CN112375237B - Functional master batch production system for polyester film - Google Patents

Functional master batch production system for polyester film Download PDF

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CN112375237B
CN112375237B CN202011067337.6A CN202011067337A CN112375237B CN 112375237 B CN112375237 B CN 112375237B CN 202011067337 A CN202011067337 A CN 202011067337A CN 112375237 B CN112375237 B CN 112375237B
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polyester
functional
master batch
preparation mechanism
acid
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CN112375237A (en
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吴培服
邓十全
吴迪
池卫
罗海洋
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Jiangsu Shuangxing Color Plastic New Materials Co Ltd
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Jiangsu Shuangxing Color Plastic New Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02Homopolymers or copolymers of hydrocarbons
    • C08J2425/04Homopolymers or copolymers of styrene
    • C08J2425/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The application discloses a function masterbatch production system for polyester film, including polyester carrier preparation mechanism and function material preparation mechanism, polyester carrier preparation mechanism includes at least one esterification reaction cauldron and at least one polycondensation reaction cauldron, and the function material slice of function material preparation mechanism preparation adds in the polycondensation reaction cauldron of polyester carrier preparation mechanism, and then the preparation obtains the function masterbatch of this application. The functional master batch production system integrates the functional material preparation mechanism and matched equipment such as extrusion, slicing, drying and connecting pipelines on the basis of the existing polyester preparation mechanism, and can be used for continuously and efficiently producing the functional master batch. The polyester film added with the functional master batch can be applied to the application fields of glass, building materials, printing, medicine and health, optics, packaging and the like.

Description

Functional master batch production system for polyester film
Technical Field
The application relates to a production system of a functional additive for a polyester film, wherein the functional additive is a functional master batch prepared into a chip form. In particular, the present application relates to a functional masterbatch production system for polyester film. The polyester film added with the functional master batch can be applied to the application fields of glass, building materials, printing, medicine and health, optics, packaging and the like.
Background
Polyesters are a generic term for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids. Polyesters include various types, and PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PTT (polytrimethylene terephthalate), PCT (poly 1, 4-cyclohexanedimethanol terephthalate), and the like are well known to the public, and particularly, a polyester film represented by PET is generally a film material obtained by using polyethylene terephthalate as a raw material, forming a thick sheet by an extrusion method, and then performing biaxial stretching, and is widely used in the fields of glass, building materials, printing, medical hygiene, optics, packaging, and the like.
CN 110684323A discloses a PET polyester film production process, which comprises the steps of firstly preparing PET copolyester resin, and then mixing polyester master batch and the PET copolyester resin according to the mass ratio of 25:100 to obtain a mixed material. And drying the mixed material, performing melt extrusion on the dried mixed material to prepare a casting sheet, stretching the casting sheet in a bidirectional stretching mode to prepare a film, and finally rolling and slitting the film to obtain a finished product. The mixing of the PET copolyester resin and the polyester master batch increases the water vapor transmission resistance of the film obtained by stretching, so that the PET polyester film is suitable for being used in a damp and hot environment. The polyester master batch mixed with the PET copolyester resin comprises two polyester master batches, wherein one polyester master batch contains 30% -50% of titanium dioxide with the particle size of 0.2-0.4 mu m, the other polyester master batch contains 0.2% -2% of silicon dioxide with the particle size of 2-3.5 mu m, and the two polyester master batches are mixed according to the weight ratio of 1: 1. The two polyester master batches in the prior art are used as partial raw materials of the polyester film, the content of the two polyester master batches in the polyester film reaches 20 percent, the content of titanium dioxide in one polyester master batch is as high as 30 to 50 percent, the master batch has too high content of insoluble inorganic matters, is difficult to disperse, can cause serious influence on the light transmittance of the film, and is difficult to obtain the high-quality polyester film.
CN 109880311A discloses an anti-blocking master batch and a preparation method thereof, wherein the anti-blocking master batch comprises 100-150 parts by weight of polyethylene terephthalate resin and 1-5 parts by weight of anti-blocking filler, the anti-blocking filler is inorganic particles with the particle size of 100-400nm, and a polyester film prepared by using the anti-blocking master batch has small and smooth surface roughness. The anti-blocking filler is modified nano calcium carbonate particles, and the preparation method comprises the steps of firstly carrying out ultrasonic dispersion by using deionized water, then carrying out reaction by using a stearic acid ethanol solution, and then carrying out suction filtration, washing, drying and grinding to obtain the modified nano calcium carbonate particles. The master batch is prepared by adding PET and anti-blocking filler into a high-speed mixer for pre-dispersion mixing, then carrying out melt extrusion by a double-screw extruder, and granulating.
CN 109054314A discloses a high-transparency polyester film and a preparation method thereof, wherein the high-transparency polyester film comprises a core layer and surface layers arranged on one side or two sides of the core layer, and the surface layers comprise 93-97% of polyethylene terephthalate, 0.08-0.25% of inorganic particles and 2.75-6.92% of other additives. The inorganic particles are coated and modified by a compatilizer. In the prior art, inorganic particles which are coated and modified by a compatilizer are added into the surface layer, so that the bonding capacity of the inorganic particles and polyethylene glycol terephthalate in the surface layer of the polyester film is improved, and gaps which are formed around the inorganic particles in the polyester film after biaxial stretching forming are reduced, so that the problem of reduction of light transmittance caused by the existence of the inorganic particles is solved; the inorganic particles coated and modified by the compatilizer have strong binding force with the polyethylene terephthalate, and a series of appearance problems caused by falling of the inorganic particles are prevented. The modification method of the inorganic particles in the prior art comprises the steps of ultrasonically dispersing the inorganic particles and a compatilizer in an organic solvent, recovering the organic solvent, and drying to obtain the inorganic particles coated by the compatilizer.
The above prior arts all mention adding various inorganic particles in the preparation process of the polyester film, and can also understand the effect of the inorganic particles on the performance of the polyester film, but the particle agglomeration problem in the actual production process of the specific polyester film is still very common, and the quality of the polyester film is greatly affected.
Disclosure of Invention
The technical problem to be solved by the present application is to provide a functional masterbatch production system for polyester film to reduce or avoid the aforementioned problems.
In order to solve the technical problem, the application provides a functional master batch production system for a polyester film, which comprises a polyester carrier preparation mechanism and a functional material preparation mechanism, wherein the polyester carrier preparation mechanism comprises at least one esterification reaction kettle and at least one polycondensation reaction kettle, and the functional material preparation mechanism comprises an aerogel particle dryer, a polylactic acid particle dryer, a first polystyrene or polyethylene particle dryer and a second polystyrene or polyethylene particle dryer; inputting the dry particles of the aerogel particle dryer, the polylactic acid particle dryer and the first polystyrene or polyethylene particle dryer into a polydimethylsiloxane stirring tank through pipelines, and inputting the paste material output from the polydimethylsiloxane stirring tank and the dry particles of the second polystyrene or polyethylene particle dryer into a first extruding machine through pipelines to prepare functional material slices; and adding the functional material slices prepared by the first extruder into a polycondensation reaction kettle of a polyester carrier preparation mechanism through a pipeline for mixing reaction, and inputting the final product in the polycondensation reaction kettle into a second extruder through a pipeline to prepare the functional master batch.
Preferably, the functional material preparation mechanism further comprises a first dicing machine and a first dryer, which are disposed between the first extruder and the polycondensation reaction kettle of the polyester carrier preparation mechanism.
Preferably, the output end of the second extruder is further connected with a second slicer and a second dryer through pipelines.
Preferably, the functional material chips are added to the polycondensation reaction kettle, and at the same time, poly m-xylylene adipamide is added.
Preferably, the content of the functional material slices in the functional master batch is 30 wt% -40 wt%; the content of the poly m-xylylene adipamide in the functional master batch is 0.1-0.2 wt%.
The functional master batch production system integrates the functional material preparation mechanism and matched equipment such as extrusion, slicing, drying and connecting pipelines on the basis of the existing polyester preparation mechanism, and can be used for continuously and efficiently producing the functional master batch.
The polyester film produced by the functional master batch prepared by the system and the method has the transverse heat shrinkage rate of not less than 65 percent at 120 ℃ within 2-3 seconds, the light transmittance of not less than 95 percent, the tensile strength of not less than 300MPa and the film surface friction coefficient of not more than 0.5; the thickness is between 10 and 75 mu m, and the width is 250-8700 mm. The polyester film prepared by the functional master batch has the advantages of high light transmittance and unidirectional thermal shrinkage, excellent strength and flame retardant property, uniform shrinkage, excellent transparency, ductility and toughness, simple raw material category, low cost and easy large-scale popularization and application, and can be produced on the existing BOPET film production line.
Drawings
The drawings are only for purposes of illustrating and explaining the present application and are not to be construed as limiting the scope of the present application. Wherein,
fig. 1 shows a schematic configuration of a functional masterbatch production system for mylar according to one embodiment of the present application.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present application, embodiments of the present application will now be described with reference to the accompanying drawings. Wherein like parts are given like reference numerals.
The application provides a production system of a functional additive for a polyester film, wherein the functional additive can be a functional master batch prepared into a chip form. The polyester film added with the functional master batch can be applied to the application fields of glass, building materials, printing, medicine and health, optics, packaging and the like. The polyester film of the present invention may have a single-layer structure or a multi-layer structure. The functional masterbatch of the present invention is preferably added as a functional additive in the form of a chip to a polyester film of a single layer structure or a surface layer of a polyester film of a multilayer structure, for example, a surface layer and/or a bottom layer of a polyester film of a three-layer structure.
The polyester referred to herein is a polyester formed from one or more species selected from among polybasic carboxylic acids containing dibasic acids and their ester-forming derivatives, and one or more species selected from among polyhydric alcohols containing dihydric alcohols; or a polyester formed from a hydroxycarboxylic acid or an ester-forming derivative thereof; or a polyester formed from a cyclic ester. The polyester can be produced by a conventionally known method. For example, taking the preparation of PET as an example, it can be obtained by: a method of performing polycondensation after esterification of terephthalic acid and ethylene glycol; or a method in which an alkyl ester of terephthalic acid such as dimethyl terephthalate is subjected to a transesterification reaction with ethylene glycol and then subjected to polycondensation.
In the process of producing the polyester film, the functional master batch can be added into common polyester in a slicing mode, so that the produced polyester film has the functional characteristics of the functional master batch. For example, 1 to 30 wt% of the functional master batch of the present invention may be added to 70 to 99 wt% of polyester containing no other component, and then a polyester film is produced by processes such as extrusion and stretching, or a surface layer structure of a heat shrinkable film, a release film or an optical film is obtained by a multilayer co-extrusion process.
The functional master batch for the polyester film comprises a polyester carrier, polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane. When the functional master batch is suitable for being added into the main polyester PET, for example, the polyester carrier of the functional master batch can be correspondingly selected to be the PET, so that the compatibility of the functional master batch and the main polyester PET is better, and the performance of the original polyester is prevented from being changed by unnecessary ester exchange. Likewise, when the functional masterbatch is suitable for addition to other host polyesters, such as PBT, PTT, PCT, or PETG, the polyester carrier in the functional masterbatch is preferably the same as the host polyester. Of course, under the conditions of similar properties and relatively good compatibility, the polyester carrier and the main polyester in the functional master batch can also be different, but the control of the product quality is possibly difficult. The silica aerogel in the functional master batch is commonly called as 'blue smoke', is a low-density silica aerogel which is porous and disordered and has a nano-scale continuous network structure, has a larger specific surface area than common silica, and is more difficult to disperse than common silica by using phosphate coupling agents and silane coupling agents (such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane and the like) in the prior art. Because of its very low density, it floats easily and cannot be dispersed into the polyester. The porous structure of the aerogel can generate strong bonding force with polylactic acid, polypropylene ethylene or polyethylene through polydimethylsiloxane, the density of the aerogel is increased, and the aerogel can be sunk into the polyester.
The polyester carrier in the functional masterbatch of the present application may be formed by, for example, polycondensation of a dibasic acid and a glycol. For example, the dibasic acid component thereof, including, but not limited to, terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 3, 4 '-diphenylether dicarboxylic acid, hexahydrophthalic acid, 2, 7-naphthalenedicarboxylic acid, phthalic acid, 4' -methylenebisbenzoic acid, oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 3-methyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1, 11-undecanedicarboxylic acid, 1, 10-decanedicarboxylic acid, undecanedicarboxylic acid, 1, 12-dodecanedicarboxylic acid, hexadecanedioic acid, docosanedicarboxylic acid, lignoceric acid, dimer acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1-cyclohexanediacetic acid, fumaric acid, maleic acid, and hexahydrophthalic acid. Further, these may be used alone or in combination of two or more.
For example, the diol component includes, but is not limited to, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 14-tetradecanediol, 1, 16-hexadecanediol, dimer diol, diethylene glycol, triethylene glycol, poly (ethylene ether) glycol, poly (butylene ether) glycol, branched diols, hexanediol, or combinations or derivatives thereof, 1, 4-cyclohexanedimethanol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-2, 4-pentanediol, neopentyl glycol, 2-methyl-1, 4-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2, 5-ethyl-1, 3-hexanediol, 2-diethyl-1, 3-propanediol, 1, 3-hexanediol. Further, these may be used alone or in combination of two or more.
The polyester carrier in the functional masterbatch of the present invention may be formed of hydroxycarboxylic acids and their ester-forming derivatives, or may be formed of cyclic esters.
For example, the hydroxycarboxylic acid component includes, but is not limited to: lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid and the like. The ester-forming derivatives of hydroxycarboxylic acids include, but are not limited to: dimethyl terephthalate, dimethyl isophthalate, dimethyl 2, 6-naphthalenedicarboxylate, dimethyl 3, 4 '-diphenylether dicarboxylate, dimethyl hexahydrophthalate, dimethyl 2, 7-naphthalenedicarboxylate, dimethyl phthalate, dimethyl 4, 4' -methylenebisbenzoate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl azelate, dimethyl 1, 3-cyclohexanedicarboxylate and dimethyl 5-sulfoisophthalate. Further, these may be used alone or in combination of two or more. For example, cyclic esters include, but are not limited to: epsilon-caprolactone, beta-propiolactone, beta-methyl-beta-propiolactone, delta-valerolactone, glycolide, lactide, and the like. Further, these may be used alone or in combination of two or more.
The polyester carrier used in the present application is preferably polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly-1, 4-cyclohexanedimethanol terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate, and a copolymer thereof, and particularly preferably polyethylene terephthalate (PET) and a copolymer thereof.
The polyester support of the present application is preferably produced industrially by a polycondensation method in which, for example, PET is esterified or transesterified with terephthalic acid or dimethyl terephthalate and ethylene glycol to produce bishydroxyethyl terephthalate, and the bishydroxyethyl terephthalate is polycondensed at high temperature under vacuum using a catalyst. In one embodiment, esterification can be carried out from terephthalic acid, ethylene glycol, cyclohexanedimethanol, a catalyst and a heat stabilizer; or esterification is carried out by taking terephthalic acid, ethylene glycol, isophthalic acid, a catalyst and a heat stabilizer as raw materials. In another embodiment, the catalyst is any one of Ti/Si series non-heavy metal catalyst and antimony trioxide, and the addition amount of the catalyst is 0.01-0.09% of the mass of the polyester. In another specific embodiment, the heat stabilizer is a phosphoric acid compound, and the addition amount of the phosphoric acid compound is 0.0003-0.030% of the mass of the polyester; the phosphoric acid compound comprises any one of phosphoric acid, phosphorous acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphate and triethyl phosphate. The preparation of the polyester support of another embodiment is as follows: adding 5.0kg of terephthalic acid, 2.2kg of ethylene glycol and 1.10g of germanium dioxide into a 20L general polymerization reaction kettle, carrying out esterification reaction at 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), releasing pressure to normal pressure when the water yield reaches 1200ml, adding 1.025g of triphenyl phosphate, stirring for 10 minutes at normal pressure, raising the temperature and reducing the pressure to 280 ℃ and below 100Pa, and after 1-3 hours of reaction, extruding, granulating and drying to obtain the polyester carrier.
In the functional master batch for the polyester film, the components except the polyester carrier can be uniformly mixed, extruded and granulated by using equipment such as an extruder to obtain functional material slices, then the functional material slices are added into the polyester carrier, and finally the functional master batch is prepared. That is, the functional masterbatch for polyester film of the present application includes a polyester carrier and a functional material chip including polystyrene or polyethylene, polylactic acid, aerogel and polydimethylsiloxane. Preferably, the functional material slice comprises the following components in parts by weight: 60-70 parts of aerogel, 10-15 parts of polylactic acid, 30-60 parts of polystyrene or polyethylene and 30-40 parts of polydimethylsiloxane. The functional material slices can be used as independent additives to be directly added into polyester to produce a polyester film, the properties of the independent functional material slices are soft, and in order to facilitate long-term storage and avoid pollution, the functional material slices are preferably added into a polyester carrier at the content of 30 wt% -40 wt% to prepare a functional master batch, namely, the content of the functional material slices in the functional master batch is 30 wt% -40 wt%. For example, in the process of preparing the polyester carrier, 60 parts by weight of functional material chips (the content of the functional material chips is 37.5 wt%) can be added into the polyester carrier per 100 parts by weight of the expected yield, and the functional material chips are uniformly mixed, extruded and cut into granules to obtain the functional master batch of the application.
In addition, because the content of the functional material slices in the prepared functional master batch is 30 wt% -40 wt%, in order to avoid the oxidation and decomposition of the effective components during storage, in the process of preparing the functional master batch, the functional material slices are preferably added into a polyester carrier at the content of 30 wt% -40 wt%, and 0.1 wt% -0.5 wt% of poly m-xylylene adipamide is simultaneously added.
When the functional material chips are added to the polyester carrier, the polylactic acid is easily decomposed into water and carbon dioxide at high temperature, thereby being separated from the aerogel. The silicon atoms of the aerogel are combined with the silicon atoms of the polydimethylsiloxane, the macromolecules at the other end of the polydimethylsiloxane can be combined with the alkane of the polyester, and the aerogel can still be kept in the polyester through the polydimethylsiloxane even if the affinity of polylactic acid is lost. And carbon dioxide generated by the decomposed polylactic acid can form bubbles to bring other solid inorganic particles in the polyester to the surface layer of the product, for example, a metal salt antioxidant, a catalyst and the like can be brought to the surface layer part of the polyester, so that a convex-concave structure can be formed on the surface of the polyester, the anti-blocking effect is realized, the adding amount of the inorganic anti-blocking particles can be reduced, and the light transmittance of the polyester is improved. For example, it is detected that the anti-blocking effect of the polyester film is not obviously changed and the light transmittance of the polyester film can be greatly improved under the condition of reducing the dosage of the anti-blocking particles by 20 to 30 percent.
In one embodiment of the present application, 60 to 70 parts by weight of aerogel particles having a particle size of 0.5 to 10 μm can be preferably dried at 120 ℃ for 4 hours; drying 10-15 parts by weight of polylactic acid particles with the particle size of less than 0.5mm at 110 ℃ for 4 hours; drying 10-15 parts by weight of polystyrene or polyethylene particles with the particle size of less than 0.5mm at 110 ℃ for 4 hours. And putting the dried particles into 30-40 parts by weight of liquid polydimethylsiloxane at normal temperature, and stirring at the speed of 1000-1500rpm for 2 hours to obtain a paste material. 20-45 parts by weight of polystyrene or polyethylene particles (which can be dried only in a purchased particle form without being crushed) dried at 110 ℃ for 4 hours are put into an extruder together with the paste material, and the mixture is melted, extruded, granulated and dried to obtain functional material slices after uniform mixing.
Polydimethylsiloxane is insoluble in water, has poor affinity with common inorganic particles, can be dispersed by shearing force of high-speed stirring, and is not suitable for being directly added into polyester. The silicon atoms of the polydimethylsiloxane can form firm molecular combination with the silicon atoms of the aerogel, the binding force is strong, and the polydimethylsiloxane and the aerogel cannot be separated by applying high-speed stirring. The polymer at the other end of the polydimethylsiloxane can be combined with the alkane of the polyester, and the binding force is strong. Not only has good dispersion effect, but also can not be separated from the combination to generate agglomeration phenomenon due to the molecular combination. While the ordinary silicon dioxide has smooth surface and insufficient bonding force with the existing coupling agent, the ordinary silicon dioxide can be separated from the coupling agent when the stirring force is too large during dispersion, and the ordinary silicon dioxide can still agglomerate when added into polyester.
The functional material slices can be selectively put into the polyester carrier in the preparation process of the polyester carrier, for example, the functional material slices can be put into the esterification stage in the preparation process of the polyester carrier, or after the esterification, or in the polycondensation stage, or after the polycondensation is completed, and finally, the functional master batch for the polyester film is obtained by extrusion granulation.
Preferably, the functional material chip selection of the present application is put into the polycondensation stage of the polyester carrier, for example, referring to the preparation steps of the polyester carrier described previously, the functional masterbatch for the polyester film of the present application can be prepared by the following steps: adding terephthalic acid, ethylene glycol and germanium dioxide into a general polymerization reaction kettle, carrying out esterification reaction at 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), after the esterification is finished, releasing the pressure to normal pressure, adding triethyl phosphate and functional material slices for polycondensation, stirring for 10 minutes at normal pressure, raising the temperature and reducing the pressure to 280 ℃ and below 100Pa, after the reaction is finished for 1-3 hours, extruding, granulating and drying to obtain the functional master batch. As described above, 0.1 to 0.5 wt% of poly (m-xylylene adipamide) may be added simultaneously with the addition of the functional pellet.
Through detection, after the functional master batch is added, the influence on the viscosity of the original polyester is small, and the stability of the parameters of the polyester film is favorably maintained. In addition, the glossiness, the wear resistance, the high temperature resistance and the heat insulation performance of the polyester film are all improved by 10 to 20 percent.
The production method of the functional masterbatch of the present application will be described in detail with reference to the functional masterbatch production system for polyester film of the present application shown in fig. 1.
As shown in the drawing, the functional masterbatch production system for mylar of the present application includes a polyester carrier preparation mechanism 100 and a functional material preparation mechanism 200.
The polyester carrier preparation mechanism 100 can adopt existing equipment to produce and prepare the polyester carrier through a known process. For example, the polyester support may be produced using a three or five pot process as is well known in the art. In a specific embodiment of the present application, the polyester carrier preparation mechanism 100 may include at least one esterification reaction kettle 101 and at least one polycondensation reaction kettle 102, the materials for polyester are firstly subjected to a high-temperature and high-pressure esterification reaction in the esterification reaction kettle 101, and after the esterification is completed, the materials are transferred to the polycondensation reaction kettle 102, at this time, the functional material slices obtained by the functional material preparation mechanism 200 may be added to the polycondensation reaction kettle 102, so as to prepare the functional masterbatch of the present application. A small amount of m-xylylene adipamide may be added simultaneously with the addition of the functional material chips. Of course, it should be understood by those skilled in the art that the polyester carrier preparation mechanism 100 of the present application is not limited to only one esterification reaction kettle and one polycondensation reaction kettle connected in series therewith, and for example, in the known five-kettle production process, two esterification reaction kettles and three polycondensation reaction kettles are generally connected in series in sequence, wherein the first two polycondensation reaction kettles are used for the pre-polycondensation reaction, and the last polycondensation reaction kettle is used for the final polycondensation reaction. The functional material slices can be selectively added into any one polycondensation reaction kettle, and preferably the functional material slices are added into the polycondensation reaction kettle of the final condensation reaction, so that unnecessary copolymerization impurities are prevented from being introduced, and the characteristics of the functional material are prevented from being influenced.
The functional masterbatch production system of this application has integrated equipment such as functional material preparation mechanism 200 and supporting extrusion, section, drying and connecting line on the basis of current polyester preparation mechanism, can be used to produce the functional masterbatch of this application in succession high-efficiently.
Specifically, as shown in fig. 1, the functional material preparation mechanism 200 of the present application includes an aerogel particle dryer 201, a polylactic acid particle dryer 202, a first polystyrene or polyethylene particle dryer 203, and a second polystyrene or polyethylene particle dryer 204. The output ends of the aerogel particle dryer 201, the polylactic acid particle dryer 202, and the first polystyrene or polyethylene particle dryer 203 are connected to a polydimethylsiloxane agitator tank 205 through pipes. The dried particles of the aerogel particle dryer 201, the polylactic acid particle dryer 202, and the first polystyrene or polyethylene particle dryer 203 are input into the polydimethylsiloxane agitator tank 205 through a pipeline, and are mixed and stirred with polydimethylsiloxane in the polydimethylsiloxane agitator tank 205 to obtain a paste. The output ends of the polydimethylsiloxane agitator tank 205 and the second polystyrene or polyethylene pellet dryer 204 are connected to the first extruder 206 by pipes. The pasty material output from the polydimethylsiloxane stirring tank 205 and the dried particles of the second polystyrene or polyethylene particle dryer 204 are input into the first extruder 206 through pipelines to prepare functional material slices.
The functional material slices prepared by the first extruder 206 are further added into the polycondensation reaction kettle 102 of the polyester carrier preparation mechanism 100 through a pipeline for mixing reaction, and after the polycondensation reaction is completed, the final product in the polycondensation reaction kettle 102 can be further input into the second extruder 106 through a pipeline to prepare the functional master batch of the present application. A small amount of m-xylylene adipamide may be added simultaneously with the addition of the functional material chips.
In a specific embodiment, the functional material preparation mechanism 200 further includes a first dicing machine 207 and a first dryer 208, and the first dicing machine 207 and the first dryer 208 are disposed between the first extruder 206 and the polycondensation reaction tank 102 of the polyester carrier preparation mechanism 100. The functional material prepared by the first extruder 206 was prepared into dried functional material chips by a first dicing machine 207 and a first dryer 208, respectively. The output end of the first dryer 208 is connected to the polycondensation reaction vessel 102 through a pipe.
In another embodiment, the output end of the second extruder 106 is further connected to a second slicer 107 and a second dryer 108 via piping. The functional masterbatch prepared by the second extruder 106 may be further prepared by a second slicer 107 and a second dryer 108, respectively, to obtain dried slices of the functional masterbatch. The prepared functional master batch slices can be further packaged and stored through a packaging mechanism.
The present application will be further described with reference to the following examples.
Example 1
Drying 60 parts by weight of aerogel particles with the particle size of 0.5 mu m at 120 ℃ for 4 hours; drying 10 parts by weight of polylactic acid particles with the particle size of less than 0.5mm at 110 ℃ for 4 hours; 10 parts by weight of polystyrene particles having a particle size of 0.5mm or less and 5 parts by weight of polyethylene particles having a particle size of 0.5mm or less were dried at 110 ℃ for 4 hours. And putting the dried particles into 30 parts by weight of liquid polydimethylsiloxane at normal temperature, and stirring at the speed of 1000-1500rpm for 2 hours to obtain a paste material. 20 parts by weight of polystyrene particles dried at 110 ℃ for 4 hours and 5 parts by weight of polyethylene particles (which can be dried only in the form of purchased particles without pulverization) are put into a mixing area of an extruder together with the paste material, and after uniform mixing, the mixture is melted, extruded, granulated and dried to obtain functional material slices.
Adding terephthalic acid, ethylene glycol and germanium dioxide into an esterification reaction kettle, carrying out esterification reaction at 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), and after the water yield reaches a theoretical value, releasing the system pressure to normal pressure and transferring the system pressure into a polycondensation reaction kettle. Reacting under the condition, adding triethyl phosphate and poly m-xylylene adipamide, adding 45 parts by weight of functional material slices according to the expected yield of 100 parts by weight of PET polyester carrier, stirring for 10 minutes under normal pressure, raising the temperature and reducing the pressure to 280 ℃ and below 100Pa, reacting for 3 hours under the condition, and finally extruding, granulating and drying the polymerization melt to obtain PET functional master batch slices with the intrinsic viscosity of 0.75 dl/g.
Slicing the prepared PET functional material according to SiO2The addition amount of the polyester resin is 3.0 percent of the total mass, and the polyester resin is melted and extruded with common PET, cast by a die head, transversely drawn by far infrared rays, cooled and shaped, rolled and cut to prepare the polyester film with the thickness of 60 mu m. The transverse heat shrinkage rate of the prepared film is 71 percent at 120 ℃ for 2-3 seconds, the light transmittance is 98 percent, the tensile strength is 305MPa, and the processing temperature (melt extrusion temperature) is 266 ℃. The film passes the flame retardant rating of UL 94V-2.
Example 2
Drying 70 parts by weight of aerogel particles with the particle size of 10 mu m at 120 ℃ for 4 hours; 15 parts by weight of polylactic acid particles with the particle size of less than 0.5mm are dried for 4 hours at the temperature of 110 ℃; 15 parts by weight of polystyrene particles having a particle size of 0.5mm or less were dried at 110 ℃ for 4 hours. And putting the dried particles into 40 parts by weight of liquid polydimethylsiloxane at normal temperature, and stirring at the speed of 1000-1500rpm for 2 hours to obtain a paste material. And (3) putting 45 parts by weight of polystyrene particles (which can be dried in a purchased particle form without crushing) dried for 4 hours at 110 ℃ and the paste material into a mixing area of an extruder, uniformly mixing, and then carrying out melt extrusion, granulation and drying to obtain functional material slices.
Adding terephthalic acid, ethylene glycol and germanium dioxide into an esterification reaction kettle, carrying out esterification reaction at 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), and after the water yield reaches a theoretical value, releasing the system pressure to normal pressure and transferring the system pressure into a polycondensation reaction kettle. Reacting under the condition, adding triethyl phosphate and poly m-xylylene adipamide, adding 65 parts by weight of functional material slices according to the expected yield of 100 parts by weight of PET polyester carrier, stirring for 10 minutes under normal pressure, raising the temperature and reducing the pressure to 280 ℃ and below 100Pa, reacting for 3 hours under the condition, and finally extruding, granulating and drying the polymerization melt to obtain PET functional master batch slices with the intrinsic viscosity of 0.75 dl/g.
Slicing the prepared functional material according to SiO2The addition amount of the polyester resin is 3.0 percent of the total mass, and the polyester resin is melted and extruded with common PET, cast by a die head, transversely drawn by far infrared rays, cooled and shaped, rolled and cut to prepare the polyester film with the thickness of 60 mu m. The prepared film has the advantages of 120 ℃, 69 percent of transverse heat shrinkage rate in 2-3 seconds, 97 percent of light transmittance, 325MPa of tensile strength and 271 ℃ of processing temperature (melt extrusion temperature). The film passes the flame retardant rating of UL 94V-2.
Example 3
Drying 65 parts by weight of aerogel particles with the particle size of 5 mu m at 120 ℃ for 4 hours; drying 12 parts by weight of polylactic acid particles with the particle size of less than 0.5mm at 110 ℃ for 4 hours; 5 parts by weight of polystyrene particles having a particle size of 0.5mm or less and 5 parts by weight of polyethylene particles having a particle size of 0.5mm or less were dried at 110 ℃ for 4 hours. And putting the dried particles into 35 parts by weight of liquid polydimethylsiloxane at normal temperature, and stirring at the speed of 1000-1500rpm for 2 hours to obtain a paste material. 15 parts by weight of polystyrene particles and 5 parts by weight of polyethylene particles (which can be dried only in the form of purchased particles without crushing) dried at 110 ℃ for 4 hours are put into a mixing area of an extruder together with the paste material, and after uniform mixing, the mixture is melted, extruded, granulated and dried to obtain functional material slices.
Adding purified terephthalic acid, ethylene glycol, 1, 4-Cyclohexanedimethanol (CHDM), tetrabutyl titanate catalyst, calcium acetate anti-bonding agent and nano-scale calcium acetate additive into an esterification reaction kettle, carrying out esterification reaction at 230-250 ℃ and 0.2-0.3 Mpa, and discharging the system pressure to normal pressure and transferring the system pressure into a polycondensation reaction kettle after the water yield reaches a theoretical value. And (2) reacting under the condition, adding a triethyl phosphate stabilizer and poly m-xylylene adipamide, adding 55 parts by weight of functional material slices according to the expected yield of 100 parts by weight of the PETG polyester carrier, stirring for 6min under normal pressure, vacuumizing, raising the temperature in the reaction kettle to 285 ℃, reducing the pressure to be below 100Pa, reacting for 3h under the condition, and finally extruding, granulating and drying the polymerized melt to obtain the PETG functional master batch slices with the intrinsic viscosity of 0.80 dl/g.
Slicing the prepared functional material according to SiO2The addition amount of the polyester resin is 3.0 percent of the total mass, and the polyester resin is melted and extruded with common PET, cast by a die head, transversely drawn by far infrared rays, cooled and shaped, rolled and cut to prepare the polyester film with the thickness of 60 mu m. The transverse heat shrinkage rate of the prepared film is 72 percent at 120 ℃ for 2-3 seconds, the light transmittance is 96 percent, the tensile strength is 315MPa, and the processing temperature (melt extrusion temperature) is 266 ℃. The film passes the flame retardant rating of UL 94V-2.
Comparative example 1
The aerogel particles of example 1 were replaced with ordinary silica particles having a particle size of also 0.5 μm, and polylactic acid and polydimethylsiloxane were removed to prepare comparative functional material chips.
Slicing the comparative functional material according to SiO2The addition amount of the polyester resin is 3.0 percent of the total mass, and the polyester resin is melted and extruded with common PET, cast by a die head, transversely drawn by far infrared rays, cooled and shaped, rolled and cut to prepare the polyester film with the thickness of 60 mu m. The transverse heat shrinkage rate of the prepared film is 51 percent at 120 ℃ for 2-3 seconds, the light transmittance is 89 percent, the tensile strength is 265MPa, and the processing temperature (melt extrusion temperature) is 301 ℃. The film failed the flame retardant rating of UL 94V-2.
Comparative example 2
The aerogel particles of example 2 were replaced with ordinary silica particles having the same particle size of 10 μm, and polylactic acid and polydimethylsiloxane were removed to prepare comparative functional material chips.
Slicing the comparative functional material according to SiO2The addition amount of the polyester resin is 3.0 percent of the total mass, and the polyester resin is melted and extruded with common PET, cast by a die head, transversely drawn by far infrared rays, cooled and shaped, rolled and cut to prepare the polyester film with the thickness of 60 mu m. The transverse heat shrinkage rate of the prepared film is 50 percent at 120 ℃ for 2-3 seconds, the light transmittance is 88 percent, the tensile strength is 285MPa, and the processing temperature (melt extrusion temperature) is 297 ℃. The film failed the flame retardant rating of UL 94V-2.
Comparative example 3
The aerogel particles in example 3 were replaced with ordinary silica particles having a particle size of 5 μm, and polylactic acid and polydimethylsiloxane were removed to prepare comparative functional material chips.
Slicing the comparative functional material according to SiO2The additive amount of the polyester film is 3.0 percent of the total mass, and the polyester film is prepared into a polyester film with the thickness of 60 mu m by melt extrusion with common PETG, die head sheet casting, transverse far infrared stretching, cooling and shaping, rolling and slitting. The transverse heat shrinkage rate of the prepared film is 49 percent at 120 ℃ for 2-3 seconds, the light transmittance is 90 percent, the tensile strength is 275MPa, and the processing temperature (melt extrusion temperature) is 302 ℃. The film failed the flame retardant rating of UL 94V-2.
The polyester film prepared by adding the functional master batch has little influence on the viscosity of the original polyester, and is beneficial to maintaining the stability of the parameters of the polyester film; the dosage of the anti-adhesion particles can be reduced; the processing property, tensile strength, light transmittance and flame retardant property of the polyester film are improved. In addition, the glossiness, the wear resistance, the high temperature resistance and the heat insulation performance of the polyester film can be improved.
It should be appreciated by those skilled in the art that while the present application is described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is thus given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including all technical equivalents which are encompassed by the claims and are to be interpreted as combined with each other in a different embodiment so as to cover the scope of the present application.
The above description is only illustrative of the present invention and is not intended to limit the scope of the present invention. Any equivalent alterations, modifications and combinations that may be made by those skilled in the art without departing from the spirit and principles of this application shall fall within the scope of this application.

Claims (2)

1. A functional masterbatch production system for polyester film, comprising a polyester carrier preparation mechanism (100) and a functional material preparation mechanism (200), wherein the polyester carrier preparation mechanism (100) comprises at least one esterification reaction kettle (101) and at least one polycondensation reaction kettle (102), and is characterized in that the functional material preparation mechanism (200) comprises an aerogel particle dryer (201), a polylactic acid particle dryer (202), a first polystyrene or polyethylene particle dryer (203) and a second polystyrene or polyethylene particle dryer (204); dry particles of the aerogel particle dryer (201), the polylactic acid particle dryer (202) and the first polystyrene or polyethylene particle dryer (203) are input into a polydimethylsiloxane stirring tank (205) through pipelines, and a paste material output from the polydimethylsiloxane stirring tank (205) and dry particles of the second polystyrene or polyethylene particle dryer (204) are input into a first extruder (206) through pipelines to prepare functional material slices; the functional material slices prepared by the first extruder (206) are further added into a polycondensation reaction kettle (102) of a polyester carrier preparation mechanism (100) through a pipeline for mixing reaction, and the final product in the polycondensation reaction kettle (102) is input into a second extruder (106) through a pipeline to prepare and obtain a functional master batch; the functional material preparation mechanism (200) further comprises a first slicer (207) and a first dryer (208), and the first slicer (207) and the first dryer (208) are arranged between the first extruder (206) and the polycondensation reaction kettle (102) of the polyester carrier preparation mechanism (100).
2. The functional masterbatch production system for mylar as claimed in claim 1, wherein the output end of the second extruder (106) is further connected to a second slicer (107) and a second dryer (108) through a pipe.
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