CN103788587B - A kind of high viscosity easily processes ethylene glycol terephthalate and preparation method thereof - Google Patents
A kind of high viscosity easily processes ethylene glycol terephthalate and preparation method thereof Download PDFInfo
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- CN103788587B CN103788587B CN201210418906.6A CN201210418906A CN103788587B CN 103788587 B CN103788587 B CN 103788587B CN 201210418906 A CN201210418906 A CN 201210418906A CN 103788587 B CN103788587 B CN 103788587B
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Abstract
The invention discloses a kind of polyethylene terephthalate compositions, be more than the polyethylene terephthalate of 0.85dl/g, little branchign of molecule agent and crystallization nucleating agent including intrinsic viscosity.According to the present invention, by adding nucleator and little branchign of molecule agent in full-bodied polyethylene terephthalate, not only on the premise of keeping material high viscosity, improve the crystal property of material, and make the molecular weight distribution of material broaden；Material also has obvious shear shinning behavior, is thus advantageous to the machine-shaping of material.
Description
Technical field
The present invention relates to a kind of pet resin, have and relate to a kind of there is excellent machinability
Ethylene glycol terephthalate resin.The invention still further relates to the preparation method of above-mentioned resin.
Background technology
Thermoplastic poly ethylene glycol terephthalate (PET) due to the mechanical strength of its excellence, transparency, heat stability and
Impact strength and permeability are low and be widely used in extrusion molding, be molded and be blow molded and the product such as biaxial tension.But due to heat
Plasticity polyethylene terephthalate melt viscosity is relatively low, and crystallization rate is slow,.Its crystalline rate is other mould relative to some
Expect that such as polybutylene terephthalate (PBT) and high density polyethylene (HDPE) want slow, therefore limit its application in engineering plastics.?
In the application of PET, on the premise of keeping its higher melt viscosity, also require that it has the same of good moulding processability
Time, there is higher degree of crystallinity to meet the requirement to its intensity.
At present in the prior art about High Viscosity PET polymer, it is common that form solid phase by follow-up PET polymerization
After, then it is polymerized further under solid state shape and prepares.But for branching PET, polymerization is easy to make molecule further
Chain cross-links, and in turn resulting in converted products defect increases.
Application number CN200510112394 discloses a kind of polyester composite and preparation method thereof, this composite be by
Polyethylene terephthalate, ultrabranching polyamide are that nucleator, polymer crystallization accelerator, filling reinforcing agent and processing help
Agent forms.But the processing characteristics of composite is not improved in this patent.
Application No. WO2006096175 discloses a kind of thermoplastic compounds with high-dimensional stability.Invention relates to
Containing the compositions of polyester, wherein contain more than 2% less than 10%(percentage by weight) mica filler.Polymer blend also contains
There are impact modifying agent, nucleator and pigment.Compositions is thermoformed into the container of food tray.The processing of material in this patent same
Performance is not improved.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of polyethylene terephthalate, it is keeping Gao Rong
Under conditions of body viscosity, improve the crystallizing power of resin, and the molecular weight distribution width of resin, fluidity of molten is good, therefore has
There is extraordinary processing characteristics.
According to an aspect of the invention, it is provided a kind of polyethylene terephthalate compositions, glue including characteristic
Degree is more than the polyethylene terephthalate of 0.85dl/g, little branchign of molecule agent and crystallization nucleating agent.
In above-mentioned composition, described polyethylene terephthalate, little branchign of molecule agent and the matter of crystallization nucleating agent
Amount ratio is 100:0.01:0.1 ~ 100:0.5:1.5, preferably 100:0.05:0.35 ~ 100:0.4:1.3.
In above-mentioned composition, described little branchign of molecule agent is selected from least having the ester of 3 functional groups, acid, alcohol and spreading out
Biological.
In above-mentioned composition, described little branchign of molecule agent selected from 1,3,5-benzenetricarboxylic acids, TMLA, 1,2,4,5-
Benzenetetracarboxylic acid, pyromellitic acid dianhydride, trimellitic anhydride, glycerol, tetramethylolmethane, dipentaerythritol, trimethylolpropane, trihydroxy acid
Propane and trimethyl trimesate.
In above-mentioned composition, described crystallization nucleating agent is selected from low molecular carboxylic acid salt and high molecular nucleating agent, described high score
Sub-nucleator is selected from polyethylene acrylic acid sodium, polyethylene acrylic acid zinc and ethylene/methacrylic acid salt resin.
According to another aspect of the present invention, it is provided that a kind of branched polyethylene terephthalate, including characteristic
Viscosity is more than the polyethylene terephthalate of 0.85dl/g, little branchign of molecule agent and crystallization nucleating agent.
In above-mentioned branched polyethylene terephthalate, described polyethylene terephthalate, little branchign of molecule
The mass ratio of agent and crystallization nucleating agent is 100:0.01:0.1 ~ 100:0.5:1.5, preferably 100:0.05:0.35 ~ 100:0.4:
1.3。
In above-mentioned branched polyethylene terephthalate, described little branchign of molecule agent is selected from least having 3 senses
Ester, acid, alcohol and the derivant of group, is preferably selected from 1,3,5-benzenetricarboxylic acids, TMLA, 1,2,4,5-benzenetetracarboxylic acids, equal benzene
Tetracarboxylic dianhydride, trimellitic anhydride, glycerol, tetramethylolmethane, dipentaerythritol, trimethylolpropane, trihydroxy acid propane and equal benzene
Tricarboxylic acid trimethyl.
In above-mentioned branched polyethylene terephthalate, described crystallization nucleating agent is selected from low molecular carboxylic acid salt and high score
Sub-nucleator, described high molecular nucleating agent is selected from polyethylene acrylic acid sodium, polyethylene acrylic acid zinc and ethylene/methacrylic acid
Salt resin.
In above-mentioned branched polyethylene terephthalate, the characteristic of described branched polyethylene terephthalate is glued
Degree > 0.80dl/g, molecular weight distribution mw/mn > 2.1, crystallisation by cooling temperature is more than 210 DEG C.Branched according to present invention offer gathers
Ethylene glycol terephthalate, its molecular weight distribution widens more than 10%, and its crystallisation by cooling temperature improves more than 20 DEG C.
The preparation method of above-mentioned branched polyethylene terephthalate, including by above-mentioned dried p-phthalic acid second
Terephthalate composition carries out frit reaction after being sufficiently mixed uniformly and prepares branched polyethylene terephthalate.
In the above-mentioned methods, described reaction temperature is 220 ~ 280 DEG C.In a specific embodiment of said method, institute
State frit reaction to carry out in double screw extruder.In an instantiation, the temperature in double screw extruder Zhong Ge district controls
As follows: a district: 220-235 DEG C, two district's temperature are 265-275 DEG C, and three district's temperature are 265-280 DEG C；Four district's temperature control
265-280；Die temperature is 270-285 DEG C.
The polyester obtained according to the present invention, viscosity is high, have branched structure.It addition, after tested this high-viscosity polyester does not has
Occurring gel particles, this just illustrates do not have gelatin phenomenon to occur.
According to the present invention, by adding nucleator and little branchign of molecule in full-bodied polyethylene terephthalate
Agent, not only on the premise of keeping material high viscosity, improves the crystal property of material, and makes the molecular weight distribution of material become
Wide；Material also has obvious shear shinning behavior, is thus advantageous to the machine-shaping of material, as being highly suitable for foaming and note
Mould technique.
Accompanying drawing explanation
Fig. 1 shows the rheological data figure of pet material.
Detailed description of the invention
From figure 1 it appears that with the polyethylene terephthalate in comparative example is compared, branched according to the present invention
Polyethylene terephthalate, its viscosity is big, and shows obviously shear shinning behavior.Therefore, have the best
Processing characteristics.
Intrinsic viscosity in the present invention is measured according to GB GB/T1632.5-2008 method, and selection solvent is phenol: tetrachloro
The mixed solvent of ethane (1: 1), test temperature is 25 DEG C.
Molecular weight distribution (MWD) in the present invention passes through gel permeation chromatography (GPC), records according to following methods:
Selecting instrument is that the U.S. produces Viscotek model302-050 type gel permeation chrommatograph, and selecting solvent is hexafluoro isopropyl
Alcohol, test temperature is 40 DEG C, and selection standard specimen is PMMA, uses laser light scattering, differential refraction index and viscosity detector three to examine
Survey combination to detect.
Crystallization temperature in the present invention passes through differential scanning calorimetry (DSC), and sample is through the most dried, at nitrogen
Protection under, by Perkin-Elmer DSC thermal analyzer test.It is increased to 300 from 25 DEG C with the heating rate of 10 DEG C/min
DEG C, it is cooled to room temperature the most at a same speed, then is increased to 300 DEG C with same speed.Take and be cooled to room temperature process by 300 DEG C
In peak temperature as crystallisation by cooling temperature.
Platelet long period in the present invention and lamellae thickness, be dried PET material 12 hours at 100 DEG C in vacuum drying oven,
Injecting batten with HAKKE minijet, injection moulding condition is melt temperature 280 DEG C, and mold temperature is 60 DEG C.The batten prepared
By the Nanostar small angle X ray scattering instrument test of Bruker company of Germany, tube voltage is 40kV, and electric current is 650A, CuK radiation
(.=0.1542nm).Testing time 10min.
Dynamic rheology measurement in the present invention is to utilize ARES-2KFRTN-FCOHR flow graph, nitrogen atmosphere, 270
Measure by the flat-panel systems of diameter 25mm at DEG C, shearing frequency 1-100rad/s, strain linear viscoelastic region carry out
Oscillatory shear is tested, and obtains complex viscosity (η*) the function that value is frequency (ω).
Gel content in the present invention is tested by the following method: the PET of random state is cut into 1mm3The granule of size, takes
The sample of pulverizing of about 1g is placed in the volumetric flask of 25ml, adds phenol/sym-tetrachloroethane (1:1) mixed solvent of about 12ml
(through filtering), dissolves 5 hours at 90 DEG C, is diluted to scale with mixed solvent after cooling.Solution is used tetrafluoro filter paper filtering, so
Clean three times with mixed solvent afterwards, then with washes of absolute alcohol three times, after vacuum drying, calculate the weightening finish of filter paper.After tested, originally
In polyester material in invention, gel particles does not exists.
Embodiment 1
Taking 500gPET section, its intrinsic viscosity is 0.98dl/g, and Yizheng Fiber Optical plant produces, and 110 DEG C are dried in a conventional oven
24 hours, then it is dried 12 hours in 100 DEG C of vacuum drying ovens.Take glycerol (production of Beijing chemical reagent factory) 0.5g, become
Core agent 1g, joins in high-speed mixer by the mixed material weighed, and mixes 4 minutes, forms homogeneous mixture.Then feeding is used
Machine joins melt blending in double screw extruder and is extruded into bar, then through pelleter pelletizing.
Processing technique is: district's temperature of double screw extruder is 230 DEG C, and two district's temperature are 270 DEG C, and three district's temperature are
275 DEG C, four district's temperature are 280 DEG C, and die temperature is 285 DEG C.
Data are shown in Table 1.
Embodiment 2
With embodiment 1, difference is that using tetramethylolmethane is branching agent, and its consumption is 0.3g.Data are shown in Table 1.
Comparative example 1
The trade mark is the general thin level PET section of FG600.By 100 DEG C be dried 1 hour, 180 DEG C pre-crystallized 2 hours,
245 DEG C of thickeninies solid-phase tack producing of 10 hours obtains the PET section that intrinsic viscosity is 0.9dl/g.
Comparative example 2
With embodiment 1, difference is that the intrinsic viscosity that PET cuts into slices is 0.9dl/g, is added without branching agent.Data are shown in
Table 1.
Table 1
Note: "-" can't detect
From table 1 it follows that the branched polyethylene terephthalate obtained according to the compositions of the present invention, it sticks
Degree height, crystallisation by cooling temperature improves more than 20 DEG C, and molecular weight distribution broadens more than 10%, and has extraordinary crystallization
Performance and good processing characteristics.
It should be noted that, embodiment described above is only used for explaining the present invention, be not intended that the present invention is any
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary rather than limited vocabulary.Within the scope of the claims the present invention can be made by regulation
Amendment, and in without departing substantially from scope and spirit of the present invention, the present invention is revised.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this
Bright can be extended to other all methods and applications with identical function.
Claims (8)
1. a polyethylene terephthalate compositions, by the intrinsic viscosity poly terephthalic acid second two more than 0.85dl/g
Alcohol ester, little branchign of molecule agent and crystallization nucleating agent composition, wherein, described polyethylene terephthalate, little branchign of molecule agent
Being 100:0.01:0.1-100:0.5:1.5 with the mass ratio of crystallization nucleating agent, wherein, little branchign of molecule agent is selected from least having 3
The ester of individual functional group, acid, alcohol and derivant, described crystallization nucleating agent is selected from low molecular carboxylic acid salt and high molecular nucleating agent.
Compositions the most according to claim 1, it is characterised in that described polyethylene terephthalate, little molecule prop up
The mass ratio of agent and crystallization nucleating agent is 100:0.05:0.35-100:0.4:1.3.
Compositions the most according to claim 1 and 2, it is characterised in that described little branchign of molecule agent is selected from 1,3,5-benzene three
Acid, 1,2,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, pyromellitic acid dianhydride, trimellitic anhydride, glycerol, tetramethylolmethane, two seasons penta 4
Alcohol, trimethylolpropane, trihydroxy acid propane and trimethyl trimesate.
Compositions the most according to claim 1 and 2, it is characterised in that described high molecular nucleating agent is selected from polyethylene-propylene
Acid sodium, polyethylene acrylic acid zinc and ethylene/methacrylic acid salt resin.
5. a branched polyethylene terephthalate, by the intrinsic viscosity polyethylene terephthalate more than 0.85dl/g
Ester, little branchign of molecule agent and crystallization nucleating agent are made, wherein, described polyethylene terephthalate, little branchign of molecule agent and
The mass ratio of crystallization nucleating agent is 100:0.01:0.1-100:0.5:1.5, and wherein, little branchign of molecule agent is selected from least having 3
The ester of functional group, acid, alcohol and derivant, described crystallization nucleating agent is selected from low molecular carboxylic acid salt and high molecular nucleating agent.
Branched polyethylene terephthalate the most according to claim 5, it is characterised in that described poly terephthalic acid
The mass ratio of glycol ester, little branchign of molecule agent and crystallization nucleating agent is 100:0.05:0.35-100:0.4:1.3.
7. according to the branched polyethylene terephthalate described in claim 5 or 6, it is characterised in that described little molecule props up
Agent is selected from 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, pyromellitic acid dianhydride, trimellitic anhydride, sweet
Oil, tetramethylolmethane, dipentaerythritol, trimethylolpropane, trihydroxy acid propane and trimethyl trimesate.
8. according to the branched polyethylene terephthalate described in claim 5 or 6, it is characterised in that described macromolecule becomes
Core agent is selected from polyethylene acrylic acid sodium, polyethylene acrylic acid zinc and ethylene/methacrylic acid salt resin.
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| CN201210418906.6A CN103788587B (en) | 2012-10-26 | 2012-10-26 | A kind of high viscosity easily processes ethylene glycol terephthalate and preparation method thereof |
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| CN201210418906.6A CN103788587B (en) | 2012-10-26 | 2012-10-26 | A kind of high viscosity easily processes ethylene glycol terephthalate and preparation method thereof |
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| TWI637976B (en) * | 2017-07-07 | 2018-10-11 | 財團法人工業技術研究院 | Branched polymer, preparation method thereof and method for preparing a foam |
| CN109553936A (en) * | 2018-11-30 | 2019-04-02 | 复旦大学 | A kind of method of quick adjusting PET melt intensity |
| CN110128796A (en) * | 2019-05-07 | 2019-08-16 | 安徽美佳新材料股份有限公司 | A kind of thermoplastic polyester resin composition |
| CN112322208A (en) * | 2020-11-09 | 2021-02-05 | 山东胜通光学材料科技有限公司 | Preparation process of high-end release protection polyester base film for OCA (optical clear adhesive) |
| CN115322528B (en) * | 2022-08-01 | 2023-12-12 | 维赛(江苏)复合材料科技有限公司 | PET foaming core material with high shear strength |
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| CN101722697A (en) * | 2008-10-29 | 2010-06-09 | 帝人化成株式会社 | Resin shaping body |
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| CN101722697A (en) * | 2008-10-29 | 2010-06-09 | 帝人化成株式会社 | Resin shaping body |
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