CN105623209B - The method that melt phase polycondensation prepares high water vapor barrier polyester film - Google Patents
The method that melt phase polycondensation prepares high water vapor barrier polyester film Download PDFInfo
- Publication number
- CN105623209B CN105623209B CN201610177157.0A CN201610177157A CN105623209B CN 105623209 B CN105623209 B CN 105623209B CN 201610177157 A CN201610177157 A CN 201610177157A CN 105623209 B CN105623209 B CN 105623209B
- Authority
- CN
- China
- Prior art keywords
- high water
- water vapor
- vapor barrier
- polyester film
- naphthalenedicarboxylic acid
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of method that melt phase polycondensation prepares high water vapor barrier polyester film, phthalic acid, naphthalenedicarboxylic acid, ethylene glycol and heat stabilizer and antioxidant are mixed with beating, the prepolymer that naphthalenedicarboxylic acid terephthalate copolymer is made in esterification is carried out under catalyst action；Grade polymer nano imvite is mixed with scattered be pressed into by nitrogen in reactor of ethylene glycol with prepolymer, vacuum state is gradually evacuated to after distilling out unnecessary ethylene glycol, polycondensation polymerized is carried out and high water vapor barrier polyester is made；Using high water vapor barrier polyester as A layers and B layer components, tri- layers of A B bilayers or ABA are combined into by T-shaped mould coextrusion head through melt pipe, high water vapor barrier polyester film is made through slab, biaxial tension, thermal finalization, cooling and winding.The present invention can reduce cost of material, solve the problems, such as PET and PEN poor compatibilities, avoid and degraded caused by the secondary operation of polyester slice, can improve the vapor water barriers performance of polyester.
Description
Technical field
The present invention relates to a kind of method that melt phase polycondensation prepares high water vapor barrier polyester film, belong to polyester film system
Make technical field.
Background technology
Common polyethylene terephthalate (PET) biaxially oriented film has preferable mechanics electric property, heat-resisting
Outstanding advantages of property, chemical resistance, it is widely used in electric insulation film, electronic component-use film, metal laminate thin film, glass
The numerous areas such as pad pasting, photosensitive material, package decoration, but the deficiency for obstructing steam breathability energy is hindered in hygrothermal environment
Under application.The water vapour that the PET polyester films that wherein thickness is 0.25mm are obtained using GB/T 21529-2008 methods passes through
Rate is generally in 1.5g/ (m2More than 24h), it is difficult to meet the performance requirement of the film under hygrothermal environment.Photovoltaic back requires water
Vapor transmission rates are less than 2g/ (m224h), and industry generally believes that GB/T 21529-2008 methods measure water vapour permeability
Generally in 1.0g/ (m2Being considered as polyester film below 24h) has high water vapor barrier property.
Because the structure of naphthalene is easier in plane so that one of performance most prominent PEN is exactly that gas barrier property is good.
PEN (PEN) is 3~4 times of PET to the barrier of water, and its barrier can be with polyvinylidene chloride
(PVDC) compare, do not influenceed by wet environment.Thus, PEN can be used as beverage and packaging material for food, and be greatly improved production
The shelf-life of product, solar battery group backing can be used as to improve weatherability.But PEN it is expensive be PET 4 times of left sides
The right side, therefore consider to cooperate with use to reduce cost with PET.CN 102225648A disclose " a kind of high-barrier polyester film and its system
Preparation Method ", such a high barrier film sandwich layer are PET, and surface layer is PEN, although improving the knot of two kinds of sections using nucleator
Brilliant speed, the simple cost for using PET material is reduced, but two kinds of polyester still can be layered because compatibility is bad
Phenomenon.CN101240107A discloses a kind of " preparation method on PET composite Nano montmorillonite composite materials " at present, passes through
Montmorillonite and PET in-situ polymerization obtain intercal type and the exfoliated modified PET material coexisted, improve montmorillonite and PET
Compatibility, heat resisting temperature, intensity and stretch modulus.CN102432985A discloses a kind of " PET organic intercalation montmorillonite Composite materials
The preparation method of material ", it was reported that the mode that the method is molded by melt blending can moisture-vapor transmission reduce
60%.But simple melt blending injection is simple mechanical agitation, can not solve nano imvite material in PET
Scattering problem, and the extent of exfoliation of its layer structure is not high.
The content of the invention
It is an object of the invention to provide one kind can reduce cost of material, solve the problems, such as PET and PEN poor compatibilities,
Avoid and degraded caused by the secondary operation of polyester slice, be prepared by the melt phase polycondensation for improving the vapor water barriers performance of polyester
The method that high water vapor obstructs polyester film.
The present invention is that the technical scheme for reaching above-mentioned purpose is：A kind of melt phase polycondensation prepares high water vapor barrier polyester
The method of film, it is characterised in that：Comprise the following steps,
The first step, the prepolymer of synthesizing naphthalic acid terephthalate copolymer,
Phthalic acid, naphthalenedicarboxylic acid, ethylene glycol and heat stabilizer and antioxidant are mixed with beating in reactor, urged
Agent effect is lower to carry out esterification, and the prepolymer of naphthalenedicarboxylic acid terephthalate copolymer is made；Wherein, it is described
The mol ratio of phthalic acid and naphthalenedicarboxylic acid is 0.1：0.9~0.9：0.1, ethylene glycol is in phthalic acid and naphthalenedicarboxylic acid total amount
Mol ratio be 1.06~2.2：1, the addition of the catalyst for 10 based on phthalic acid and naphthalenedicarboxylic acid total amount~
500ppm；The addition of the heat stabilizer is phthalic acid and 0.001~0.02wt% of naphthalenedicarboxylic acid gross mass；It is described anti-
The addition of oxidant is phthalic acid and 0.001~0.03wt% of naphthalenedicarboxylic acid gross mass；
Second step, add grade polymer nano imvite and carry out polycondensation reaction,
Grade polymer nano imvite and ethylene glycol is fully dispersed, it is pressed into by nitrogen in reactor and naphthalenedicarboxylic acid benzene
The prepolymer mixing of naphthalate copolymer, and grade polymer nano imvite is the 0.1wt% of prepolymer gross mass
~10wt%, after distilling out unnecessary ethylene glycol, vacuum state is gradually evacuated to, carries out polycondensation reaction, polymerize and high water vapor resistance is made
Every polyester；
3rd step, high water vapor obstruct polyester machine-shaping into film,
The high water vapor of preparation is obstructed into polyester as A layer components and B layer components, wherein in A layer components, 40%≤naphthalene nucleus
In molar content≤80%, B layer component, 10%≤naphthalene nucleus molar content≤20%, answered by melt pipe by T-shaped mould coextrusion head
Tri- layers of AB bilayers or ABA are synthesized, the height of 20 μm~500 μm of thickness is made through slab, biaxial tension, thermal finalization, cooling and winding
Vapor water barriers polyester film, the layer structure of organo montmorillonite add the passage path of vapor by expansion after stretching,
For improving the vapor water barriers performance of polyester.
Wherein：A thickness degree obstructs the ratio between polyester film gross thickness 1~20 with high water vapor：100.
The catalyst is the one of which of butyl titanate, titanium ethylene glycolate, antimony oxide, antimony acetate or antimony glycol
It is or two or more.
The heat stabilizer be trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters one of which or
Person is two or more.
The antioxidant is antioxidant 1010, the one of which of antioxidant 168 or antioxidant 616 or two kinds
More than.
Esterification reaction temperature control during esterification described in the first step is at 220 DEG C~250 DEG C, reaction time of esterification
Stress control in 2~4h, reactor is controlled to reach theory more than 98%, ester in esterification water yield in 0kpa~300kPa
Change reaction to terminate.
In polycondensation reaction described in second step, the temperature control of polycondensation reaction at 270~285 DEG C, polycondensation reaction it is exhausted
To pressure in 2~25kPa, the time of polycondensation reaction is in 2~4h.
Grade polymer nano imvite described in second step exchanges the Ca being hydrated in montmorillonite for organic cation2+、Na+
Product afterwards.
For the melt pipe extrusion temperature at 220~290 DEG C, the temperature of slab roller is less than 35 DEG C, when carrying out longitudinal stretching
Draft temperature is 70~100 DEG C, and draw ratio is 3 times, then draft temperature when carrying out cross directional stretch is 100~130 DEG C, stretching
Multiple is 3 times, and the temperature of thermal finalization is 220~245 DEG C, and the temperature of cooling is less than 80 DEG C, and rolling after cooling is made high water and steamed
Vapour lock is every polyester film.
Phthalic acid, naphthalenedicarboxylic acid, ethylene glycol are carried out esterification by the present invention under catalyst action, and naphthalene diformazan is made
The prepolymer of sour terephthalate copolymer, thoroughly solve polyethylene terephthalate (PET) and poly- naphthalene two
The problem of formic acid glycol ester (PEN) capacitive difference, then prepolymer and grade polymer nano imvite are subjected to bunching reaction, avoid
Degraded caused by the secondary operation of polyester slice, and by the mode of in-situ polymerization can montmorillonite layered structure more
Peel off well, and the composite material film Jing Guo biaxial tension, can also be to the stripping of nano imvite during stretching
Play a role, making compound post-consumer polymer level nano imvite, those compatible is good together, is uniformly dispersed, is not easy to reunite,
Layer structure after montmorillonite stretching also increases the passage path of water vapour, can reach the effect of barrier, further carry
The water vapor barrier property of superpolyester, the nano montmorillonite modified copolymer composite of grade polymer simultaneously improve vapor water barriers effect
The patent and document of fruit are rarely reported.
The present invention is using the polyester of high naphthalene nucleus content as A layer materials, and the polyester of low naphthalene nucleus content is as B layer materials,
Tri- layers of ABA or AB is prepared into by the compound progress slab of T-shaped mould coextrusion head, longitudinal stretching, cross directional stretch by melt pipe
Two layers of high water vapor barrier polyester film, reduces cost of material, solves PEN manufacturing cost mistake
While high, the vapor water barriers effect of polyethylene terephthalate is added again.The present invention had taken the mode of copolymerization both
Two kinds of polyester compatibilities are added, also improve PET vapor water barriers performance, both serve the effect of complementation.
Brief description of the drawings
Embodiments of the invention are described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the nuclear magnetic resonance figures that high water vapor barrier polyester is made in the embodiment of the present invention 2.
Fig. 2 is the path schematic diagram that vapor of the present invention obstructs polyester film by high water vapor.
Embodiment
The method that the melt phase polycondensation of the present invention prepares high water vapor barrier polyester film, comprises the following steps.
The first step, synthetic prepolymer.
Phthalic acid, naphthalenedicarboxylic acid, ethylene glycol and heat stabilizer and antioxidant are mixed with beating in reactor, this is anti-
Answer kettle to use existing reaction kettle of the esterification, esterification is carried out under catalyst action, naphthalenedicarboxylic acid ethylene is made
The prepolymer of ethylene terephthalate copolymers.Wherein, the mol ratio of phthalic acid and naphthalenedicarboxylic acid of the present invention is 0.10：0.90~0.90：
0.10, ethylene glycol is 1.06~2.2 in the mol ratio of phthalic acid and naphthalenedicarboxylic acid total amount：1, the addition of catalyst is base
In phthalic acid and 10~500ppm of naphthalenedicarboxylic acid gross mass, the catalyst is butyl titanate, titanium ethylene glycolate, three oxidations two
Antimony, antimony acetate, the one of which or two or more of antimony glycol, unlimited ratio during two or more mixing.The heat of the present invention is steady
Phosphoric acid can be used for phthalic acid and 0.001~0.02wt% of naphthalenedicarboxylic acid gross mass, the heat stabilizer by determining the addition of agent
The one of which or two or more of trimethyl, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters, and two or more mixing
When unlimited ratio, the addition of antioxidant of the present invention is phthalic acid, 0.001~0.03wt% of naphthalenedicarboxylic acid gross mass,
Unlimited ratio during the same two or more mixing above.
The mol ratio of phthalic acid and naphthalenedicarboxylic acid can be 0.2 in A layer components of the present invention：0.8~0.6：0.4, and B layer groups
The mol ratio of the middle phthalic acid and naphthalenedicarboxylic acid that divide is can be 0.9：0.1~0.8：0.2, ethylene glycol and phthalic acid and naphthalene two
The mol ratio of formic acid total amount is 1.2~2.0：1, the addition of its catalyst for phthalic acid and naphthalenedicarboxylic acid gross mass 10~
450ppm；The addition of its heat stabilizer is phthalic acid and 0.005~0.015wt% of naphthalenedicarboxylic acid gross mass；And antioxygen
The addition of agent is phthalic acid and 0.005~0.025wt% of naphthalenedicarboxylic acid gross mass.A layer components of the present invention it is specific
Component and proportioning are shown in Table 1, and the concrete component and proportioning of B layer components are shown in Table 2.
Table 1
Table 2
During esterification of the present invention, esterification reaction temperature control at 220 DEG C~250 DEG C, reaction time of esterification control 2~
4h, the Stress control in reactor in 0kpa~300kPa, esterification reaction temperature control preferably of the present invention at 225 DEG C~245 DEG C,
Reaction time of esterification is controlled in 2~4h, and pressure control of the Stress control in reactor in 0kpa~300kPa, the reactor
System is in 150kpa~265kPa, when esterification water yield reaches theory more than 98%, obtained naphthalenedicarboxylic acid phthalic acid ethylene glycol
The prepolymer of ester copolymer, specific process parameter during esterification of the present invention are shown in Table 3.
Table 3
As shown in Figure 1, it is to use obtained naphthalenedicarboxylic acid terephthalate copolymer in the embodiment of the present invention 2
The nuclear magnetic resonance figures of prepolymer, from figure 1 it appears that solving asking for PET and PEN poor compatibilities by the way of copolymerization
Topic.
Second step, the polycondensation reaction added in the presence of organo montmorillonite.
Grade polymer nano imvite and ethylene glycol is fully dispersed, and the amount of filling of grade polymer nano imvite is pre-polymerization
0.1wt%~10wt% of thing gross mass, the amount of filling of the grade polymer nano imvite are the 0.5wt% of prepolymer gross mass
~8wt%.The grade polymer nano imvite of the present invention exchanges the Ca being hydrated in montmorillonite for organic cation2+、Na+Production afterwards
Thing, the organic cation is using 12~OTAC, 12~octadecyldimethyl ammonium chloride, double ten
Eight alkyl dimethyl ammonium chloride types, the first base phosphonium bromide of 12~octadecane base three, the butyl phosphonium bromide of 12~octadecyl three, ten
The phenyl-bromide Phosphonium of two~octadecyl three, 12~octadecyl trimethyl phosphonium chloride, the tributyl chlorination of 12~octadecyl
One or both of Phosphonium and 12~octadecyl triphenyl phosphonium chloride are mixed above, and montmorillonite is exchanged by organic cation
The Ca of middle hydration2+、Na+And obtain grade polymer nano imvite.
The present invention can be disperseed in another kettle grade polymer nano imvite with ethylene glycol, and pass through feed pipe
Delivered under nitrogen effect in reactor, make it is scattered after grade polymer nano imvite be pressed into by nitrogen in reactor and naphthalene
The prepolymer of dioctyl phthalate terephthalate copolymer is mixed, and the fashionable pressure controllable system of nitrogen pressure of the present invention exists
0.2~0.8Mpa, after distilling out unnecessary ethylene glycol, vacuum state is gradually evacuated to, carries out polycondensation reaction, polymerize and high water vapor is made
Obstruct polyester.Grade polymer nano imvite passes through in-situ polymerization so that and montmorillonite layered structure is preferably peeled off, and by double
To the composite material film of stretching, the stripping of nano imvite can also be played a role, solved during stretching
Scattering problem of the nano imvite material in PET.
The temperature of polycondensation reaction of the present invention is at 270~285 DEG C, and the vacuum absolute pressure of polycondensation reaction is in 0~50Pa, polycondensation
The time of reaction is in 2~4h.The specific amount of filling of Inventive polymers level nano imvite and prepolymer is shown in Table 4, polycondensation
Specific process parameter during reaction response is shown in Table 5.
Table 4
Table 5
The present invention enters the prepolymer of naphthalenedicarboxylic acid terephthalate copolymer with grade polymer nano imvite
Row polycondensation reaction, make grade polymer nano imvite and naphthalenedicarboxylic acid terephthalate copolymer compatibility good, no
Easily reunite.
3rd step, high water vapor obstruct polyester machine-shaping into film.
The high water vapor of preparation is obstructed into polyester as A layer components and B layer components, wherein in A layer components, 40%≤naphthalene nucleus
In molar content≤80%, B layer component, 10%≤naphthalene nucleus molar content≤20%, answered by melt pipe by T-shaped mould coextrusion head
Tri- layers of AB bilayers or ABA are synthesized, the height of 20 μm~500 μm of thickness is made through slab, biaxial tension, thermal finalization, cooling and winding
Vapor water barriers polyester film.Melting tube extrusion temperature of the present invention is 220~290 DEG C, and the temperature of slab roller is less than 35 DEG C, carries out
Draft temperature during longitudinal stretching is 70~100 DEG C, and draw ratio is 3 times, then draft temperature when carrying out cross directional stretch is 100
~130 DEG C, draw ratio is 3 times, and the temperature of thermal finalization is 220~245 DEG C, and the temperature of cooling is less than 80 DEG C, is received after cooling
Roll to obtain the ratio between high water vapor barrier polyester film, A thickness degree of the present invention and high water vapor barrier polyester film gross thickness 1~
20：100.As shown in Figure 2, the inventors discovered that deploying to add vapor after the layer structure of organo montmorillonite is by stretching
Passage path, improve the vapor water barriers performance of polyester.
Naphthalene nucleus molar content in specific thickness and the A layer and B layers of high water vapor barrier polyester film produced by the present invention
It is shown in Table 6.
Table 6
By 21529-2008 pairs of high water vapor barrier polyester films produced by the present invention of GB/T and the routine of condition of equivalent thickness
PET film is detected, and for the moisture-vapor transmission of each embodiment and conventional PET film with being shown in Table 7, its performance is shown in Table 8 institutes
Show.
Table 7
Table 8
As can be seen that high water vapor barrier polyester film barrier property produced by the present invention is far above the mark of photovoltaic back
Standard, there is higher vapor water barriers performance.
Claims (9)
1. a kind of method that melt phase polycondensation prepares high water vapor barrier polyester film, it is characterised in that：Comprise the following steps,
The first step, the prepolymer of synthesizing naphthalic acid terephthalate copolymer,
Phthalic acid, naphthalenedicarboxylic acid, ethylene glycol and heat stabilizer and antioxidant are mixed with beating in reactor, in catalyst
Effect is lower to carry out esterification, and the prepolymer of naphthalenedicarboxylic acid terephthalate copolymer is made；Wherein, described benzene two
The mol ratio of formic acid and naphthalenedicarboxylic acid is 0.1：0.9~0.9：0.1, ethylene glycol rubs in phthalic acid and naphthalenedicarboxylic acid total amount
You are than being 1.06~2.2：1, the addition of the catalyst is 10~500ppm based on phthalic acid and naphthalenedicarboxylic acid total amount；
The addition of the heat stabilizer is phthalic acid and 0.001~0.02wt% of naphthalenedicarboxylic acid gross mass；The antioxidant
Addition for phthalic acid and naphthalenedicarboxylic acid gross mass 0.001~0.03wt%；
Second step, add grade polymer nano imvite and carry out polycondensation reaction,
Grade polymer nano imvite and ethylene glycol is fully dispersed, it is pressed into by nitrogen in reactor and naphthalenedicarboxylic acid benzene diformazan
Sour glycol ester copolymer prepolymer mixing, and grade polymer nano imvite be prepolymer gross mass 0.1wt%~
10wt%, after distilling out unnecessary ethylene glycol, vacuum state is gradually evacuated to, carries out polycondensation reaction, polymerize and high water vapor barrier is made
Polyester；
3rd step, high water vapor obstruct polyester machine-shaping into film,
The high water vapor of preparation is obstructed into polyester as A layer components and B layer components, wherein in A layer components, 40%≤naphthalene nucleus mole
In content≤80%, B layer component, 10%≤naphthalene nucleus molar content≤20%, it is combined into by melt pipe by T-shaped mould coextrusion head
A B are double-deck or tri- layers of ABA, the high water that 20 μm~500 μm of thickness is made through slab, biaxial tension, thermal finalization, cooling and winding steam
For vapour lock every polyester film, the layer structure of organo montmorillonite adds the passage path of vapor by expansion after stretching, is used for
Improve the vapor water barriers performance of polyester.
2. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
A thickness degree obstructs the ratio between polyester film gross thickness 1~20 with high water vapor：100.
3. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
The catalyst is butyl titanate, titanium ethylene glycolate, antimony oxide, antimony acetate or the one of which of antimony glycol or two kinds
More than.
4. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
The heat stabilizer be trimethyl phosphate, the one of which of alkyl phosphoric acid diester or three (nonyl phenyl) phosphite esters or two kinds with
On.
5. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
The antioxidant is antioxidant 1010, the one of which or two or more of antioxidant 168 or antioxidant 616.
6. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
Esterification reaction temperature control described in the first step during esterification at 220 DEG C~250 DEG C, reaction time of esterification control 2~
4h, reach theory more than 98% in esterification water yield, esterification terminates.
7. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
In polycondensation reaction described in second step, the temperature control of polycondensation reaction is at 270~285 DEG C, and the absolute pressure of polycondensation reaction is 2
~25kPa, Stress control in reactor is in 0kpa~300kPa, and the time of polycondensation reaction is in 2~4h.
8. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
Grade polymer nano imvite described in second step exchanges the Ca being hydrated in montmorillonite for organic cation2+、Na+Production afterwards
Thing.
9. the method that melt phase polycondensation according to claim 1 prepares high water vapor barrier polyester film, it is characterised in that：
For the melt pipe extrusion temperature at 220~290 DEG C, the temperature of slab roller is less than 35 DEG C, carries out draft temperature during longitudinal stretching
For 70~100 DEG C, draw ratio is 3 times, then draft temperature when carrying out cross directional stretch is 100~130 DEG C, draw ratio 3
Times, the temperature of thermal finalization is 220~245 DEG C, and the temperature of cooling is less than 80 DEG C, and it is poly- that high water vapor barrier is made in rolling after cooling
Ester film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610177157.0A CN105623209B (en) | 2016-03-25 | 2016-03-25 | The method that melt phase polycondensation prepares high water vapor barrier polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610177157.0A CN105623209B (en) | 2016-03-25 | 2016-03-25 | The method that melt phase polycondensation prepares high water vapor barrier polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105623209A CN105623209A (en) | 2016-06-01 |
| CN105623209B true CN105623209B (en) | 2018-02-02 |
Family
ID=56038581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610177157.0A Active CN105623209B (en) | 2016-03-25 | 2016-03-25 | The method that melt phase polycondensation prepares high water vapor barrier polyester film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105623209B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910788B (en) * | 2017-03-10 | 2018-08-17 | 宁波长阳科技股份有限公司 | A kind of high resistant water type solar energy backboard polyester film and preparation method thereof |
| CN107134502B (en) * | 2017-05-04 | 2019-04-05 | 宁波长阳科技股份有限公司 | A kind of three-layer co-extruded high reflection type solar cell backboard film and preparation method thereof |
| CN109054311B (en) * | 2018-07-23 | 2020-11-06 | 杭州大华塑业有限公司 | High-temperature-resistant polyester film and preparation method thereof |
| CN110577631A (en) * | 2019-09-11 | 2019-12-17 | 重庆晟淦新材料科技有限公司 | industrial preparation method of polyethylene naphthalate |
| CN115710410B (en) * | 2022-08-24 | 2023-08-22 | 中山市泓溢薄膜科技有限公司 | Preparation method and application of polybutylene adipate-terephthalate material |
| CN115710412B (en) * | 2022-10-31 | 2023-10-13 | 安徽金田高新材料股份有限公司 | High-barrier biaxially oriented degradable polyester film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710926B2 (en) * | 1989-07-11 | 1995-02-08 | 帝人株式会社 | Polyester hollow molding |
| JP2863570B2 (en) * | 1989-10-06 | 1999-03-03 | 三井化学株式会社 | Copolymerized polyethylene terephthalate and its use |
| CN100500522C (en) * | 2005-03-03 | 2009-06-17 | 徐跃 | High-barrier double-wall plastic bottle and method for manufacturing same |
-
2016
- 2016-03-25 CN CN201610177157.0A patent/CN105623209B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105623209A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105623209B (en) | The method that melt phase polycondensation prepares high water vapor barrier polyester film | |
| JP5862055B2 (en) | Polyolefin resin film | |
| CN102873954B (en) | A kind of polyester film that can directly seal and preparation method | |
| CN103203934A (en) | Heat shrinkage copolyester film and preparation method thereof | |
| CN106132692B (en) | Multilayer structure making and its manufacture method, packaging material and product, the protection sheet material of the electronic equipment and coating fluid obtained using it | |
| CN103627150A (en) | Preparation method of polyether material, polyether film and preparation method thereof | |
| JP2013046805A (en) | Method for manufacturing gel mat | |
| TWI545144B (en) | Hydrolysis-resistant polyester film | |
| WO2010100959A1 (en) | Polyester film for solar cell, and process for producing same | |
| CN101910287A (en) | Polypropylene resin composition, molded article produced from the resin composition, and method for production of the molded article | |
| WO2013088728A1 (en) | Heat-resistant food container, and manufacturing method for same | |
| CN106832823B (en) | A kind of high temperature resistant PET polyester film and preparation method thereof | |
| CN106573446A (en) | Multilayer structure, packaging material including same, and method for manufacturing said multilayer structure | |
| CN102597075A (en) | Biaxially oriented film for electrical insulation purposes, and film capacitor produced using biaxially oriented film for electrical insulation purposes | |
| JP2011021180A (en) | Polyester film for solar cell and method for producing the same | |
| CN104292776A (en) | Raw material and technique for making copolyester film | |
| EP3013583B1 (en) | Coextruded multilayer film with propylene-based polymer and ethylene-based polymer | |
| CN101550247B (en) | Stretched film | |
| CN102596570B (en) | Multi-layer structure | |
| CN109648966B (en) | High-barrier polyester film | |
| CN104788822A (en) | Polymeric membrane material for packaging and preparation method thereof | |
| CN105504249A (en) | Hydrolysis-resistant fluorine-containing copolyester resin, hydrolysis-resistant fluorine-containing copolyester composite basal membrane and preparation method thereof | |
| CN115584043A (en) | High-barrier biodegradable film and preparation method and application thereof | |
| CN100369745C (en) | Biaxially oriented polyester film | |
| EP3148800B1 (en) | Coextruded multilayer film with beta-propylene-based barrier layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |