CN103113562A - Green environment-friendly ternary copolymerization PET-A and quaternary copolymerization PET-AG polyester and method for preparing transverse blow-molding thermal shrinkage film by using same - Google Patents
Green environment-friendly ternary copolymerization PET-A and quaternary copolymerization PET-AG polyester and method for preparing transverse blow-molding thermal shrinkage film by using same Download PDFInfo
- Publication number
- CN103113562A CN103113562A CN2013100433041A CN201310043304A CN103113562A CN 103113562 A CN103113562 A CN 103113562A CN 2013100433041 A CN2013100433041 A CN 2013100433041A CN 201310043304 A CN201310043304 A CN 201310043304A CN 103113562 A CN103113562 A CN 103113562A
- Authority
- CN
- China
- Prior art keywords
- pet
- pta
- polyester
- terpolymer
- monomer
- 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.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/9155—Pressure rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to green environment-friendly AA (adipic acid) and NPG ternary/quaternary copolymerization modified PET-A/PET-AG polyester and a method for preparing a blow-molding thermal shrinkage film which the PET-A/PET-AG polyester is specifically applicable to. According to the invention, accessible, green, environment-friendly and non-toxic AA is used to replace a terephthalic acid raw material having benzene ring toxin side effect; NPE is used to reduce the consumption of an ethylene glycol monomer; and copolymerization modification is performed to obtain the PET-A/PET-AG semi-crystalline or non-crystalline copolyester and the blow-molding thermal shrinkage film which the polyester is specifically applicable to. The copolyester product has the advantages of high flexibility, high transparency, favorable printing property and high freezing resistance, and still has favorable functionality and processing property at -40 DEG C; and the transverse shrinkage rates of thermal shrinkage films of the semi-crystalline and non-crystalline polyester products are respectively 45-60% and 60-80%. Thus, the invention is suitable for large-scale popularization.
Description
Technical field
The present invention relates to polymer random block modification by copolymerization chemical preparation field, be particularly related to a kind of AA of environmental protection and NPG ternary and quarternary copolymerized modified PET-A, PET-AG polyester macromolecule material preparation method, and the process of preparing that specially is applicable to the blowing heat-shrinkable film by this PET-A, PET-AG.
Background technology
Develop rapidly along with the plastics chemical engineering industry, environmental pollution goes from bad to worse, and progressively jeopardizes natural, ecological and health of human body safety, and this causes the extensive concern in the world, therefore, the improvement of environmental pollution and natural, ecological, eliminate outmoded backwardness and have the malicious plastics of serious environment pollution very urgent.Both at home and abroad must adopt the macromolecular material of environmental protection ecology to substitute severe contamination by legislation and the method statement of promulgating the forbidding file endangers natural, ecological, particularly poisonous and serious environment pollution and endangers the wrapping material such as backward plastic pvc of health of human body.at present, although developed ternary both at home and abroad, quaternary PET modification by copolymerization environment-friendly PE TG, PETA series macromolecular novel material, but it is only applicable to the preliminary mature industry production of stretching method heat-shrinkable film, being applicable to blow moulding produces heat-shrinkable film and there is no method and reach suitability for industrialized production, this be due to: one, blow moulding prepares heat-shrinkable film, both at home and abroad there is the hundreds of thousands of of annual output per year ton to be used for various wrapping material the preparation technology of the more outmoded backwardness of PVC is industrial, two, the PETG of the environmental protection modification by copolymerization of developing both at home and abroad at present, PETA series novel material stretching method has at home reached suitability for industrialized production, but invest excessive, cost is high, three, the preparation method of PVC blowing heat-shrinkable film is applicable to PETG, the PET-A novel material is distinct two frock preparation methods, therefore, only developing both at home and abroad, still belonging to blank.PETA of the present invention, the new macromolecular material of PETAG modification by copolymerization specially are applicable to blow moulding and prepare heat-shrinkable film.
Summary of the invention
Technical problem to be solved by this invention is: based on deficiency of the prior art, propose the preparation method of a kind of environmental protection terpolymer PET-A and quarternary copolymerized PET-AG polyester and horizontal blowing heat-shrinkable film thereof.
Technical scheme of the present invention is screening a kind of hydrocarbon molecules compound monomer and NPG modified PET ternary, quarternary copolymerized ester, the terpolymer modification is take terephthalic acid (PTA), hexanodioic acid (AA), ethylene glycol (MEG) as principal monomer, quarternary copolymerized modification is take terephthalic acid (PTA), hexanodioic acid (AA), neopentyl glycol (NPG), ethylene glycol (MEG) as the principal monomer raw material, more auxiliaryly has catalyzer and stablizer to carry out the reaction of monomer esterification chain link and two stages of high vacuum polyreaction under existing; The preparation method of a kind of environmental protection terpolymer PET-A and quarternary copolymerized PET-AG polyester has following steps:
(1) prepare the comonomer batching, wherein,
A. terpolymer PET-A configuration, meter in molar ratio:
PTA：AA=1：0.08～0.35；
（PTA+AA）：MEG=1：1.25～1.75；
B. quarternary copolymerized PET-AG configuration, count in molar ratio:
PTA：AA=1：0.009～0.30；
（PTA+AA）：NPG=1：0.015～0.45；
（PTA+AA）：MEG=1：1.20～1.50；
Above terpolymer PET-A, quarternary copolymerized PET-AG are by catalyst S b
2O
3There is lower configuration with the stablizer trimethyl phosphite 99, by weight:
Sb
2O
3:（PTA+AA）=0.0003～0.00055:1；
Trimethyl phosphite 99: (PTA+AA)=0.0003～0.0005:1;
(2) monomer molecule esterification
With above-mentioned ready monomer accurate weighing, drop in order terpolymer PET-A raw material: MEG, PTA, AA, Sb
2O
3, trimethyl phosphite 99; First mix making beating 30min, then slurries are pressed into the heating that heats up in chemical reaction kettle and carry out the esterification of monomer, temperature is controlled to be 190～255 ℃, the reactor tower top temperature is controlled at below 90～110 ℃, reaction times is controlled to be 180～350min, reacts to get 2molH by 1mol (PTA+AA)
2The total acid of O and input and alcohol meter are calculated and are drawn theoretical aquifer yield, with the aquifer yield of reactor overhead streams water outlet reach theoretical aquifer yield 95% the time, tower top temperature drops to 40～50 ℃ gradually by 105 ℃, and the reactor tower top is reaction and completes terminal point without water outlet or when seldom oozing;
Drop in order quaternary polyester raw material: MEG, PTA, AA, NPG, Sb
2O
3, trimethyl phosphite 99; First mix making beating 30min, then slurries are pressed into the heating that heats up in chemical reaction kettle and carry out the esterification of monomer, temperature is controlled to be 190～255 ℃, the reactor tower top temperature is controlled at below 90～110 ℃, reaction times is controlled to be 180～350min, reacts to get 2molH by 1mol (PTA+AA)
2The total acid of O and input and alcohol meter are calculated and are drawn theoretical aquifer yield, with the aquifer yield of reactor overhead streams water outlet reach theoretical aquifer yield 95% the time, tower top temperature drops to 40～50 ℃ gradually by 105 ℃, and the reactor tower top is reaction and completes terminal point without water outlet or when seldom oozing;
(3) polymer copolymerization reaction
The liquid material that above-mentioned esterification is complete is pressed into nitrogen the heating that heats up in polymerization reaction kettle respectively separately, temperature in the kettle begins to take out rough vacuum 45～60min when reaching 260 ℃, as 275 ℃ of Nei Wenduda, when vacuum tightness reaches 0.1MPa, being polyreaction begins, temperature is controlled at 275～285 ℃, reaction times is 180～350min, and along with the reaction times extends, in still, polyester viscosity rises gradually, polyester viscosity is 0.68～0.80 in still, when fusing point is 170～235 ℃, stop polyreaction, remove vacuum, termination reaction, cooling discharging;
(4) finished product packing
After above-mentioned copolyreaction is finished, the material of discharging is pressed out to the underwater pelletizer cooling and dicing with nitrogen, drying, packing after the assay was approved.
The preparation method of the horizontal blowing heat-shrinkable film of a kind of environmental protection PET-A and PET-AG polyester, concrete steps are as follows: with PEG-A, PET-AG polyester raw material not drying directly add in the two vacuum-extruders of twin screw, through fusion plastification extrude, melt coarse filtration, volume pump metering, essence filtration, periosteum blow molding, two roller are cooling, four times of blowings of secondary, two roller are cooling, thermal treatment, rolling, detection, finished product packing.
The two vacuum-extruders of described twin screw respectively to distinguish Temperature Setting as follows: 100～120 ℃, a district, two 150～180 ℃, districts, three 220～230 ℃, districts, four 230～245 ℃, districts, five 245～255 ℃, districts, six 245～255 ℃, districts, seven 240～250 ℃, districts; 245～255 ℃ of strainers, 245～255 ℃ of volume pumps, 245～255 ℃, periosteum mould, 80～90 ℃ of blowings, cooling 35～50 ℃ of two rollers, 85～90 ℃ of four times of blowings of secondary, cooling 35～55 ℃ of two rollers, 60～130 ℃ of heat treatment box temperature.
The present invention selects terephthalic acid (PTA) raw material, the NPE of hydrocarbon polymer monomer hexanodioic acid (AA) the Substitute For Partial band phenyl ring toxin side effect that a kind of raw material is easy to get (domestic), environmental protection is nontoxic to reduce ethylene glycol monomer consumption, and modification by copolymerization obtains the copolyesters of PET-A, PET-AG hypocrystalline or amorphism environmental protection and specially is suitable for the blowing heat-shrinkable film by this polyester; The more environmental protection of described copolyesters product, safety, have high-flexibility, height is transparent, printing good, winter hardiness is strong, can be-40 ℃ of advantages that still have good functional and processing characteristics, the lateral shrinkage of the heat-shrinkable film of this semicrystalline polyester product is 45～60%, the lateral shrinkage of the heat-shrinkable film of non-crystalline polyester product is 60～80%, be applicable to the range of application in each field, be specially adapted to blowing, stretching heat-shrinkable film injection moulding curtain coating etc.The present invention has filled up the blank that domestic and international blow moulding prepares PET modified poly ester film, is suitability for industrialized production route better in prior art, is suitable for large-scale promotion.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples;
Fig. 1 is the horizontal blow molding process schematic diagram of polyester of the present invention;
In figure, 1. two vacuum-extruders of twin screw, 2. melt coarse filtration, 3. volume pump, 4. essence is filtered, 5. periosteum blow molding, 6. pair roller is cooling, 7. four times of blowings of secondary, 8. thermal treatment, 9. rolling.
Embodiment
Below enumerate respectively two routine embodiment for terpolymer PET-A and quarternary copolymerized PET-AG polyester, specifically fill a prescription as shown in table 1 below:
Table 1
With above-mentioned ready monomer accurate weighing, drop in order terpolymer PETA raw material: MEG, PTA, AA, Sb
2O
3, trimethyl phosphite 99; First mix making beating 30min, then slurries are pressed into the heating that heats up in chemical reaction kettle and carry out the esterification of monomer, temperature is controlled to be 190～255 ℃, the reactor tower top temperature is controlled at below 90～110 ℃, reaction times is controlled to be 180～350min, reacts to get 2molH by 1mol (PTA+AA)
2The total acid of O and input and alcohol meter are calculated and are drawn theoretical aquifer yield, with the aquifer yield of reactor overhead streams water outlet reach theoretical aquifer yield 95% the time, tower top temperature drops to 40～50 ℃ gradually by 105 ℃, and the reactor tower top is reaction and completes terminal point without water outlet or when seldom oozing;
Drop in order quaternary polyester raw material: MEG, PTA, AA, NPG, Sb
2O
3, trimethyl phosphite 99; All the other steps are the same.
The liquid material that above-mentioned esterification is complete is pressed into nitrogen the heating that heats up in polymerization reaction kettle respectively separately, temperature in the kettle begins to take out rough vacuum 45～60min when reaching 260 ℃, as 275 ℃ of Nei Wenduda, when vacuum tightness reaches 0.1MPa, being polyreaction begins, temperature is controlled at 275～285 ℃, reaction times is 180～350min, and along with the reaction times extends, in still, polyester viscosity rises gradually, polyester viscosity is 0.68～0.80 in still, when fusing point is 170～235 ℃, stop polyreaction, remove vacuum, termination reaction, cooling discharging;
After above-mentioned copolyreaction is finished, the material of discharging is pressed out to the underwater pelletizer cooling and dicing with nitrogen, drying, packing after the assay was approved.
The preparation method of the horizontal blowing heat-shrinkable film of a kind of environmental protection PET-A and PET-AG polyester, concrete steps are as follows: with PEG-A, PET-AG polyester raw material not drying directly add in as shown in Figure 1 two vacuum-extruders 1 of twin screw, through fusion plastification extrude, melt coarse filtration 2, volume pump 3 meterings, essence filter 4, periosteum blow molding 5, two roller are cooling 6, four times of blowings 7 of secondary, two roller are cooling 6, thermal treatment 8, rolling 9, detection, finished product packing.
The two vacuum-extruders of described twin screw respectively to distinguish Temperature Setting as follows: 100～120 ℃, a district, two 150～180 ℃, districts, three 220～230 ℃, districts, four 230～245 ℃, districts, five 245～255 ℃, districts, six 245～255 ℃, districts, seven 240～250 ℃, districts; 245～255 ℃ of strainers, 245～255 ℃ of volume pumps, 245～255 ℃, periosteum mould, 80～90 ℃ of blowings, cooling 35～50 ℃ of two rollers, 85～90 ℃ of four times of blowings of secondary, cooling 35～55 ℃ of two rollers, 60～130 ℃ of heat treatment box temperature.
Above-mentioned four routine embodiment the detection data of product as shown in table 2 below:
Table 2
The invention is characterized in and adopt AA and NPG to make ternary, quarternary copolymerized monomer; be in no way limited in mol ratio of the present invention or weight ratio scope; everyly utilize in patent copolyesters of the present invention two kinds of monomer A A, NPG and utilize the two vacuum blown film legal systems of twin screw standby; perhaps do equivalent structure or equivalent flow process conversion or directly or indirectly use other correlative technology field expansions; no matter use which kind of mode, all belong to the more clearly demarcation of clear protection that the scope of the claims of the present invention is in like manner made.
Claims (6)
1. terephthalic acid (PTA) and a neopentyl glycol (NPG) that adopts six hydrocarbon polymer monomer hexanodioic acids (AA) to replace part to contain phenyl ring toxicity reduces ethylene glycol monomer consumption, the environmental protection ternary PET-A of modification by copolymerization and the PET-AG copolyesters of quarternary copolymerized modification, it is characterized in that: terpolymer is with terephthalic acid (PTA), hexanodioic acid (AA), ethylene glycol (MEG) monomer is main raw material, quarternary copolymerized with terephthalic acid (PTA), hexanodioic acid (AA), neopentyl glycol (NPG), ethylene glycol (MEG) is main raw material, being aided with metal-salt or organic metal salt is catalyzer, antimony glycol or antimonous oxide and phosphoric acid ester are thermo-stabilizer, carry out chemical random copolymerization reaction, obtain the preparation method of the polymer novel material of environmental type.
2. environmental protection terpolymer PET-A as claimed in claim 1 and quarternary copolymerized PET-AG polyester is characterized in that: have following formula:
A. terpolymer PET-A configuration, meter in molar ratio:
PTA：AA=1：0.08～0.35；
（PTA+AA）：MEG=1：1.25～1.75；
B. quarternary copolymerized PET-AG configuration, count in molar ratio:
PTA：AA=1：0.009～0.30；
（PTA+AA）：NPG=1：0.015～0.45；
（PTA+AA）：MEG=1：1.20～1.50；
Above terpolymer PET-A, quarternary copolymerized PET-AG are by catalyst S b
2O
3There is lower configuration with the stablizer trimethyl phosphite 99, by weight:
Sb
2O
3:（PTA+AA）=0.0003～0.00055:1；
Trimethyl phosphite 99: (PTA+AA)=0.0003～0.0005:1.
3. the preparation method of environmental protection terpolymer PETA as claimed in claim 1 and quarternary copolymerized PETAG polyester, it is characterized in that: preparation process is as follows:
(1) monomer molecule esterification
With above-mentioned ready monomer accurate weighing, drop in order terpolymer PET-A raw material: MEG, PTA, AA, Sb
2O
3, trimethyl phosphite 99; First mix making beating 30min, then slurries are pressed into the heating that heats up in chemical reaction kettle and carry out the esterification of monomer, temperature is controlled to be 190～255 ℃, the reactor tower top temperature is controlled at below 90～110 ℃, reaction times is controlled to be 180～350min, reacts to get 2molH by 1mol (PTA+AA)
2The total acid of O and input and alcohol meter are calculated and are drawn theoretical aquifer yield, with the aquifer yield of reactor overhead streams water outlet reach theoretical aquifer yield 95% the time, tower top temperature drops to 40～50 ℃ gradually by 105 ℃, and the reactor tower top is reaction and completes terminal point without water outlet or when seldom oozing;
Drop in order quarternary copolymerized PET-AG raw material: MEG, PTA, AA, NPG, Sb
2O
3, trimethyl phosphite 99; First mix making beating 30min, then slurries are pressed into the heating that heats up in chemical reaction kettle and carry out the esterification of monomer, temperature is controlled to be 190～255 ℃, the reactor tower top temperature is controlled at below 90～110 ℃, reaction times is controlled to be 180～350min, reacts to get 2molH by 1mol (PTA+AA)
2The total acid of O and input and alcohol meter are calculated and are drawn theoretical aquifer yield, with the aquifer yield of reactor overhead streams water outlet reach theoretical aquifer yield 95% the time, tower top temperature drops to 40～50 ℃ gradually by 105 ℃, and the reactor tower top is reaction and completes terminal point without water outlet or when seldom oozing;
(2) polymer copolymerization reaction
The liquid material that above-mentioned esterification is complete is pressed into nitrogen the heating that heats up in polymerization reaction kettle respectively separately, temperature in the kettle begins to take out rough vacuum 45～60min when reaching 260 ℃, as 275 ℃ of Nei Wenduda, when vacuum tightness reaches 0.1MPa, being polyreaction begins, temperature is controlled at 275～285 ℃, reaction times is 180～350min, and along with the reaction times extends, in still, polyester viscosity rises gradually, polyester viscosity is 0.68～0.80 in still, when fusing point is 170～235 ℃, stop polyreaction, remove vacuum, termination reaction, cooling discharging;
(3) finished product packing
After above-mentioned copolyreaction is finished, to the underwater pelletizer cooling and dicing, pack after the assay was approved by drying with nitrogen for the material of discharging;
In sum, adopting the mol ratio combination of monomers of PTA, AA, NPG is feature of the present invention place, obtain high-flexibility, high plasticity, high percent thermal shrinkage polyester, can require to make the shrinking percentage of film more than 45～75% in 65～130 ℃ of scopes according to Application Areas, and the polyphosphazene polymer ester material that good heat-sealing cementability characteristic is arranged is applicable to the heat-shrinkable film of all trades and professions and goods and the wrapping material of other Application Areas.
4. the preparation method of environmental protection terpolymer PET-A as claimed in claim 1 and quarternary copolymerized PET-AG polyester, it is characterized in that: the comonomer combined sorting adopts six hydrocarbon chain molecular structure monomer hexanodioic acids (AA), reduce the terephthalic acid (PTA) with toxic phenyl ring monomer molecule structure, reach the high-molecular copolymer of long hydrocarbon chain segment structure, make copolyesters of the present invention have more environmentally-friendly sanitary, plasticity-, snappiness and high transparent characteristics.
5. the preparation method of the horizontal blowing heat-shrinkable film of environmental protection terpolymer PET-A as claimed in claim 1 and quarternary copolymerized PETAG polyester, it is characterized in that: concrete steps are as follows: with PEGA, PETAG polyester raw material not drying directly add in the two vacuum-extruders of twin screw, through fusion plastification extrude, melt coarse filtration, volume pump metering, essence filtration, periosteum blow molding, two roller are cooling, four times of blowings of secondary, two roller are cooling, thermal treatment, rolling, detection, finished product packing;
The two vacuum-extruders of described twin screw respectively to distinguish Temperature Setting as follows: 100～120 ℃, a district, two 150～180 ℃, districts, three 220～230 ℃, districts, four 230～245 ℃, districts, five 245～255 ℃, districts, six 245～255 ℃, districts, seven 240～250 ℃, districts; 245～255 ℃ of strainers, 245～255 ℃ of volume pumps, 245～255 ℃, periosteum mould, 80～90 ℃ of blowings, cooling 35～50 ℃ of two rollers, 85～90 ℃ of four times of blowings of secondary, cooling 35～55 ℃ of two rollers, 60～130 ℃ of heat treatment box temperature.
6. the preparation method of the horizontal blowing heat-shrinkable film of terpolymer PET-A as claimed in claim 5 and quarternary copolymerized PET-AG polyester, still be blank at present both at home and abroad, the present invention is the most effective preparation method, and this preparation is with blowing heat-shrinkable film technique preparation process and be applicable to the serial copolyesters such as all kinds of PET, PETG, PET-A and prepare effective ways and all belong in this scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100433041A CN103113562A (en) | 2013-02-04 | 2013-02-04 | Green environment-friendly ternary copolymerization PET-A and quaternary copolymerization PET-AG polyester and method for preparing transverse blow-molding thermal shrinkage film by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100433041A CN103113562A (en) | 2013-02-04 | 2013-02-04 | Green environment-friendly ternary copolymerization PET-A and quaternary copolymerization PET-AG polyester and method for preparing transverse blow-molding thermal shrinkage film by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103113562A true CN103113562A (en) | 2013-05-22 |
Family
ID=48411986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100433041A Pending CN103113562A (en) | 2013-02-04 | 2013-02-04 | Green environment-friendly ternary copolymerization PET-A and quaternary copolymerization PET-AG polyester and method for preparing transverse blow-molding thermal shrinkage film by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103113562A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804177A (en) * | 2015-04-09 | 2015-07-29 | 中国纺织科学研究院 | Modified PET (polyethylene terephthalate) copolymer for high-toughness heat-shrinkable film and preparation method of modified PET copolymer |
| CN113754874A (en) * | 2021-08-13 | 2021-12-07 | 浙江恒澜科技有限公司 | Preparation method of high molecular weight biodegradable poly (terephthalic acid-adipic acid-ethylene glycol ester) |
| CN115636928A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Polyester material and preparation method and application thereof |
| CN115678213A (en) * | 2021-07-22 | 2023-02-03 | 远东新世纪股份有限公司 | Heat-shrinkable polyester film and method for producing same |
| WO2023070754A1 (en) * | 2021-10-29 | 2023-05-04 | 浙江晶通新材料集团有限公司 | Halogen-free modified high-filling recyclable plastic plate and forming method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735437A (en) * | 2008-11-04 | 2010-06-16 | 中富(广汉)化工实业有限公司 | Copolyester with low melting point and synthesis method thereof |
| CN102251312A (en) * | 2011-06-17 | 2011-11-23 | 江苏鹰翔化纤股份有限公司 | Adipic acid (AA) modified polyester fully drawn yarn (FDY) |
-
2013
- 2013-02-04 CN CN2013100433041A patent/CN103113562A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735437A (en) * | 2008-11-04 | 2010-06-16 | 中富(广汉)化工实业有限公司 | Copolyester with low melting point and synthesis method thereof |
| CN102251312A (en) * | 2011-06-17 | 2011-11-23 | 江苏鹰翔化纤股份有限公司 | Adipic acid (AA) modified polyester fully drawn yarn (FDY) |
Non-Patent Citations (2)
| Title |
|---|
| 封怀兵等: "低熔点聚酯的研制及分析", 《化纤与纺织技术》 * |
| 王加龙: "《塑料挤出制品生产工艺手册》", 31 January 2002 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804177A (en) * | 2015-04-09 | 2015-07-29 | 中国纺织科学研究院 | Modified PET (polyethylene terephthalate) copolymer for high-toughness heat-shrinkable film and preparation method of modified PET copolymer |
| CN104804177B (en) * | 2015-04-09 | 2016-05-11 | 中国纺织科学研究院 | A kind of high tenacity amorphous modified PET copolymer and preparation method thereof |
| CN115636928A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Polyester material and preparation method and application thereof |
| CN115636928B (en) * | 2021-07-20 | 2024-05-28 | 中国石油天然气股份有限公司 | Polyester material, and preparation method and application thereof |
| CN115678213A (en) * | 2021-07-22 | 2023-02-03 | 远东新世纪股份有限公司 | Heat-shrinkable polyester film and method for producing same |
| CN115678213B (en) * | 2021-07-22 | 2024-06-11 | 远东新世纪股份有限公司 | Heat-shrinkable polyester film and method for producing the same |
| CN113754874A (en) * | 2021-08-13 | 2021-12-07 | 浙江恒澜科技有限公司 | Preparation method of high molecular weight biodegradable poly (terephthalic acid-adipic acid-ethylene glycol ester) |
| WO2023070754A1 (en) * | 2021-10-29 | 2023-05-04 | 浙江晶通新材料集团有限公司 | Halogen-free modified high-filling recyclable plastic plate and forming method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113562A (en) | Green environment-friendly ternary copolymerization PET-A and quaternary copolymerization PET-AG polyester and method for preparing transverse blow-molding thermal shrinkage film by using same | |
| KR101799132B1 (en) | Polyester resin composition and process for manufacturing the same | |
| CN104136485A (en) | Process for preparing a high molecular weight heteroaromatic polyester or copolyester | |
| RU2008145894A (en) | RESINS BASED ON COMPLEX POLYESTER FOR PRODUCTION OF PACKAGING, PRODUCED WITHOUT USING SOLID-PHASE POLYMERIZATION, METHOD OF PROCESSING RESINS BASED ON COMPLEX POLYESTER WITH CHANGE OF CONFERRED SUMMARY | |
| CN103203934A (en) | Heat shrinkage copolyester film and preparation method thereof | |
| EP3320017B1 (en) | Process for the production of glycol-modified polyethylene therephthalate from recycled raw materials | |
| CN102153756B (en) | Production process and equipment of methyl vinyl silicone rubber | |
| CN101845214A (en) | Polycarbonate alloy and preparation method thereof | |
| CN103848980B (en) | Special section of a kind of PET medical treatment and preparation method thereof | |
| CN104804177A (en) | Modified PET (polyethylene terephthalate) copolymer for high-toughness heat-shrinkable film and preparation method of modified PET copolymer | |
| CN104098762A (en) | Bottle-grade PET (polyethylene glycol terephthalate) device and production technology thereof | |
| CN102558517B (en) | Ecological multifunctional ternary copolymerization PETG (Polyethylene Terephthalate Glycol) polyester, preparation method of polyester, and method for preparing unidirectional stretching heat-shrinkable film from polyester | |
| CN104017338A (en) | Polyester slices for manufacturing vacuum blood collection tube and preparation method of polyester slices | |
| CN104193989A (en) | Preparation method of bio-based polyamide copolymer elastomer | |
| CN115536851B (en) | Gel-free self-adhesive PETG (polyethylene terephthalate glycol), preparation method thereof and application thereof in 3D (three-dimensional) printing | |
| CN105860038A (en) | Production technology of novel medical section | |
| CN103102647B (en) | Preparation method of polyester film with high heat shrinkage | |
| CN110920188A (en) | Bio-based PTT/PLA heat-shrinkable label film and preparation method thereof | |
| CN105504249A (en) | Hydrolysis-resistant fluorine-containing copolyester resin, hydrolysis-resistant fluorine-containing copolyester composite basal membrane and preparation method thereof | |
| CN102604293B (en) | Thermoplastically processable polyvinyl alcohol composite and preparation method thereof | |
| CN101475673B (en) | Transparent phenylethylene-dialkene star shaped copolymer and continuous preparation thereof | |
| KR101405871B1 (en) | Method for preparing polyester blends with high molecular weight and polyester blends produced with the same | |
| CN103772679A (en) | Preparation method for modified copolyester shrink film | |
| CN102660004A (en) | Method for preparing neopentyl glycol (NPG) and SiO2 copolymerization-modified polyethylene terephthalate glycol (PETG) polyester | |
| JP2010083957A (en) | Method for production of polybutylene terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130522 |