CN102757549B - 1, 6-hexanediol modified copolyester for hot shrink films - Google Patents
1, 6-hexanediol modified copolyester for hot shrink films Download PDFInfo
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- CN102757549B CN102757549B CN201110108937.7A CN201110108937A CN102757549B CN 102757549 B CN102757549 B CN 102757549B CN 201110108937 A CN201110108937 A CN 201110108937A CN 102757549 B CN102757549 B CN 102757549B
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Abstract
The invention relates to 1, 6-hexanediol modified copolyester for hot shrink films. 1, 6-hexanediol used as a third monomer is added to a synthetic system of pure terephthalic acid and hexanediol, and the mixture is synthesized into polyethylene terephthalate 1, 6-hexanediol copolyester under catalysis of a catalyst by esterification and polycondensation reaction; the molar ratio of the hexanediol and the 1, 6-hexanediol is 40:60-90:10; the mole number ratio of the sum of the mole numbers of the pure terephthalic acid, the hexanediol and the 1, 6-hexanediol is 1:1.0-1.8; the catalyst is a composite catalyst of titanium compound, antimony compound, cobalt compound and germanium compound; and the melting point of the copolymer is 160-230 DEG C, and the intrinsic viscosity is 0.55-0.75 d L/g. The 1, 6-hexanediol modified copolyester overcomes the defects of poor color and adhesion easiness, bending performance and tensile performance of polyester products are increased, the melting point of the polyester products is reduced, and the 1, 6-hexanediol modified copolyester can be used to process hot shrink films.
Description
Technical field:
The present invention relates to a kind of 1,6-hexylene glycol modification heat-shrinkable film copolyesters.
Background technology:
Heat Shrinkage Film Polyester is a kind of novel copolymerized ester of developing in recent years both at home and abroad, the unilateral stretching heat-shrinkable film made from it has unidirectional shrinkage and excellent printing performance, not only can prevent the abnormal deformation of printed patterns, and can embody preferably the appearance characteristics of product, be highly suitable for making the various telescoping shrink labels of current international popular.Polyester thermal contraction film is when the outer label as polyethylene terephthalate (PET) bottle, can reclaim together with bottle and regenerate, the required operation that label film is peeled off from PET bottle while having removed employing polyvinyl chloride (PVC) thermal shrink film label from, it is convenient to reclaim, can be to environment.And PVC heat-shrinkable film can produce the Toxic of contaminate environment in processing and waste disposal process, therefore, in countries and regions such as Japan, West Europe and North Americas, be prohibited from using.Along with growing to even greater heights of domestic and international environmental protection tide, the high-performance environment protection type wrapping material of this novelty of polyester thermal contraction film will obtain applying more and more widely undoubtedly.
Normal polyester (PET) has been widely used in the every field of people's daily life as engineering materials, it can make the materials such as fiber, beverage bottle, film.But the fusing point of PET is higher, rigidity strong, post-treatment temperature is high, and energy consumption is large.In the prior art, by copolymerization, in normal polyester, introduce rigidity and symmetry that soft segment and unsymmetrical structure can change polyester macromolecule, thereby change the crystal property of polyester, make it to be conducive to prepare the shrinkable film of low-crystallinity, high-orientation.
Current disclosed use 1, the copolyesters form and aspect that the modification of 6-hexylene glycol obtains are poor, and easily adhesion should not be used as heat-shrinkable film.
Summary of the invention:
Disclosed by the invention 1, the heat-shrinkable film copolyesters of 6-hexylene glycol modification is by pure terephthalic acid (PTA), ethylene glycol (EG) and 1, a kind of polyester macromolecule material that three kinds of comonomers of 6-hexylene glycol (HD) prepare under catalyst compounded catalysis, owing to having added 1 in synthetic, 6-hexylene glycol soft segment monomer, fusing point and the rigidity of PET have been reduced, thereby improve crystal property and the stretch-proof performance of conventional polyester, and catalyst compounded adding improved color and the rebound resilience of polyester slice greatly, it is high that this kind of novel polyester for film overcome conventional polyester fusing point, rigidity is strong waits the shortcoming that should not process etc., given this kind of material melting point low, the premium propertiess such as good springiness, and greatly reduce post-treatment application cost, China in pay attention to day by day energy-saving and emission-reduction work, succeeding in developing of this material will have very important significance.
Provided by the invention 1, the heat-shrinkable film copolyesters of 6-hexylene glycol modification is with 1,6-hexylene glycol is that the 3rd monomer adds in the synthetic system of pure terephthalic acid (PTA), ethylene glycol (EG), catalyze and synthesize polyethylene terephthalate 1,6-hexylene glycol copolyesters, its process for catalytic synthesis comprises the following steps:
(1) esterification
By pure terephthalic acid (PTA), ethylene glycol (EG), 1,6-hexylene glycol (HD) and catalyst compoundedly directly join in reactor, in gauge pressure, be 0.25-0.30MPa (normal pressure), at 205～285 ℃ of temperature, carry out esterification, deviate from water byproduct, generate terephthalic acid 1,6-hexylene glycol ester, ethylene glycol terephthalate and oligopolymer thereof, when total esterification yield reaches 95% when above, esterification finishes; The mol ratio of EG and HD is 40: 60～90: 10; The mole ratio of PTA and EG and HDG mole number sum is 1: 1.0～1.8.
(2) polycondensation
Reactor was constantly decompressed in 40 minutes to high vacuum 10～150Pa, in this process, constantly distillate small molecular by product dibasic alcohol and oligopolymer, reaction final temperature is controlled at 265～285 ℃, then with rare gas element, make reactor return to normal pressure, obtain polymer melt, polymer melt is carried out to Cast Strip pelletizing, obtain limiting viscosity at 0.55～0.75dL/g and the good copolyester section of form and aspect.60～120 minutes high vacuum polycondensation time.
Catalyzer is the composite catalyst of titanium compound, zn cpds, cobalt compound and germanide;
Described titanium compound is metatitanic acid tetramethyl ester, titanium isopropylate or tetrabutyl titanate.
Described zn cpds is zinc acetate, zinc oxide, zinc nitrate.
Described germanium compound is Germanium tetraacetate, germanium oxide.
Described cobalt compound is Cobaltous diacetate, cobaltous phosphate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
The add-on of described titanium compound is that to take the content of titanium compound in terephthalic acid (PTA) weight be 100～800ppm, and being preferably 200～400ppm is benchmark.
The add-on of described zn cpds is that to take zn cpds content in terephthalic acid (PTA) weight be 100～500ppm, and being preferably 150～300ppm is benchmark.
The add-on of described cobalt compound is that to take the content of cobalt compound in terephthalic acid (PTA) weight be 50～300ppm, and being preferably 100～200ppm is benchmark.
The add-on of described germanium compound is that to take the content of germanium compound in terephthalic acid (PTA) weight be 50～300ppm, and being preferably 100～200ppm is benchmark.
Invention effect:
The present invention is that the 3rd monomer adds in the synthetic system of terephthalic acid (PTA) and ethylene glycol with 1,6-hexylene glycol (HD), has prepared polyethylene terephthalate 1,6-hexylene glycol ester.Main innovate point of the present invention is the catalyst compounded application 1 of selecting oneself to develop, and 6-hexylene glycol carries out modification to conventional polyester, and prepares processing characteristics and the superior modified poly ester product of mechanical property.
In the present invention, modified poly ester limiting viscosity is tested by GB/T14189-93.Acquired results is as follows: limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.The tensile strength of copolyesters, tensile modulus, elongation at break are tested by GB/T1040-2000, and flexural strength, modulus in flexure are tested by GB/T9341-2000.Gained test result is as follows: tensile strength 42～65MPa, tensile modulus 1181～1450MPa, elongation at break 293～465%, flexural strength 85～95MPa, modulus in flexure 2650～2800MPa.The copolyester section that the present invention obtains can be used for processing various heat-shrinkable film.
Embodiment
The umber that the following examples are all and percentage ratio are all that to take the weight of PTA be benchmark.
Embodiment 1:
At one, nitrogen inlet is housed, condensation product outlet, in the 5L stainless steel cauldron of agitator and temperature indication, add 996 grams of pure terephthalic acids (PTA), 99 gram 1, 6-hexylene glycol (HD), the zinc acetate of 421ml ethylene glycol (EG) and 200ppm, the Cobaltous diacetate of 100ppm, the Germanium tetraacetate of 100ppm is catalyst compounded, then with nitrogen, be pressurized to 0.25MPa-0.3MPa, keep constant voltage, temperature rise to 240 ℃ in reactor, when the amount that distillates water byproduct in question response still reaches theoretical aquifer yield, still internal pressure reverts to normal pressure, then in still, add, vacuumize the pressure making in polymeric kettle and be down to 50-100Pa in 20-30 minute, under this pressure, react 60 minutes, reaction is controlled at 275-285 ℃, then with nitrogen, make reactive system return to normal pressure, polymer melt obtains water white transparency product after the pelletizing of Cast Strip.Its limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.
Embodiment 2:
At one, nitrogen inlet is housed, condensation product outlet, in the 5L stainless steel cauldron of agitator and temperature indication, add 996 grams of pure terephthalic acids (PTA) 199 gram 1, 6-hexylene glycol (HD), 387ml ethylene glycol and 100ppm germanium oxide and 100ppm Cobaltous diacetate, 100ppm zinc acetate catalyst compounded, then with nitrogen, be pressurized to 0.25MPa-0.3MPa, keep constant voltage, temperature rise to 240 ℃ in reactor, when the amount that distillates water byproduct in question response still reaches theoretical aquifer yield, still internal pressure reverts to normal pressure, then to the pressure that adds 300ppm tetrabutyl titanate to vacuumize in still to make in polymeric kettle, in 20-30 minute, be down to 50-100Pa, under this pressure, react 60 minutes, reaction is controlled at 275-285 ℃, then with nitrogen, make reactive system return to normal pressure, polymer melt obtains water white transparency product after the pelletizing of Cast Strip.Its limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.
Embodiment 3:
At one, nitrogen inlet is housed, condensation product outlet, in the 5L stainless steel cauldron of agitator and temperature indication, add 996 grams of pure terephthalic acids (PTA), 199 gram 1, 6-hexylene glycol (HD), the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 374ml ethylene glycol and 100ppm, the germanium oxide of 100ppm, the zinc acetate of 200ppm catalyst compounded, then with the nitrogen 0.25MPa-0.3MPa that pressurizes, keep constant voltage, temperature rise to 240 ℃ in reactor, when the amount that distillates water byproduct in question response still reaches theoretical aquifer yield, still internal pressure reverts to normal pressure, then in still, add 400ppm tetrabutyl titanate, vacuumize the pressure making in polymeric kettle and be down to 50-100Pa in 20-30 minute, under this pressure, react 60 minutes, reaction is controlled at 275-285 ℃, then with nitrogen, make reactive system return to normal pressure, polymer melt obtains water white transparency product after the pelletizing of Cast Strip.Its limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.
Embodiment 4:
At one, nitrogen inlet is housed, in the 5L stainless steel cauldron of condensation product outlet and agitator, add 996 grams of pure terephthalic acids (PTA), 296 gram 1, 6-hexylene glycol (HD), 337ml ethylene glycol and 200ppm Germanium tetraacetate, the Cobaltous diacetate of 100ppm, the zinc acetate of 200ppm catalyst compounded, then with nitrogen, be pressurized to 0.25MPa-0.3MPa, keep constant voltage, temperature rise to 240 ℃ in reactor, when the amount that distillates water byproduct in question response still reaches theoretical aquifer yield, still internal pressure reverts to normal pressure, then to the titanium isopropylate that adds 300ppm in still, vacuumize the pressure making in polymeric kettle and be down to 50-100Pa in 20-30 minute, under this pressure, react 60 minutes, reaction is controlled at 275-285 ℃, then with nitrogen, make reactive system return to normal pressure, polymer melt obtains water white transparency product after the pelletizing of Cast Strip.Its limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.
Embodiment 5:
At one, nitrogen inlet is housed, in the 5L stainless steel cauldron of condensation product outlet and agitator, add 996 grams of pure terephthalic acids (PTA), 394 gram 1, 6-hexylene glycol (HD), the zinc acetate of 287ml ethylene glycol and 200ppm, the cobaltous phosphate of 100ppm, the Germanium tetraacetate of 200ppm catalyst compounded, then with nitrogen, be pressurized to 0.25MPa-0.3MPa, keep constant voltage, temperature rise to 240 ℃ in reactor, when the amount that distillates water byproduct in question response still reaches theoretical aquifer yield, still internal pressure reverts to normal pressure, then to the titanium isopropylate that adds 400ppm in still, vacuumize the pressure making in polymeric kettle and be down to 50-100Pa in 20-30 minute, under this pressure, react 60 minutes, reaction is controlled at 275-285 ℃, then with nitrogen, make reactive system return to normal pressure, polymer melt obtains water white transparency product after the pelletizing of Cast Strip.Its limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.
Embodiment 6
At one, nitrogen inlet is housed, in the 5L stainless steel cauldron of condensation product outlet and agitator, add 996 grams of pure terephthalic acids (PTA), 394 gram 1, 6-hexylene glycol (HD), the zinc acetate of 287ml ethylene glycol and 200ppm, the Germanium tetraacetate of 1500ppm, the Cobaltous diacetate of 100ppm catalyst compounded, then with nitrogen, be pressurized to 0.25MPa-0.3MPa, keep constant voltage, temperature rise to 240 ℃ in reactor, when the amount that distillates water byproduct in question response still reaches theoretical aquifer yield, still internal pressure reverts to normal pressure, then to the tetrabutyl titanate that adds 400ppm in still, vacuumize the pressure making in polymeric kettle and be down to 50-100Pa in 20-30 minute, under this pressure, react 60 minutes, reaction is controlled at 275-285 ℃, then with nitrogen, make reactive system return to normal pressure, polymer melt obtains water white transparency product after the pelletizing of Cast Strip.Its limiting viscosity 0.55～0.75dL/g, 160 ℃-230 ℃ of fusing points.
Claims (1)
1. a 6-hexylene glycol modification heat-shrinkable film copolyesters, it is characterized in that: be by 1,6-hexylene glycol, pure terephthalic acid and ethylene glycol, under catalyst compounded catalysis, through esterification and the synthetic polyethylene terephthalate 1 of polycondensation, 6-hexylene glycol copolyesters; The mol ratio of ethylene glycol and 1,6-hexylene glycol is 40: 60～90: 10; The mol ratio of pure terephthalic acid and ethylene glycol and 1,6-hexylene glycol mole number sum is 1: 1.0～1.8; Catalyzer is the composite catalyst of titanium compound, zn cpds, cobalt compound, germanide;
The add-on of described titanium compound be take titanium compound weight in terephthalic acid content as 100～800ppm be benchmark;
The add-on of described zn cpds be take zn cpds in terephthalic acid weight content as 100～500ppm be benchmark;
The add-on of described cobalt compound be take cobalt compound weight in terephthalic acid content as 50～300ppm be benchmark;
The add-on of described germanium compound be take germanium compound weight in terephthalic acid content as 50～300ppm be benchmark;
Esterification reaction pressure is 0.25-0.30MPa, and temperature is at 205～285 ℃;
Polycondensation reaction pressure is 10～150Pa, and reaction final temperature is controlled at 265～285 ℃, 60～120 minutes time; The fusing point of multipolymer is that 160 ℃-230 ℃, limiting viscosity are 0.55～0.75dL/g, and elongation at break is greater than 100%.
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| CN201110108937.7A CN102757549B (en) | 2011-04-28 | 2011-04-28 | 1, 6-hexanediol modified copolyester for hot shrink films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1630674A (en) * | 2002-02-14 | 2005-06-22 | 三井化学株式会社 | Polyester resin and catalyst for polyester production, process for producing polyester resin with the catalyst, polyester resin obtained with the catalyst, and hollow molded container comprising the p |
| CN101597373A (en) * | 2008-06-06 | 2009-12-09 | 常利红 | The processing method of preparation aliphatic copolyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1630674A (en) * | 2002-02-14 | 2005-06-22 | 三井化学株式会社 | Polyester resin and catalyst for polyester production, process for producing polyester resin with the catalyst, polyester resin obtained with the catalyst, and hollow molded container comprising the p |
| CN101597373A (en) * | 2008-06-06 | 2009-12-09 | 常利红 | The processing method of preparation aliphatic copolyester |
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