CN103102646A - Low-melting point and high-crystallization temperature PET copolyester, its preparation method and application - Google Patents
Low-melting point and high-crystallization temperature PET copolyester, its preparation method and application Download PDFInfo
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- CN103102646A CN103102646A CN201110352151XA CN201110352151A CN103102646A CN 103102646 A CN103102646 A CN 103102646A CN 201110352151X A CN201110352151X A CN 201110352151XA CN 201110352151 A CN201110352151 A CN 201110352151A CN 103102646 A CN103102646 A CN 103102646A
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Abstract
The invention discloses a low-melting point and high-crystallization temperature PET (polyethylene terephthalate) copolyester, its preparation method and application. The PET copolyester comprises, by mass: 70%-88% of PET, 5%-10% of a melting point adjusting agent, and 7%-20% of a crystallization accelerating agent. According to the preparation method, in a synthesis process of PET, based on p-phthalic acid (PTA) and ethylene glycol (EG), the melting point adjusting agent and the crystallization accelerating agent are added to undergo a chemical reaction together, thus obtaining the low-melting point and high-crystallization temperature PET copolyester. The PET copolyester provided by the invention has a low melting point and a high crystallization temperature, and has improved processing molding performance, thus being widely applicable in injection molding products.
Description
Technical field
The present invention relates to a kind of PET copolyesters, be specifically related to a kind of low melting point, high crystallization temperature PET copolyesters and its preparation method and application.
Background technology
Polyethylene terephthalate PET low price, excellent property are so its usage quantity increases year by year.Because PET main chain rigidity is large, sub-chain motion is slow, and crystallization velocity is slow, and then causes that its injection mould temperature is high, injection cycle is long, the easy warpage of goods, makes its application in engineering plastics be subject to serious restriction.
In order to solve the problems such as the Mo Wengao of PET in injection moulding process, shaping cycle be long, can be by reducing fusing point, improving Tc and realize.In the prior art, can reduce by the method for copolymerization the fusing point of PET, a kind of preparation method who is applied to the high-flexibility PET copolymer of spunlace non-woven cloth is disclosed as Chinese patent 200910185316.1, method by terephthalic acid, m-phthalic acid, ethylene glycol, polyoxyethylene glycol copolymerization, the flexible group PEG400-600 of access on the PET main chain, generate the PEG-PET segmented copolymer, this polyester has good flexibility, but it is mainly used in spunlace non-woven cloth.
improving the PET Tc is mainly by adding additive to adopt the method for physical blending to realize, a kind of polyethylene terephthalate matrix material and preparation method thereof is disclosed as Chinese patent 200610116598.6, utilize PET and high molecular nucleating agent, crystallization promoter and other auxiliary agents drop into twin screw extruder after high-speed stirring is mixed, plasticizing, melting is by extruding, tie rod, cooling, pelletizing, oven dry obtains finished product, the method has the crystallization rate that improves polyethylene terephthalate, convenient for production, but the method by blend is introduced high molecular nucleating agent in polyester material, can it Uniform Dispersion in resin matrix, and whether can move in processing and use procedure, reunite, all can affect the performance of PET.In addition, high molecular nucleating agent crust liquid crystal cost is higher, to temperature sensitive, do not meet actual production.
Summary of the invention
For solving above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of low melting point, high crystallization temperature PET copolyesters and its preparation method and application.
The present invention is achieved through the following technical solutions:
A kind of low melting point, high crystallization temperature PET copolyesters is characterized in that: by mass percentage, comprise following component:
PET：70%~88%
Fusing point conditioning agent: 5 ~ 10%
Crystallization promoter: 7 ~ 20%.
Described fusing point conditioning agent is selected from one or more the mixture in following compound: m-phthalic acid, dimethyl isophthalate, phthalic acid, oxalic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, SA, 1,4-butyleneglycol, neopentyl glycol, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid or its carboxylate.
Described crystallization promoter is selected from one or more the mixture in following compound: polyoxyethylene glycol, polytetrahydrofuran, poly(propylene oxide), polycaprolactone and poly(lactic acid).
The molecular weight of described crystallization promoter is between 2000 ~ 100000, and preferred molecular weight is between 4000 ~ 10000.In this molecular weight ranges, can obviously improve the Tc of PET copolyesters, can guarantee the processing characteristics that the PET copolyesters is good simultaneously.
The limiting viscosity of described PET copolyesters is 0.8 ~ 1.2dL/g, and fusing point is 220 ~ 240 ℃, and Tc is 180 ~ 210 ℃.
The preparation method of a kind of low melting point, high crystallization temperature PET copolyesters is characterized in that: comprise the following steps:
A, esterification: terephthalic acid PTA, ethylene glycol EG, fusing point conditioning agent are put in esterifying kettle, at 240 ~ 260 ℃, carried out esterification under 0.2 ~ 0.4MPa, generate carboxylate;
B, polycondensation; After the water quantity of distillate of esterification generation reaches target value, its carboxylate is transferred in polycondensation vessel, add the catalytic antimony trioxide, tetrabutyl titanate, stablizer triphenylphosphate TPP, antioxidant 1010 and crystallization promoter, normal pressure polycondensation 45 ~ 60 minutes, in 45 minutes, reacting kettle inner pressure is reduced to 60Pa gradually, temperature is increased to 265 ~ 275 ℃ simultaneously, high vacuum polycondensation 2 hours, be filled with nitrogen, under nitrogen pressure, material extruded from reactor, obtain the polycondensate pelletizing through water-cooled, tie rod, pelletizing;
C, solid-phase tack producing: with pre-crystallized 2 hours at 130 ℃ after polycondensate pelletizing oven dry, then below 20Pa, 160 ~ 190 ℃ of lower solid phase polycondensations carried out in 15 ~ 20 hours, after limiting viscosity reached target value, cooling, discharging namely obtained low melting point, high crystallization temperature PET copolyesters.
Preparation process of the present invention comprises esterification stage and polycondensation stage, and fusing point conditioning agent and crystallization promoter are before any one step of reaction, in step of reaction or add after step of reaction and prepare the PET copolyesters; Described fusing point conditioning agent and the crystallization promoter of adding be for once all adding or gradation adds, and it is that before the differential responses stage, in step of reaction or after step of reaction, gradation adds that described gradation adds.
The present invention both had been applicable to intermittently esterification, polycondensation, also can be used for continuous esterification, discontinuous polycondensation, and continuous esterification, continuous condensed technique.
Low melting point claimed in claim 1, the application of high crystallization temperature PET copolyesters in the preparation injection moulded products, the PET copolyesters for preparing can be joined in the hopper of twin screw extruder, the screw zones temperature is respectively 250 ~ 270 ℃, wherein leading portion is 250 ~ 260 ℃, 255 ~ 265 ℃, stage casing, 255 ~ 265 ℃ of back segments are injected resin after mould coolingly, obtain inner and outer decorative parts, car door, bicycle assembly parts, electronic sensor shell of injection-molded item such as automobile etc.
The present invention compared with prior art has following advantage:
(1) its fusing point of PET copolyesters of the present invention is low to moderate 220 ℃, Tc is higher than 180 ℃, the problems such as Mo Wengao, the shaping cycle of PET in injection moulding process be long have been solved, improved the machine-shaping property of PET copolyesters, made it have better modulus in flexure, tensile strength and elongation at break;
(2) the present invention is in the building-up process of polyethylene terephthalate (PET), adds fusing point conditioning agent and crystallization promoter jointly to carry out chemical reaction and generates, and its production technique is simple, has reduced production cost, is fit to industrial production.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the better embodiment of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.
Testing method:
Limiting viscosity: take phenol 50%(wt) and sym.-tetrachloroethane (50%) be solvent, strength of solution is 0.5g/dL, measures under 25 ℃;
Melt temperature and Tc: adopt Perkins Elmer DSC-6 analysis-e/or determining, nitrogen atmosphere is warming up to 260 ℃ from 20 ℃ with 10 ℃/min, constant temperature 3min, then be cooled to 20 ℃ with 10 ℃/min, then 10 ℃/min is warming up to 260 ℃.
Embodiment 1
Terephthalic acid 3.74kg, m-phthalic acid 0.42kg, ethylene glycol 2.02kg are dropped in esterifying kettle, carry out esterification under 0.2 ~ 0.4MPa, 260 ℃; After the water quantity of distillate of esterification generation reaches target value, it is transferred in polycondensation vessel, add catalyzer 0.5g antimonous oxide, 0.24g tetrabutyl titanate, stablizer 0.72g triphenylphosphate TPP, 1.2g antioxidant 1010 and crystallization promoter 332g PEG20000, normal pressure polycondensation 45 minutes was reduced to 60Pa gradually with reacting kettle inner pressure in 45 minutes, temperature is increased to 275 ℃ simultaneously, high vacuum polycondensation 2 hours; After limiting viscosity reaches target value, be filled with nitrogen, under nitrogen pressure, resin is extruded from reactor, obtain copolyester section through water-cooled, tie rod, pelletizing; Then will cut into slices after oven dry 130 ℃ pre-crystallized 2 hours, be warming up to 210 ℃, the following high vacuum solid phase polycondensation of pressure 20Pa 20 hours, be cooled to 60 ℃ with bottom discharge; With the section after solid-phase tack producing oven dry, join in the hopper of twin screw extruder and carry out injection moulding, the screw zones temperature is respectively 250 ~ 270 ℃, and wherein leading portion is 250 ~ 260 ℃, 255 ~ 265 ℃, stage casing, 255 ~ 265 ℃ of back segments.The performance test results sees Table 1.
Embodiment 2
Terephthalic acid 4.98kg, ethylene glycol 2.41kg, BDO 0.28kg are dropped in the esterification axe, carry out esterification under 0.2 ~ 0.4MPa, 260 ℃; After the water quantity of distillate of esterification generation reaches target value, it is transferred in polycondensation vessel, add catalyzer 0.6g antimonous oxide, 0.32g tetrabutyl titanate, stablizer 1.05g triphenylphosphate TPP, 0.95g antioxidant 1010 and crystallization promoter 348g Macrogol 4000, the normal pressure polycondensation was reduced to 60Pa with reacting kettle inner pressure after 60 minutes gradually in 45 minutes, temperature is increased to 275 ℃ simultaneously, high vacuum polycondensation 2 hours; After limiting viscosity reaches target value, be filled with nitrogen, under nitrogen pressure, resin is extruded from reactor, obtain copolyester section through water-cooled, tie rod, pelletizing; Then will cut into slices after oven dry 130 ℃ pre-crystallized 2 hours, be warming up to 210 ℃, the following high vacuum solid phase polycondensation of pressure 20Pa 20 hours, be cooled to 60 ℃ with bottom discharge; With the section after solid-phase tack producing oven dry, join in the hopper of twin screw extruder and carry out injection moulding, the screw zones temperature is respectively 250 ~ 270 ℃, and wherein leading portion is 250 ~ 260 ℃, 255 ~ 265 ℃, stage casing, 255 ~ 265 ℃ of back segments.The performance test results sees Table 1.
Embodiment 3
with terephthalic acid 4.64kg, m-phthalic acid 0.35kg, ethylene glycol 2.41kg, polytetrahydrofuran 2000 996g and catalyzer 1.16g antimonous oxide, 0.26g tetrabutyl titanate, stablizer 1.05g triphenylphosphate TPP, 0.95g antioxidant 1010 drops in the esterification axe, at 0.2 ~ 0.4MPa, carry out esterification under 260 ℃, after the quantity of distillate of the water that esterification generates reaches target value, it is transferred in polycondensation vessel, 260 ℃ of normal pressure polycondensations after 60 minutes, in 45 minutes, reacting kettle inner pressure is reduced to 60Pa gradually, temperature is increased to 270 ℃ simultaneously, high vacuum polycondensation 2 hours, after limiting viscosity reaches target value, be filled with nitrogen, under nitrogen pressure, resin is extruded from reactor, obtain copolyester section through water-cooled, tie rod, pelletizing, then will cut into slices after oven dry 130 ℃ pre-crystallized 2 hours, be warming up to 210 ℃, the following high vacuum solid phase polycondensation of pressure 20Pa 20 hours, be cooled to 60 ℃ with bottom discharge, with the section after solid-phase tack producing oven dry, join in the hopper of twin screw extruder and carry out injection moulding, the screw zones temperature is respectively 250 ~ 270 ℃, and wherein leading portion is 250 ~ 260 ℃, 255 ~ 265 ℃, stage casing, 255 ~ 265 ℃ of back segments.The performance test results sees Table 1.
Embodiment 4
Terephthalic acid 4.98kg, ethylene glycol 2.37kg, neopentyl glycol 0.18kg are dropped in the esterification axe, carry out esterification under 0.2 ~ 0.4MPa, 260 ℃, after the water quantity of distillate of esterification generation reaches target value, it is transferred in polycondensation vessel, add catalyzer, stablizer, oxidation inhibitor and 498g polytetrahydrofuran 1000, normal pressure polycondensation 60 minutes, in 45 minutes, reacting kettle inner pressure is reduced to 60Pa gradually, temperature is increased to 275 ℃ simultaneously, high vacuum polycondensation 2 hours after limiting viscosity reaches target value, is filled with nitrogen.Under nitrogen pressure, resin is extruded from reactor, obtain copolyester section through water-cooled, tie rod, pelletizing; Then will cut into slices after oven dry 130 ℃ pre-crystallized 2 hours, be warming up to 175 ℃, the following high vacuum solid phase polycondensation of pressure 20Pa 20 hours, be cooled to 60 ℃ with bottom discharge; With the section after solid-phase tack producing oven dry, join in the hopper of twin screw extruder and carry out injection moulding, the screw zones temperature is respectively 250 ~ 270 ℃, and wherein leading portion is 250 ~ 260 ℃, 255 ~ 265 ℃, stage casing, 255 ~ 265 ℃ of back segments.The performance test results sees Table 1.
The performance test results of the prepared PET copolyesters of table 1 embodiment 1 ~ 4
Can see from above-described embodiment, described PET copolyesters, its fusing point are low to moderate 220 ℃, and Tc has been improved the machine-shaping property of PET copolyesters higher than 180 ℃, and it has better modulus in flexure, tensile strength and elongation at break.
Claims (8)
1. a low melting point, high crystallization temperature PET copolyesters is characterized in that: by mass percentage, comprise following component:
PET：70%~88%
Fusing point conditioning agent: 5 ~ 10%
Crystallization promoter: 7 ~ 20%.
2. low melting point according to claim 1, high crystallization temperature PET copolyesters, it is characterized in that: described fusing point conditioning agent is selected from m-phthalic acid, dimethyl isophthalate, phthalic acid, oxalic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, SA, 1,4-butyleneglycol, neopentyl glycol, 1,2-cyclohexane dicarboxylic acid, 1, the mixture of one or more in 3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid or its carboxylate.
3. low melting point according to claim 1, high crystallization temperature PET copolyesters is characterized in that: described crystallization promoter is selected from one or more the mixture in polyoxyethylene glycol, polytetrahydrofuran, poly(propylene oxide), polycaprolactone and poly(lactic acid).
4. low melting point according to claim 1, high crystallization temperature PET copolyesters, it is characterized in that: the molecular weight of described crystallization promoter is between 2000 ~ 100000.
5. low melting point according to claim 4, high crystallization temperature PET copolyesters, it is characterized in that: the molecular weight of described crystallization promoter is between 4000 ~ 10000.
6. low melting point according to claim 1, high crystallization temperature PET copolyesters, it is characterized in that: the limiting viscosity of described PET copolyesters is 0.8 ~ 1.2dL/g, and fusing point is 220 ~ 240 ℃, and Tc is 180 ~ 210 ℃.
7. the preparation method of the described low melting point of claim 1 ~ 6 any one, high crystallization temperature PET copolyesters is characterized in that: comprise the following steps:
A, esterification: terephthalic acid PTA, ethylene glycol EG, fusing point conditioning agent are put in esterifying kettle, at 240 ~ 260 ℃, carried out esterification under 0.2 ~ 0.4MPa, generate carboxylate;
B, polycondensation: after the water quantity of distillate of esterification generation reaches target value, its carboxylate is transferred in polycondensation vessel, add catalyzer, stablizer, oxidation inhibitor and crystallization promoter, normal pressure polycondensation 45 ~ 60 minutes, in 45 minutes, reacting kettle inner pressure is reduced to 60Pa gradually, temperature is increased to 265 ~ 275 ℃ simultaneously, high vacuum polycondensation 2 hours is filled with nitrogen, under nitrogen pressure, material is extruded from reactor, obtain the polycondensate pelletizing through water-cooled, tie rod, pelletizing;
C, solid-phase tack producing: with pre-crystallized 2 hours at 130 ℃ after polycondensate pelletizing oven dry, then below 20Pa, 160 ~ 190 ℃ of lower solid phase polycondensations carried out in 15 ~ 20 hours, after limiting viscosity reached target value, cooling, discharging namely obtained low melting point, high crystallization temperature PET copolyesters.
8. low melting point claimed in claim 1, the application of high crystallization temperature PET copolyesters in the preparation injection moulded products.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987498A (en) * | 2015-04-02 | 2015-10-21 | 沈阳工业大学 | Low-melting point copolyester preparation method |
| CN108164933A (en) * | 2016-12-07 | 2018-06-15 | 南京科技职业学院 | A kind of preparation method of low-melting point polyester |
| CN109153473A (en) * | 2016-04-11 | 2019-01-04 | 美国达克有限责任公司 | Polyester container and film with reduced gas permeability |
| CN109651605A (en) * | 2018-12-12 | 2019-04-19 | 上海天洋热熔粘接材料股份有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN114380993A (en) * | 2020-10-05 | 2022-04-22 | 财团法人工业技术研究院 | Copolymers and methods of forming the same |
| CN114474909A (en) * | 2022-01-27 | 2022-05-13 | 广东汇天航空航天科技有限公司 | Flame-retardant carpet substrate layer and flame-retardant carpet |
| CN115181402A (en) * | 2022-08-17 | 2022-10-14 | 华润化学材料科技股份有限公司 | Copolyester composition easy to extrude and blow and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463123A (en) * | 2009-01-05 | 2009-06-24 | 浙江理工大学 | Low-melting point PTT copolyester and manufacturing method thereof |
| 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 |
-
2011
- 2011-11-09 CN CN201110352151XA patent/CN103102646A/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 |
| CN101463123A (en) * | 2009-01-05 | 2009-06-24 | 浙江理工大学 | Low-melting point PTT copolyester and manufacturing method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987498A (en) * | 2015-04-02 | 2015-10-21 | 沈阳工业大学 | Low-melting point copolyester preparation method |
| CN109153473A (en) * | 2016-04-11 | 2019-01-04 | 美国达克有限责任公司 | Polyester container and film with reduced gas permeability |
| CN109153473B (en) * | 2016-04-11 | 2021-08-17 | 美国达克有限责任公司 | Polyester containers and films with reduced gas permeability |
| US11186713B2 (en) | 2016-04-11 | 2021-11-30 | Dak Americas Llc | Polyester containers and films with reduced gas permeability |
| CN108164933A (en) * | 2016-12-07 | 2018-06-15 | 南京科技职业学院 | A kind of preparation method of low-melting point polyester |
| CN109651605A (en) * | 2018-12-12 | 2019-04-19 | 上海天洋热熔粘接材料股份有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN114380993A (en) * | 2020-10-05 | 2022-04-22 | 财团法人工业技术研究院 | Copolymers and methods of forming the same |
| CN114474909A (en) * | 2022-01-27 | 2022-05-13 | 广东汇天航空航天科技有限公司 | Flame-retardant carpet substrate layer and flame-retardant carpet |
| CN115181402A (en) * | 2022-08-17 | 2022-10-14 | 华润化学材料科技股份有限公司 | Copolyester composition easy to extrude and blow and preparation method thereof |
| CN115181402B (en) * | 2022-08-17 | 2023-10-27 | 华润化学材料科技股份有限公司 | Copolyester composition easy to extrude and blow and preparation method thereof |
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Application publication date: 20130515 |