CN102286195B - Rapidly crystallized polyethylene glycol terephthalate composite material and preparation method thereof - Google Patents
Rapidly crystallized polyethylene glycol terephthalate composite material and preparation method thereof Download PDFInfo
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- CN102286195B CN102286195B CN 201110191114 CN201110191114A CN102286195B CN 102286195 B CN102286195 B CN 102286195B CN 201110191114 CN201110191114 CN 201110191114 CN 201110191114 A CN201110191114 A CN 201110191114A CN 102286195 B CN102286195 B CN 102286195B
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Abstract
The invention discloses a rapidly crystallized polyethylene glycol terephthalate composite material which is characterized in that the composite material is prepared from 90 to 98.5 weight percent of polyethylene glycol terephthalate, 0.3 to 5 weight percent of expanded graphite and 1 to 5 percent of polyethylene glycol by melting blending; the melting crystallizing temperature of the composite material is in the range of 215 to 221 DEG C; the glass transition temperature of the composite material is in the range of 50 to 65 DEG C; and the cold crystallization temperature of the composite material is in the range of 90 to 108 DEG C. The invention also discloses a preparation method of the composite material. The expanded graphite can be rapidly crystallized in the cooling process, the polyethylene glycol can reduce the glass transition temperature of PET (polyethylene glycol terephthalate) by improving the motion activity of a polymer chain segment and ensure the PET crystals to still grow at high speed when being cooled to a die temperature, so that the overall crystallizing speed of the composite material is greatly improved, the forming period is shortened and the production cost is reduced. The preparation method disclosed by the invention has simple process. The production process is easy to control.
Description
Technical field
The invention belongs to polyethylene terephthalate matrix material and preparing technical field thereof, be specifically related to a kind of nucleator and the collaborative method of polyethylene terephthalate (PET) rapid crystallization and PET matrix material of corresponding rapid crystallization of promoting of crystallization promoter of utilizing.
Background technology
Come out in nineteen forty-one from PET, realize the earliest industrialization in nineteen fifty-three by Dupont company, though PET can keep good physicals and mechanical property because of it in wide temperature range, and resistance to fatigue, rub resistance, ageing resistance is excellent, electrical insulating property is outstanding, stable to most of organic solvents and mineral acid, and production energy consumption is low, processibility well is celebrated and mainly is used as fiber, sheet material and beverage bottle, but exist when PET uses as engineering plastics: second-order transition temperature is high, the nucleation ability, crystallization rate waits problem slowly, especially with other crystalline polymer such as polyethylene (PE), polypropylene (PP) is compared with polybutylene terephthalate (PBT), and it is very low that the crystallization rate of PET more seems.Maximum spherulite growth rate such as PE is 5000 μ m/min, and that PET only is 10 μ m/min.The Tc of PET is high in addition, makes its injection mould temperature need reach 120～140 ℃, so less economical, make PET slow as the application development of engineering plastics.
The key issue that solves the PET through engineering approaches is to improve its crystallizing power, Chinese scholars has been done a large amount of research and developments for this reason, for example patent US.Pat.No.4272475 discloses and a kind ofly can control cylinder temperature in PET injection molding, nozzle temperature, the method of injection temperature and inject time obtains to have the product of mechanical property preferably and unified quality, but when the molecular weight of used PET is too low, but can not be applied to the engineering plastics field, and use the PET of high molecular higher because of its Tc, die needed temperature is higher, need the oil bath system to cooperate when injection molding, this increases the danger of cost and operation again.In order to improve the crystallization rate of PET, though people have worked out more effective organic nucleating agent, mostly be aromatic monocarboxylic acid sodium salt.Reported the organic nucleating agent of a kind of PET such as US.Pat.No.4451606---the multipolymer of polyalkylene terephthalate and aromatic sulphonate, this organic nucleating agent can be total to molten and Uniform Dispersion with PET, although its nucleating effect is better, can make flexible chain shorten 50%, but this organic nucleating agent not only can lose the nucleation ability because of degraded in the course of processing of PET, also can cause simultaneously the local chain rupture of PET molecular chain, and cost is also higher.For fear of the problem that organic nucleating agent brings, inorganic particulate begins to be widely adopted as the nucleator of PET.Report the relevant inorganic nucleator of PET such as US.Pat.No.5886088, comprised talcum, mica, wollastonite, clay, kaolin, diatomite, wilkinite, polynite, hydrotalcite, calcium carbonate, titanium trioxide, potassium titanate, asbestos, barium oxide etc.Inorganic nucleator is not only cheap, and resistance to chemical attack, good processing stability, but its nucleation efficient of the relative organic nucleating agent of inorganic nucleator is relatively poor, and melt crystallization temperature is the highest can only to improve 10 ℃; Simultaneously in injection molding, because die temperature guarantees that goods have higher degree of crystallinity near usually all wishing to be arranged on cold crystallization temperature, and lower die temperature can shorten shaping cycle, reduce production costs, though and the use inorganic particulate also can reduce cold crystallization temperature to a certain extent as nucleator, but since during Added Nucleating Agents to reducing the DeGrain of cold crystallization temperature, the setting of die temperature just can not be hanged down and both be guaranteed that goods have higher degree of crystallinity, shorten again shaping cycle, reduce production costs.
Summary of the invention
The objective of the invention is the deficiency for existing PET nucleator existence, provide a kind of with expanded graphite as nucleator, polyoxyethylene glycol is as crystallization promoter, the collaborative crystal property that improves PET, but the PET matrix material that decrease cold crystallization temperature, acquisition can rapid crystallizations.
Another object of the present invention provides a kind of method for preparing the PET matrix material of rapid crystallization
The polyethylene terephthalate matrix material of rapid crystallization provided by the invention, it is characterized in that this matrix material is to be formed through melt blending by the polyethylene terephthalate of 90-98.5wt%, the expanded graphite of 0.3-5wt%, the polyoxyethylene glycol of 1-5%, 215-221 ℃ of its melt crystallization temperature, second-order transition temperature 50-65 ℃, cold crystallization temperature 90-108 ℃.
The method of the polyethylene terephthalate matrix material of the above-mentioned rapid crystallization of preparation provided by the invention, processing step and the condition of the method are as follows:
1) polyethylene terephthalate pellet 90-98.5wt% and expanded graphite 0.3-5wt% are put into high-speed stirring mixer, under the high speed shear effect of 15000-18000rpm, mix 4-6min;
2) first with the 1st) go on foot the compound and the polyoxyethylene glycol 1-5wt% premix that make, and then Preblend is namely got the polyethylene terephthalate matrix material in 265-280 ℃ of melt blending 6-8min.
The preferred 0.5-5wt% of the add-on of expanded graphite in the aforesaid method, the preferred 3-5wt of the add-on of polyoxyethylene glycol, and the melt crystallization temperature of the matrix material of corresponding preparation is 218-221 ℃, second-order transition temperature 55-65 ℃, and cold crystallization temperature 90-101 ℃.
The intrinsic viscosity of the polyethylene terephthalate that uses in the aforesaid method is 0.80～0.90.
The number-average molecular weight of the polyoxyethylene glycol that uses in the aforesaid method is 1000-2000.
The particle diameter of the expanded graphite that uses in the aforesaid method is the 80-100 order, and expansion multiple is 200-300 times.
The present invention compared with prior art has following beneficial effect:
1, because the expanded graphite nucleator in the polyethylene terephthalate matrix material provided by the invention can cause crystallization fast when cooling, and Polyethylene glycol crystal promotor can be by improving the locomotor activity of polymer segment, reduce the second-order transition temperature of PET, when being cooled to the mould temperature, make the PET crystal still keep high-speed rapid growth, thereby polyethylene terephthalate composites crystallization rate is greatly improved.
2, owing to polyethylene terephthalate matrix material cold crystallization temperature provided by the invention decrease, thereby both can realize being lowered into the mould temperature and guaranteed that goods had higher degree of crystallinity, can really shorten shaping cycle again, reduce production costs.
3, be the higher PET of molecular weight owing to what adopt in the polyethylene terephthalate matrix material provided by the invention, thereby this material can be used for the engineering plastics field.
4, because the inventive method had both adopted expanded graphite as nucleator, adopt again PEG to prepare the PET matrix material as crystallization promoter, thereby not only make the crystal property of the matrix material that obtains all want high more than independent Added Nucleating Agents or crystallization promoter, and also there is obvious synergy in both to glass transition.Can be brought up to 221 ℃ by initial 205 ℃ such as its melt crystallization temperature, second-order transition temperature is reduced to 50 ℃ by initial 70 ℃, and cold crystallization temperature is reduced to 90 ℃ by initial 123 ℃.
5, because the present invention not only adopts the inorganic particulate expanded graphite as the nucleator of PET, also adopted PEG as crystallization promoter, thereby the problems such as high temperature failure of both effectively having avoided organic nucleating agent to bring, effectively avoided again the relatively poor problem of inorganic nucleator nucleation efficient.
6, since the expanded graphite that the present invention uses and PEG both originated abundant, cheap again, thereby the production cost that can further reduce.
7, preparation method's process provided by the invention is simple, and production technique is controlled easily.
Description of drawings
Fig. 1 is that flexible chain in the isothermal cold crystallization process of the embodiment of the invention 5 and Comparative Examples is to the Tc graphic representation.As can be seen from the figure, collaboration system not only can improve the cold crystallization speed of matrix PET, and can enlarge the scope of its Tc, and the die temperature when this just can reduce injection molding shortens shaping cycle, reduces production costs.
Fig. 2 is the embodiment of the invention 5 and the degree of crystallinity test curve of Comparative Examples after differing temps is annealed half an hour.Show among the figure, in whole annealing region, all there is synergy in the compound system of 0.5%EG and 5%PEG to the raising of PET degree of crystallinity, when annealing temperature is 90 ℃, hardly crystallization of pure PET, and its degree of crystallinity can reach 25wt% after having adopted collaboration system, and this has just guaranteed that goods also have higher degree of crystallinity after reducing die temperature.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to the content of the invention described above still belong to protection scope of the present invention.
What deserves to be explained is in addition, 1) sample for the test crystal property is that the material of inciting somebody to action is respectively first put into dull and stereotyped moulding press in 270 ℃ of temperature in following each embodiment and the Comparative Examples, hot-forming 6min under the pressure 0.4Mpa, the sample that then will take out and be molten state put into liquid nitrogen and quench and namely obtain testing the amorphous PET film of usefulness; 2) the amorphous PET film of each embodiment and Comparative Examples gained is to test its crystal property with differential scanning calorimeter (DSC).Concrete test process is: amorphous PET film is put into differential scanning calorimeter, then be warming up to 280 ℃ from 20 ℃ of normal temperature with 10 ℃/min, stop 3min to eliminate thermal history at 280 ℃, be down to normal temperature with 10 ℃/min again.Temperature-rise period records second-order transition temperature and cold crystallization temperature, and temperature-fall period records melt crystallization temperature.Melt crystallization temperature is higher, and the crystal property of the lower interpret sample of cold crystallization temperature is better.
Embodiment 1
Be that 0.80 PET pellet 56.82g and particle diameter are that 90 orders, expansion multiple are that 300 times 0.18g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 15000rpm, mix 6min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 2000 the PEG 3g premix with this powders mixture and number-average molecular weight, and in 265 ℃ of lower melt blending 8min, namely get the PET matrix material.
It is 219 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 55 ℃, and cold crystallization temperature is 94 ℃.
Embodiment 2
Be that 0.85 PET pellet 59.1g and particle diameter are that 80 orders, expansion multiple are that 250 times 0.3g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 18000rpm, mix 4min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 1000 the PEG 0.6g premix with this powders mixture and number-average molecular weight, and in 270 ℃ of lower melt blending 6min, namely get the PET matrix material.
It is 215 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 65 ℃, and cold crystallization temperature is 108 ℃.
Embodiment 3
Be that 0.85 PET pellet 57.9g and particle diameter are that 100 orders, expansion multiple are that 300 times 0.3g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 16000rpm, mix 4min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 1500 the PEG 1.8g premix with this powders mixture and number-average molecular weight, and in 280 ℃ of lower melt blending 6min, namely get the PET matrix material.
It is 218 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 60 ℃, and cold crystallization temperature is 101 ℃.
Embodiment 4
Be that 0.85 PET pellet 56.7g and particle diameter are that 80 orders, expansion multiple are that 250 times 0.3g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 18000rpm, mix 5min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 1000 the PEG 3g premix with this powders mixture and number-average molecular weight, and in 270 ℃ of lower melt blending 7min, namely get the PET matrix material.
It is 221 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 50 ℃, and cold crystallization temperature is 90 ℃.
Embodiment 5
Be that 0.90 PET pellet 56.4g and particle diameter are that 90 orders, expansion multiple are that 250 times 0.6g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 17000rpm, mix 6min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 1500 the PEG 3g premix with this powders mixture and number-average molecular weight, and in 275 ℃ of lower melt blending 7min, namely get the PET matrix material.
It is 219 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 55 ℃, and cold crystallization temperature is 97 ℃.
Embodiment 6
Be that 0.90 PET pellet 55.2g and particle diameter are that 80 orders, expansion multiple are that 200 times 1.8g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 16000rpm, mix 5min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 1000 the PEG 3g premix with this powders mixture and number-average molecular weight, and in 280 ℃ of lower melt blending 6min, namely get the PET matrix material.
It is 219 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 55 ℃, and cold crystallization temperature is 99 ℃.
Embodiment 7
Be that 0.80 PET pellet 54g and particle diameter are that 100 orders, expansion multiple are that 300 times 3g expanded graphite is put into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 18000rpm, mix 6min, obtain the powders mixture of PET and expanded graphite; Be to put into again the Haake torque rheometer behind 2000 the PEG 3g premix with this powders mixture and number-average molecular weight, and in 280 ℃ of lower melt blending 6min, namely get the PET matrix material.
It is 218 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 55 ℃, and cold crystallization temperature is 101 ℃.
Comparative Examples 1
Be that 0.85 PET pellet 60g puts into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 18000rpm, mix 5min, obtain the PET powder; This powder is put into the Haake torque rheometer again, and in 280 ℃ of lower melt blending 6min, namely get pure PET material.
It is 205 ℃ that this material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 70 ℃, and cold crystallization temperature is 123 ℃.
Comparative Examples 2
Be that 0.85 PET pellet 59.87g and particle diameter are that 80 orders, expansion multiple are that 250 times expanded graphite 0.3g puts into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 18000rpm, mix 5min, obtain the powders mixture of PET and expanded graphite; This powders mixture is put into the Haake torque rheometer again, and in 270 ℃ of lower melt blending 7min, namely get the PET matrix material.
It is 214 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 70 ℃, and cold crystallization temperature is 110 ℃.
Comparative Examples 3
Be that 0.85 PET pellet 57g puts into high-speed stirring mixer with intrinsic viscosity, under the high speed shear effect of 18000rpm, mix 5min, obtain the PET powder; Be to put into again the Haake torque rheometer behind 1000 the PEG 3g premix with this powder and molecular weight, and in 270 ℃ of lower melt blending 7min, namely get the PET matrix material.
It is 210 ℃ that this matrix material is tested its melt crystallization temperature through DSC, and second-order transition temperature is 55 ℃, and cold crystallization temperature is 103 ℃.
If it is large that institute adds inventory, can adopt screw extrusion press to carry out melt blending.
Claims (4)
1. the polyethylene terephthalate matrix material of a rapid crystallization, it is characterized in that this matrix material is to be formed through melt blending by the polyethylene terephthalate of 90-98.5 wt%, the expanded graphite of 0.3-5wt%, the polyoxyethylene glycol of 1-5 wt%, 215-221 ℃ of its melt crystallization temperature, second-order transition temperature 50-65 ℃, cold crystallization temperature 90-108 ℃, the intrinsic viscosity of use therein polyethylene terephthalate is 0.80～0.90.
2. method for preparing the polyethylene terephthalate matrix material of rapid crystallization claimed in claim 1, processing step and the condition of the method are as follows:
1) polyethylene terephthalate pellet 90-98.5 wt% and expanded graphite 0.3-5wt% are put into high-speed stirring mixer, under the high speed shear effect of 15000-18000 rpm, mix 4-6min;
2) first with the 1st) go on foot the compound and the polyoxyethylene glycol 1-5wt% premix that make, and then Preblend is namely got the polyethylene terephthalate matrix material in 265-280 ℃ of melt blending 6-8 min,
The intrinsic viscosity of use therein polyethylene terephthalate is 0.80～0.90.
3. the method for the polyethylene terephthalate matrix material of preparation rapid crystallization according to claim 2, the number-average molecular weight of the polyoxyethylene glycol that uses in the method is 1000-2000.
4. according to claim 2 or the method for the polyethylene terephthalate matrix material of 3 described preparation rapid crystallizations, the particle diameter of the expanded graphite that uses in the method is the 80-100 order, expansion multiple be 200-300 doubly.
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| 崔正.阻燃增强聚对苯二甲酸乙二醇酯（PET）工程塑料结晶性能及配方优化研究.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2011,(第1期),正文第2.3.1、3.2节、表3-10. * |
| 李大军.聚合物/石墨导电复合材料的制备及其性能研究.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2008,(第2期),正文第二章第2.2、2.3.3节、表1. * |
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