial orientation process are as follows: sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature along sheet plane
Extending direction stretches 2 ~ 4 times, and being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating temperature 98 ~ 100
DEG C, 100 ~ 120 DEG C of draft temperature, draw ratio 2.5 ~ 4.0,230 ~ 240 DEG C of heat setting temperature, the film after vertically and horizontally stretching also needs
By thermal finalization, is deformed with eliminating by stretching the film generated, organic-silicon-modified PET optical transparent film is made.
When the present invention is using direct esterification preparation PET, two are added into raw material terephthalic acid (TPA) and ethylene glycol mixture
End is the organosilicon materials of hydroxyl, and it is organic-silicon-modified poly- to benzene two that low polymerization degree (such as X=1 ~ 4) is first esterified at 180 ~ 220 DEG C
Formic acid glycol ester, then at 260 ~ 300 DEG C final minification be polymerized to high polymerization degree final polyester product it is organic-silicon-modified poly- to benzene
Naphthalate (n=100 ~ 200).The organic-silicon-modified PET resin of gained is first then sliced predrying, to prevent hydrolysis, so
Unformed sheet is squeezed out through T shape mould in 260 DEG C in an extruder afterwards, by being quenched 2 ~ 8min in 20 ~ 40 DEG C of cooling waters, makes its guarantor
Amorphous state is held, so as to stretch orientation.Sheet is again through stenter biaxial tension, just at PET film.
The introducing of silicone segments in the method for the present invention, reduces the crystal property of PET, so that the contraction for reducing PET becomes
Shape improves the heat sealability of pet polymer.Meanwhile because organosilicon material has ageing-resistant, cold-resistant thermal shock resistance properties preferably etc.
Advantage, with organic block modification by copolymerization, can be improved PET copolymer material ageing-resistant performance and cold-resistant thermal shock resistance properties.Separately
Outside, the introducing of silicone segments, so that PET copolymer material possesses polysiloxanes segment, to improve the coating of pet sheet face
The bonding force of organosilicon and PET copolymer film.
Compared with prior art, the beneficial effects of the present invention are:
(1) introducing of silicone segments, reduces the crystal property of PET, to reduce the contraction distortion of PET, it is poly- to improve PET
Close the heat sealability of object；
(2) ageing-resistant performance of PET copolymer material is improved；
(3) make PET copolymer material possess polysiloxanes segment, be total to improve the organosilicon that pet sheet face is coated with PET
The bonding force of homopolymer film.
Specific embodiment
Below by embodiment, invention is further described in detail, but embodiment is not to the scope of the present invention
Limitation.
Embodiment 1
(1) in clean, to have stirring, decompression vacuum pumping and condenser system reaction kettle, addition 166.13Kg terephthalic acid (TPA),
62.068Kg ethylene glycol, 0.31Kg Diphenylsilanediol and 0.04587Kg germanium oxide, the first ester at 133mmHg, 200 DEG C
Change reaction 2h and obtains low polymerization degree (X=1 ~ 4), organic-silicon-modified polyethylene terephthalate.
(2) 133mmHg, the final polyester product organosilicon that final polycondensation reaction 8h obtains high polymerization degree at 280 ~ 285 DEG C change
Property polyethylene terephthalate (PET, n=150).
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, to prevent hydrolysis, then in an extruder in 280 DEG C
Unformed sheet is squeezed out through T shape mould, 2min is quenched by 25 DEG C of cooling waters, so that it is kept amorphous state, so as to stretch orientation.It is thick
Piece is again through stenter biaxial tension, just at PET film.Sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature
3 times or so are stretched along sheet plane extending direction, being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating
98 ~ 100 DEG C of temperature, 100 ~ 120 DEG C of draw ratios 2.5 ~ 4.0 of draft temperature, 230 ~ 240 DEG C of heat setting temperature.After vertically and horizontally stretching
Film also need by thermal finalization, deformed with eliminating by stretching the film generated, organic-silicon-modified PET optical transparent film be made.
The contraction shape of the organic-silicon-modified PET optical transparent film of gained becomes 1.2%, through ultraviolet ageing 1000h without xanthochromia.
Embodiment 2
(1) in clean, to have stirring, decompression vacuum pumping and condenser system reaction kettle, addition 166.13Kg terephthalic acid (TPA),
The α of 80.00Kg ethylene glycol, 2.42Kg viscosity 80cp, alpha, omega-dihydroxy dimethicone and 0.124Kg antimony oxide,
180mmHg, 180 DEG C of elder generation esterification 4h obtain low polymerization degree (X=1 ~ 4) organic-silicon-modified polyethylene terephthalate.
(2) at 180mmHg, 280 ~ 285 DEG C final polycondensation reaction 12h obtain high polymerization degree final polyester product organosilicon
Modified polyethylene terephthalate (PET, n=200).
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, to prevent hydrolysis, then in an extruder in 280 DEG C
Unformed sheet is squeezed out through T shape mould, 6min is quenched by 40 DEG C of cooling waters, so that it is kept amorphous state, so as to stretch orientation.It is thick
Piece is again through stenter biaxial tension, just at PET film.Sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature
3 times or so are stretched along sheet plane extending direction, being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating
98 ~ 100 DEG C of temperature, 100 ~ 120 DEG C of draw ratios 2.5 ~ 4.0 of draft temperature, 230 ~ 240 DEG C of heat setting temperature.After vertically and horizontally stretching
Film also need by thermal finalization, deformed with eliminating by stretching the film generated, organic-silicon-modified PET optical transparent film be made.
The contraction shape of the organic-silicon-modified PET optical transparent film of gained becomes 1.5%, through ultraviolet ageing 1000h without xanthochromia.
Embodiment 3
(1) in clean, to have stirring, decompression vacuum pumping and condenser system reaction kettle, addition 166.13Kg terephthalic acid (TPA),
The α of 69.078Kg ethylene glycol, 10.3617Kg viscosity 800cp, alpha, omega-dihydroxy methyl phenyl silicone oil and 0.00235Kg ethylene glycol
Antimony, elder generation esterification 3h obtains low polymerization degree (X=1 ~ 4) organic-silicon-modified poly terephthalic acid second two at 160mmHg, 200 DEG C
Alcohol ester.
(2) at 160mmHg, 290 ~ 295 DEG C final polycondensation reaction 6h obtain high polymerization degree final polyester product organosilicon
Modified polyethylene terephthalate (PET, n=130).
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, to prevent hydrolysis, then in an extruder in 260 DEG C
Unformed sheet is squeezed out through T shape mould, 2min is quenched by 30 DEG C of cooling waters, so that it is kept amorphous state, so as to stretch orientation.It is thick
Piece is again through stenter biaxial tension, just at PET film.Sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature
3 times or so are stretched along sheet plane extending direction, being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating
98 ~ 100 DEG C of temperature, 100 ~ 120 DEG C of draw ratios 2.5 ~ 4.0 of draft temperature, 230 ~ 240 DEG C of heat setting temperature.After vertically and horizontally stretching
Film also need by thermal finalization, deformed with eliminating by stretching the film generated, organic-silicon-modified PET optical transparent film be made.
The contraction shape of the organic-silicon-modified PET optical transparent film of gained becomes 0.8%, through ultraviolet ageing 1000h without xanthochromia.
Embodiment 4
(1) in clean, to have stirring, decompression vacuum pumping and condenser system reaction kettle, addition 166.13Kg terephthalic acid (TPA),
The α of 62.068Kg ethylene glycol, 3.6034Kg viscosity 1000cp, alpha, omega-dihydroxy dimethyl fluorine containing silicone oil and 0.0235Kg antimony acetate,
Elder generation esterification 2h obtains low polymerization degree (X=1 ~ 4) organic-silicon-modified polyethylene terephthalate at 160mmHg, 190 DEG C
Ester.
(2) at 160mmHg, 295 ~ 300 DEG C final polycondensation reaction 10h obtain high polymerization degree final polyester product organosilicon
Modified polyethylene terephthalate (PET, n=180).
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, to prevent hydrolysis, then in an extruder in 290 DEG C
Unformed sheet is squeezed out through T shape mould, 2min is quenched by 30 DEG C of cooling waters, so that it is kept amorphous state, so as to stretch orientation.It is thick
Piece is again through stenter biaxial tension, just at PET film.Sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature
3 times or so are stretched along sheet plane extending direction, being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating
98 ~ 100 DEG C of temperature, 100 ~ 120 DEG C of draw ratios 2.5 ~ 4.0 of draft temperature, 230 ~ 240 DEG C of heat setting temperature.After vertically and horizontally stretching
Film also need by thermal finalization, deformed with eliminating by stretching the film generated, organic-silicon-modified PET optical transparent film be made.
The contraction shape of the organic-silicon-modified PET optical transparent film of gained becomes 1.6%, through ultraviolet ageing 800h without xanthochromia.
Embodiment 5
(1) in clean, to have stirring, decompression vacuum pumping and condenser system reaction kettle, addition 166.13Kg terephthalic acid (TPA),
The α of 62.068Kg ethylene glycol, 2.6034Kg viscosity 1000cp, the α of alpha, omega-dihydroxy dimethyl fluorine containing silicone oil, 1kg viscosity 10cp,
Alpha, omega-dihydroxy dimethicone and 0.01Kg butyl titanate, 0.02Kg potassium fluotitanate, are first esterified at 150mmHg, 220 DEG C
It reacts 2h and obtains low polymerization degree (X=1 ~ 4) organic-silicon-modified polyethylene terephthalate.
(2) at 150mmHg, 290 ~ 295 DEG C final polycondensation reaction 10h obtain high polymerization degree final polyester product organosilicon
Modified polyethylene terephthalate (PET, n=180).
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, to prevent hydrolysis, then in an extruder in 290 DEG C
Unformed sheet is squeezed out through T shape mould, 5min is quenched by 35 DEG C of cooling waters, so that it is kept amorphous state, so as to stretch orientation.It is thick
Piece is again through stenter biaxial tension, just at PET film.Sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature
3 times or so are stretched along sheet plane extending direction, being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating
98 ~ 100 DEG C of temperature, 100 ~ 120 DEG C of draw ratios 2.5 ~ 4.0 of draft temperature, 230 ~ 240 DEG C of heat setting temperature.After vertically and horizontally stretching
Film also need by thermal finalization, deformed with eliminating by stretching the film generated, organic-silicon-modified PET optical transparent film be made.
The contraction shape of the organic-silicon-modified PET optical transparent film of gained becomes 1.4%, through ultraviolet ageing 800h without xanthochromia.
Embodiment 6
(1) in clean, to have stirring, decompression vacuum pumping and condenser system reaction kettle, addition 166.13Kg terephthalic acid (TPA),
The α of 62.068Kg ethylene glycol, 2.000Kg viscosity 200cp, alpha, omega-dihydroxy aminomethyl phenyl fluorine containing silicone oil, 1.000Kg viscosity 300cp
α, alpha, omega-dihydroxy methyl phenyl silicone oil and 0.0235Kg potassium fluotitanate, elder generation esterification 2h is obtained low at 280Pa, 200 DEG C
The degree of polymerization (X=1 ~ 4) organic-silicon-modified polyethylene terephthalate.
(2) at 140mmHg, 280 ~ 285 DEG C final polycondensation reaction 10h obtain high polymerization degree final polyester product organosilicon
Modified polyethylene terephthalate (PET, n=180).
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, to prevent hydrolysis, then in an extruder in 280 DEG C
Unformed sheet is squeezed out through T shape mould, 8min is quenched through 25 DEG C of cooling waters, so that it is kept amorphous state, so as to stretch orientation.Sheet
Again through stenter biaxial tension, just at PET film.Sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and edge at this temperature
Sheet plane extending direction stretches 3 times or so, and being allowed to orientation can be improved crystallinity and reach higher temperature: cross directional stretch preheating temperature
98 ~ 100 DEG C of degree, 100 ~ 120 DEG C of draw ratios 2.5 ~ 4.0 of draft temperature, 230 ~ 240 DEG C of heat setting temperature.After vertically and horizontally stretching
Film also needs to be deformed to eliminate by stretching the film generated by thermal finalization, organic-silicon-modified PET optical transparent film is made.
The contraction shape of the organic-silicon-modified PET optical transparent film of gained becomes 0.7%, through ultraviolet ageing 1200h without xanthochromia.
Claims (10)
1. a kind of preparation method of organic-silicon-modified PET optical transparent film, which is characterized in that the preparation method is following
Step:
(1) organosilicon materials that both ends are hydroxyl are added into terephthalic acid (TPA) and ethylene glycol mixture, under catalyst,
133 ~ 180mmHg, the organic-silicon-modified polyethylene terephthalate of low polymerization degree is first esterified at 180 ~ 220 DEG C；
(2) the organic-silicon-modified PET resin that then final minification is polymerized to high polymerization degree at 133 ~ 180mmHg, 280 ~ 300 DEG C is sliced；
(3) the organic-silicon-modified PET resin of gained is first sliced predrying, is then squeezed out in an extruder in 260 ~ 300 DEG C, then
2 ~ 8min in 20 ~ 40 DEG C of water, then through biaxial tension, obtain organic-silicon-modified PET optical transparent film.
2. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 1, which is characterized in that
Terephthalic acid (TPA), ethylene glycol, the organosilicon materials that both ends are hydroxyl usage amount according to carboxyl and hydroxyl molar ratio 1:1.05 ~
1.3, both ends are that the organosilicon materials of hydroxyl are 0.5 ~ 15wt% of quality of glycol.
3. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 1 or 2, feature exist
It is that the organosilicon materials of hydroxyl are selected from α in, both ends, ω-diphenyl dihydroxy silicone oil, α, alpha, omega-dihydroxy dimethicone, α,
Alpha, omega-dihydroxy methyl phenyl silicone oil, α, alpha, omega-dihydroxy dimethyl fluorosilicon oil, α, one in alpha, omega-dihydroxy aminomethyl phenyl fluorosilicon oil
Kind is several.
4. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 3, which is characterized in that
Both ends are α in the organosilicon materials of hydroxyl, alpha, omega-dihydroxy dimethicone, α, alpha, omega-dihydroxy methyl phenyl silicone oil, α, ω-two
Hydroxyl dimethyl fluorosilicon oil, α, the viscosity of alpha, omega-dihydroxy aminomethyl phenyl fluorosilicon oil are 10 ~ 1000cp.
5. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 1, which is characterized in that
The catalyst be selected from one of germanium oxide, antimony oxide, antimony acetate, antimony glycol, butyl titanate, potassium fluotitanate or
It is several.
6. a kind of preparation method of organic-silicon-modified PET optical transparent film, feature exist according to claim 1 or 5
In 10 that, the catalyst usage amount is the organosilicon materials gross mass that terephthalic acid (TPA), ethylene glycol and both ends are hydroxyl ~
500ppm。
7. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 1, which is characterized in that
Oligomeric degree is X=1 ~ 4 in step (1), and the reaction time is 1 ~ 6h.
8. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 1, which is characterized in that
High polymerization degree is n=100 ~ 200 in step (2), and the poly- reaction time is 4 ~ 12h eventually.
9. a kind of preparation method of organic-silicon-modified PET optical transparent film according to claim 1, which is characterized in that
Step (3) squeezes out unformed sheet through T shape mould in extruder.
10. according to claim 1 or a kind of preparation method of organic-silicon-modified PET optical transparent film, feature described in 9 exist
In biaxial orientation process in step (3) are as follows: sheet is exactly preheated to 86 ~ 87 DEG C by longitudinal stretching, and at this temperature along sheet
2 ~ 4 times: 98 ~ 100 DEG C of cross directional stretch preheating temperature of plane extending direction stretching, 100 ~ 120 DEG C of draft temperature, draw ratio 2.5 ~
4.0,230 ~ 240 DEG C of heat setting temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811392212.3A CN110272550B (en) | 2018-11-21 | 2018-11-21 | Preparation method of organic silicon modified PET optical transparent film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811392212.3A CN110272550B (en) | 2018-11-21 | 2018-11-21 | Preparation method of organic silicon modified PET optical transparent film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110272550A true CN110272550A (en) | 2019-09-24 |
| CN110272550B CN110272550B (en) | 2022-05-27 |
Family
ID=67958011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811392212.3A Active CN110272550B (en) | 2018-11-21 | 2018-11-21 | Preparation method of organic silicon modified PET optical transparent film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110272550B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132392A (en) * | 1991-12-24 | 1992-07-21 | Union Carbide Chemicals & Plastics Technology Corporation | Hydrophilic silicone-modified polyester resin and fibers and films made therefrom |
| CN102604026A (en) * | 2011-02-17 | 2012-07-25 | 浙江深蓝轻纺科技有限公司 | Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof |
| CN104387546A (en) * | 2014-12-17 | 2015-03-04 | 武汉大学 | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof |
| CN105175769A (en) * | 2015-09-21 | 2015-12-23 | 常州大学 | Preparing method for silicon-containing optical anti-reflection polyester film |
| WO2018102805A1 (en) * | 2016-12-02 | 2018-06-07 | Ppg Industries Ohio, Inc. | Silicone-containing polyesters, coating compositions containing the same, and coatings formed therefrom |
-
2018
- 2018-11-21 CN CN201811392212.3A patent/CN110272550B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132392A (en) * | 1991-12-24 | 1992-07-21 | Union Carbide Chemicals & Plastics Technology Corporation | Hydrophilic silicone-modified polyester resin and fibers and films made therefrom |
| JPH06100676A (en) * | 1991-12-24 | 1994-04-12 | Union Carbide Chem & Plast Technol Corp | Hydrophilic-silicone-modified polyester resin and its production |
| CN102604026A (en) * | 2011-02-17 | 2012-07-25 | 浙江深蓝轻纺科技有限公司 | Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof |
| CN104387546A (en) * | 2014-12-17 | 2015-03-04 | 武汉大学 | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof |
| CN105175769A (en) * | 2015-09-21 | 2015-12-23 | 常州大学 | Preparing method for silicon-containing optical anti-reflection polyester film |
| WO2018102805A1 (en) * | 2016-12-02 | 2018-06-07 | Ppg Industries Ohio, Inc. | Silicone-containing polyesters, coating compositions containing the same, and coatings formed therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110272550B (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI503349B (en) | Polycarbonate resin and transparency film containing the same | |
| JP2018059108A (en) | Polycarbonate resin, method for producing the same and optical molding | |
| JP5587617B2 (en) | Polycarbonate resin and film with low photoelastic constant | |
| TWI591092B (en) | Polyester resin, optical lens and poptical lens system | |
| CN108556441A (en) | A kind of optical polyester film | |
| US9234986B2 (en) | Polyester resin and optical lens | |
| WO2013147091A1 (en) | Long retardation film, circularly polarizing plate and organic el panel | |
| JP6597158B2 (en) | Thermoplastic resin and optical molded body comprising the same | |
| KR20180003963A (en) | Polymethylpropylene terephthalate and preparation method thereof | |
| CN110272550A (en) | A kind of preparation method of organic-silicon-modified PET optical transparent film | |
| JP4048955B2 (en) | Polyester and its production method | |
| KR101705241B1 (en) | White polyester film and preparation method thereof | |
| CN117304459B (en) | Bio-based sulfur-containing high-refraction polyester and preparation method and application thereof | |
| AU2013245537B2 (en) | Method for producing heat shrinkable polyester film | |
| JP6136810B2 (en) | Polyethylene terephthalate film and method for producing the same | |
| TWI542629B (en) | Polyester | |
| KR102242647B1 (en) | Copolyester containing cyclic aliphatic units, preparing method of the same, and optical film with low water absorption and low birefringence including the same | |
| CN111040211B (en) | Preparation method and application of biaxially oriented polyester film | |
| KR101127951B1 (en) | Biaxially-oriented polyester film and preparation method thereof | |
| JP2010174089A (en) | Optical polyester resin | |
| CN117510922A (en) | High-light-transmittance polyester film and preparation method thereof | |
| TW202302699A (en) | Polyester resin | |
| KR20020055550A (en) | Method for producing industrial polyethylene naphthalate | |
| CN101671433A (en) | Method for preparing transparent alicyclic polyester with low stress optical coefficient | |
| KR20120107646A (en) | Biaxially oriented polyester film having improved color property |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230627 Address after: Room 204, No. 9, Tianyuan Lane, Gongshu District, Hangzhou, Zhejiang 310000 Patentee after: Zhejiang Boliheng Technology Co.,Ltd. Address before: 2318 yuhangtang Road, Yuhang District, Hangzhou City, Zhejiang Province Patentee before: Hangzhou Normal University |