CN117165053A - High-low temperature resistant modified PET material and preparation method thereof - Google Patents
High-low temperature resistant modified PET material and preparation method thereof Download PDFInfo
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- CN117165053A CN117165053A CN202311321565.5A CN202311321565A CN117165053A CN 117165053 A CN117165053 A CN 117165053A CN 202311321565 A CN202311321565 A CN 202311321565A CN 117165053 A CN117165053 A CN 117165053A
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000003365 glass fiber Substances 0.000 claims abstract description 28
- -1 poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester Chemical class 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 18
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- ZDHWTWWXCXEGIC-UHFFFAOYSA-N 2-ethenylpyrimidine Chemical compound C=CC1=NC=CC=N1 ZDHWTWWXCXEGIC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims abstract description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 9
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 9
- XXZAEGBIGLZHDA-UHFFFAOYSA-N B(O)(O)O.C(=C)(C)CC(O)(C)C(C)(C)O Chemical compound B(O)(O)O.C(=C)(C)CC(O)(C)C(C)(C)O XXZAEGBIGLZHDA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 claims description 14
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical group CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 13
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WEQURJQENFWZLR-UHFFFAOYSA-N 2,3-dimethylbutane-2,3-diol prop-1-en-2-yloxyboronic acid Chemical compound CC(=C)OB(O)O.CC(C)(O)C(C)(C)O WEQURJQENFWZLR-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229940100608 glycol distearate Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HUBMBNGODLWSPA-UHFFFAOYSA-N prop-1-en-2-yloxyboronic acid Chemical compound CC(=C)OB(O)O HUBMBNGODLWSPA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 1
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010015866 Extravasation Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036251 extravasation Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical group C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LLJOGUQSRXUDCC-UHFFFAOYSA-N methyl formate Chemical compound COC=O.COC=O LLJOGUQSRXUDCC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a high-low temperature resistant modified PET material, which relates to the technical field of high polymer materials and is prepared from the following raw materials in parts by weight: 70-80 parts of PET resin, 8-10 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1-2 parts of phosphorus pentoxide, 0.3-0.6 part of polyphosphoric acid, 5-8 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1-3 parts of isopropenyl pinacol borate, 1-3 parts of methacryloxypropyl triethoxysilane, 10-15 parts of glass fibers, 1-3 parts of 2-vinyl pyrimidine, 0.1-0.5 part of antioxidant, 0.2-0.5 part of lubricant, 0.5-1 part of compatilizer and 0.1-0.3 part of initiator. The high-low temperature resistant modified PET material has the advantages of good high-low temperature resistance, sufficient heat aging resistance, good mechanical properties and good flame retardance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-low temperature resistant modified PET material and a preparation method thereof.
Background
PET polyester resin is used as one of the earliest linear thermoplastic polymers for realizing industry, and is widely applied to the fields of plastic packaging, electronic appliances, automobiles, meters and the like because of excellent mechanical properties, physical properties and thermal properties and better acid, alkali and solvent resistance. However, the common PET materials in the market have technical defects of low mechanical strength, insufficient toughness, high and low temperature resistance and aging resistance to be further improved.
In order to solve the problems, the prior method is to modify the common PET material by adding various functional auxiliary agents, and the modified PET material can improve the high and low temperature resistance, the mechanical properties and the ageing resistance to a certain extent. However, the addition of a large amount of auxiliary agents with single functions not only can influence the processing fluidity of the material, but also can lead to insufficient application of the auxiliary agent functions due to antagonism among the auxiliary agents with different functions. In addition, the compatibility problem of the modified PET materials on the market also leads to the defects of poor product performance stability and short service life caused by the extravasation phenomenon of the manufactured product in the long-term use process.
For example, the Chinese patent application No. 200810208104.6 discloses a thermoplastic polyester elastomer with high and low temperature resistance and a preparation method thereof, which mainly comprises aromatic dimethyl diformate, alpha, omega-diol, hydroxyl-terminated polydimethylsiloxane and a chain extender. The chain extender is used for converting the hydroxyl groups with weak activity at two ends of the polydimethylsiloxane into high-activity isocyanate groups. As more stable and flexible silica bond is introduced into polyester molecular chain, the high and low temperature resistance and oxidation resistance of the material are greatly improved, the glass transition temperature is 40 ℃ lower than that of a common polyester elastomer, and the material can be used in an environment of minus 80 ℃ for a long time. The maximum use temperature can reach 250 ℃ and is 30 ℃ higher than the temperature of the common polyester elastomer. Moreover, the cost is lower than silicone. Therefore, the product has wide market development prospect. However, the mechanical properties, flame retardance and ageing resistance of the material still need to be further improved.
Therefore, the development of the high-low temperature resistant modified PET material with good high-low temperature resistance, sufficient heat aging resistance, good mechanical properties and flame retardance and the preparation method thereof meet the realization requirements, have wide market value and application prospect, and have very important significance in promoting the development of the PET material field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the high-low temperature resistant modified PET material with good high-low temperature resistance, sufficient heat aging resistance, good mechanical properties and good flame retardance and the preparation method thereof.
The invention can be realized by the following technical scheme:
the invention relates to a high-low temperature resistant modified PET material which is prepared from the following raw materials in parts by weight: 70-80 parts of PET resin, 8-10 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1-2 parts of phosphorus pentoxide, 0.3-0.6 part of polyphosphoric acid, 5-8 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1-3 parts of isopropenyl pinacol borate, 1-3 parts of methacryloxypropyl triethoxysilane, 10-15 parts of glass fibers, 1-3 parts of 2-vinyl pyrimidine, 0.1-0.5 part of antioxidant, 0.2-0.5 part of lubricant, 0.5-1 part of compatilizer and 0.1-0.3 part of initiator.
Preferably, the initiator is tert-butyl peroxybenzoate.
Preferably, the compatilizer is compatilizer KO-311.
Preferably, the lubricant is at least one of zinc stearate and glycol distearate.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
Preferably, the glass fibers are alkali-free glass fibers having an average diameter of 3-8 microns and an aspect ratio of (30-90): 1.
Preferably, the PET resin is at least one of Xiamen Tenglong DSR TL-103, zhejiang Wankai WK811 and Hainan Yisheng petrochemical YS-W01.
Preferably, the preparation method of the poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid comprises the following steps: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring for 2-4 hours at 115-135 ℃ to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring and reacting for 4-6 hours at 130-160 ℃ under normal pressure, reducing the pressure to 50-100Pa, heating to 280-300 ℃, keeping the temperature and the pressure, stirring and reacting for 10-16 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, performing rotary evaporation to remove the ethanol, and finally drying to constant weight at 85-95 ℃ in vacuum drying to obtain the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester.
Preferably, the molar ratio of the 1, 4-cyclohexanedimethanol to the 2,3,5, 6-tetrafluoroterephthalic acid to the catalyst to the high boiling point solvent is 1:1 (0.5-1): 8-15; the catalyst is at least one of tetrabutyl titanate, p-toluenesulfonic acid and antimony acetate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is any one of nitrogen, helium, neon and argon.
The invention also aims at providing a preparation method of the high-low temperature resistant modified PET material, which comprises the following steps: and uniformly mixing the raw materials in parts by weight to obtain a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain the high-low temperature resistant modified PET material.
Preferably, the extrusion molding temperature is 210-260 ℃, and the screw rotating speed of the double screw extruder is 280-350rpm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the high-low temperature resistant modified PET material disclosed by the invention can be realized by adopting conventional equipment, does not need complex process and equipment, has low energy consumption, high preparation efficiency and yield, is convenient to operate, and is easy to realize industrialized mass production.
(2) The invention discloses a high-low temperature resistant modified PET material which is prepared from the following raw materials in parts by weight: 70-80 parts of PET resin, 8-10 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1-2 parts of phosphorus pentoxide, 0.3-0.6 part of polyphosphoric acid, 5-8 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1-3 parts of isopropenyl pinacol borate, 1-3 parts of methacryloxypropyl triethoxysilane, 10-15 parts of glass fibers, 1-3 parts of 2-vinyl pyrimidine, 0.1-0.5 part of antioxidant, 0.2-0.5 part of lubricant, 0.5-1 part of compatilizer and 0.1-0.3 part of initiator. Through the mutual cooperation and coaction of the raw materials, the prepared product has the advantages of good high and low temperature resistance, sufficient heat aging resistance, good mechanical properties and flame retardance and long service life.
(3) According to the high-low temperature resistant modified PET material disclosed by the invention, a multiple interpenetrating network structure is formed in the molecular structure of the material through the interaction among the raw materials, and meanwhile, PET, tetrafluorobenzene, cyclohexane, amide, pinacol borate, triethoxysilane and pyrimidine structures are also introduced, and under the multiple effects of electronic effect, steric effect, conjugation effect and the like, the high-low temperature resistant performance, ageing resistant performance, mechanical property and flame retardance of the prepared PET resin are further improved, and the service life is further prolonged.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
Example 1
A high-low temperature resistant modified PET material is prepared from the following raw materials in parts by weight: 70 parts of PET resin, 8 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1 part of phosphorus pentoxide, 0.3 part of polyphosphoric acid, 5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1 part of isopropenyl pinacol borate, 1 part of methacryloxypropyl triethoxysilane, 10 parts of glass fiber, 1 part of 2-vinyl pyrimidine, 0.1 part of antioxidant, 0.2 part of lubricant, 0.5 part of compatilizer and 0.1 part of initiator.
The initiator is tert-butyl peroxybenzoate; the compatilizer is compatilizer KO-311; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; the glass fiber is alkali-free glass fiber, the average diameter of the glass fiber is 3 microns, and the length-diameter ratio is 30:1; the PET resin is Xiamen Tenglong DSR TL-103 in China.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester comprises the following steps ofThe steps are as follows: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring at 115 ℃ for 2 hours to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring at 130 ℃ under normal pressure for reaction for 4 hours, reducing the pressure to 50Pa, heating to 280 ℃, keeping the temperature and the pressure for stirring for reaction for 10 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, removing the ethanol by rotary evaporation, and finally drying to constant weight at 85 ℃ in vacuum drying to obtain poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid; the molar ratio of the 1, 4-cyclohexanedimethanol to the 2,3,5, 6-tetrafluoroterephthalic acid to the catalyst to the high boiling point solvent is 1:1:0.5:8; the catalyst is tetrabutyl titanate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen. Mn=13725 g/mol, M of the poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid by GPC W /M n ＝1.324；
The preparation method of the high-low temperature resistant modified PET material comprises the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixed material, and adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-low temperature resistant modified PET material; the extrusion molding temperature is 210-260 ℃, and the screw rotating speed of the double screw extruder is 280rpm.
Example 2
A high-low temperature resistant modified PET material is prepared from the following raw materials in parts by weight: 73 parts of PET resin, 8.5 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1.2 parts of phosphorus pentoxide, 0.4 part of polyphosphoric acid, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1.5 parts of isopropenyl boric acid pinacol ester, 1.5 parts of methacryloxypropyl triethoxysilane, 11 parts of glass fiber, 1.5 parts of 2-vinyl pyrimidine, 0.2 part of antioxidant, 0.3 part of lubricant, 0.6 part of compatilizer and 0.15 part of initiator.
The initiator is tert-butyl peroxybenzoate; the compatilizer is compatilizer KO-311; the lubricant is glycol distearate; the antioxidant is antioxidant 168; the glass fiber is alkali-free glass fiber, the average diameter of the glass fiber is 4 microns, and the length-diameter ratio is 40:1; the PET resin is Xiamen Tenglong DSR TL-103 in China.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester comprises the following steps: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring at 120 ℃ for 2.5 hours to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring at 140 ℃ under normal pressure for 4.5 hours, reducing the pressure to 60Pa, heating to 285 ℃, keeping the temperature and the pressure for 12 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, removing the ethanol by rotary evaporation, and finally drying to constant weight at 86 ℃ in vacuum drying to obtain poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid; the molar ratio of the 1, 4-cyclohexanedimethanol to the 2,3,5, 6-tetrafluoroterephthalic acid to the catalyst to the high boiling point solvent is 1:1:0.6:10; the catalyst is p-toluenesulfonic acid; the high boiling point solvent is dimethyl sulfoxide; the inert gas is helium.
The preparation method of the high-low temperature resistant modified PET material comprises the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixed material, and adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-low temperature resistant modified PET material; the extrusion molding temperature was 220 ℃, and the screw speed of the twin-screw extruder was 300rpm.
Example 3
A high-low temperature resistant modified PET material is prepared from the following raw materials in parts by weight: 75 parts of PET resin, 9 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1.5 parts of phosphorus pentoxide, 0.45 part of polyphosphoric acid, 6.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2 parts of isopropenyl boric acid pinacol ester, 2 parts of methacryloxypropyl triethoxysilane, 13 parts of glass fiber, 2 parts of 2-vinyl pyrimidine, 0.35 part of antioxidant, 0.35 part of lubricant, 0.75 part of compatilizer and 0.2 part of initiator.
The initiator is tert-butyl peroxybenzoate; the compatilizer is compatilizer KO-311; the lubricant is zinc stearate; the antioxidant is antioxidant 1076; the glass fiber is alkali-free glass fiber, the average diameter of the glass fiber is 5 microns, and the length-diameter ratio is 60:1; the PET resin is Tsuo LongDSR TL-103 of Xiamen in China.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester comprises the following steps: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring for 3 hours at 125 ℃ to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring for reacting for 5 hours at 145 ℃ under normal pressure, reducing the pressure to 75Pa, heating to 290 ℃, keeping the temperature and the pressure, stirring for reacting for 13 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 5 times, removing the ethanol by rotary evaporation, and finally drying to constant weight at 90 ℃ in vacuum drying to obtain poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid; the molar ratio of the 1, 4-cyclohexanedimethanol to the 2,3,5, 6-tetrafluoroterephthalic acid to the catalyst to the high boiling point solvent is 1:1:0.8:11; the catalyst is antimony acetate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is neon.
The preparation method of the high-low temperature resistant modified PET material comprises the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixed material, and adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-low temperature resistant modified PET material; the extrusion molding temperature was 235 ℃, and the screw speed of the twin-screw extruder was 320rpm.
Example 4
A high-low temperature resistant modified PET material is prepared from the following raw materials in parts by weight: 78 parts of PET resin, 9.5 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1.8 parts of phosphorus pentoxide, 0.55 part of polyphosphoric acid, 7.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2.5 parts of isopropenyl boric acid pinacol ester, 2.5 parts of methacryloxypropyl triethoxysilane, 14 parts of glass fiber, 2.5 parts of 2-vinyl pyrimidine, 0.4 part of antioxidant, 0.45 part of lubricant, 0.9 part of compatilizer and 0.25 part of initiator.
The initiator is tert-butyl peroxybenzoate; the compatilizer is compatilizer KO-311; the lubricant is a mixture formed by mixing zinc stearate and glycol distearate according to a mass ratio of 1:3; the antioxidant is a mixture formed by mixing an antioxidant 1010, an antioxidant 168 and an antioxidant 1076 according to a mass ratio of 2:1:1; the glass fiber is alkali-free glass fiber, the average diameter of the glass fiber is 7 microns, and the length-diameter ratio is 80:1; the PET resin is Xiamen Tenglong DSR TL-103 in China.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester comprises the following steps: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring at 130 ℃ for 3.5 hours to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring at 155 ℃ under normal pressure for 5.5 hours, reducing pressure to 90Pa, heating to 295 ℃, keeping the temperature and the pressure for 15 hours, stirring for reaction, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 6 times, removing the ethanol by rotary evaporation, and finally drying to constant weight at 93 ℃ in vacuum drying to obtain poly (1, 4-cyclohexanedimethanol 2,3,5, 6-tetrafluoroterephthalic acid); the molar ratio of the 1, 4-cyclohexanedimethanol to the 2,3,5, 6-tetrafluoroterephthalic acid to the catalyst to the high boiling point solvent is 1:1:0.9:14; the catalyst is a mixture formed by mixing tetrabutyl titanate, p-toluenesulfonic acid and antimony acetate according to a mass ratio of 1:3:5; the high boiling point solvent is dimethyl sulfoxide; the inert gas is argon.
The preparation method of the high-low temperature resistant modified PET material comprises the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixed material, and adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-low temperature resistant modified PET material; the extrusion molding temperature was 250℃and the screw speed of the twin-screw extruder was 340rpm.
Example 5
A high-low temperature resistant modified PET material is prepared from the following raw materials in parts by weight: 80 parts of PET resin, 10 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 2 parts of phosphorus pentoxide, 0.6 part of polyphosphoric acid, 8 parts of 2-acrylamido-2-methylpropanesulfonic acid, 3 parts of isopropenyl boric acid pinacol ester, 3 parts of methacryloxypropyl triethoxysilane, 15 parts of glass fiber, 3 parts of 2-vinyl pyrimidine, 0.5 part of antioxidant, 0.5 part of lubricant, 1 part of compatilizer and 0.3 part of initiator.
The initiator is tert-butyl peroxybenzoate; the compatilizer is compatilizer KO-311; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; the glass fiber is alkali-free glass fiber, the average diameter of the glass fiber is 8 micrometers, and the length-diameter ratio is 90:1; the PET resin is Xiamen Tenglong DSR TL-103 in China.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester comprises the following steps: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring for 4 hours at 135 ℃ to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring for reaction for 6 hours at 160 ℃ under normal pressure, reducing the pressure to 100Pa, heating to 300 ℃, keeping the temperature and the pressure, stirring for reaction for 16 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 6 times, removing the ethanol by rotary evaporation, and finally drying to constant weight at 95 ℃ in vacuum drying to obtain poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid; the molar ratio of the 1, 4-cyclohexanedimethanol to the 2,3,5, 6-tetrafluoroterephthalic acid to the catalyst to the high boiling point solvent is 1:1:1:15; the catalyst is tetrabutyl titanate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The preparation method of the high-low temperature resistant modified PET material comprises the following steps: uniformly mixing the raw materials in parts by weight to obtain a mixed material, and adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-low temperature resistant modified PET material; the extrusion molding temperature was 260℃and the screw speed of the twin-screw extruder was 350rpm.
Comparative example 1
A high and low temperature resistant modified PET material was substantially the same as example 1 except that pinacol isopropenylborate was not added.
Comparative example 2
A high and low temperature resistant modified PET material was substantially the same as example 1 except that no 2-vinyl pyrimidine was added.
Meanwhile, in order to evaluate the specific technical effects of the high and low temperature resistant modified PET material, the high and low temperature resistant modified PET material prepared by each example is subjected to relevant performance test, the test results are shown in table 1, and the test method is as follows:
(1) Tensile properties: tensile property tests were performed with reference to GB/T1040.1-2006.
(2) Low temperature resistance: the high and low temperature resistant modified PET materials produced in each example are respectively placed in an environment of minus 30 ℃ for 24 hours and then cooled to room temperature, the tensile strength at the moment is tested again by referring to the tensile property test method (1), the retention rate of the tensile strength is calculated, and the higher the value is, the better the low temperature resistant performance is.
(3) High temperature aging resistance: the high-low temperature resistant modified PET materials produced in each example are respectively placed in hot air at 150 ℃ for artificial accelerated aging for 24 hours, then cooled to room temperature, the tensile strength at the moment is tested by referring to the tensile property test method (1), the retention rate of the tensile strength is calculated, and the higher the value is, the better the high-temperature resistant aging performance is.
(4) Heat resistance: the detection was performed using UL-94.
TABLE 1
| Project | Tensile Strength (MPa) | Low temperature resistance (%) | Aging resistance (%) | Flame retardancy (grade) |
| Example 1 | 105.6 | 98.7 | 99.1 | V-0 |
| Example 2 | 106.8 | 99.3 | 99.5 | V-0 |
| Example 3 | 107.5 | 99.5 | 99.6 | V-0 |
| Example 4 | 108.5 | 99.8 | 99.8 | V-0 |
| Example 5 | 110.0 | 99.9 | 99.9 | V-0 |
| Comparative example 1 | 100.3 | 96.7 | 97.0 | V-1 |
| Comparative example 2 | 102.9 | 97.2 | 97.8 | V-1 |
As can be seen from Table 1, the high and low temperature resistant modified PET material disclosed in the examples of the present invention has better mechanical properties, low temperature resistance, flame retardance and high temperature aging resistance than the comparative examples, and the addition of pinacol isopropenylborate and 2-vinyl pyrimidine is beneficial to improving the above properties.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those of ordinary skill in the art will readily implement the invention as described above; however, those skilled in the art will appreciate that many modifications, adaptations, and variations of the present invention are possible in light of the above teachings without departing from the scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (10)
1. The high-low temperature resistant modified PET material is characterized by being prepared from the following raw materials in parts by weight: 70-80 parts of PET resin, 8-10 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester, 1-2 parts of phosphorus pentoxide, 0.3-0.6 part of polyphosphoric acid, 5-8 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1-3 parts of isopropenyl pinacol borate, 1-3 parts of methacryloxypropyl triethoxysilane, 10-15 parts of glass fibers, 1-3 parts of 2-vinyl pyrimidine, 0.1-0.5 part of antioxidant, 0.2-0.5 part of lubricant, 0.5-1 part of compatilizer and 0.1-0.3 part of initiator.
2. The high and low temperature resistant modified PET material of claim 1, wherein the initiator is t-butyl peroxybenzoate.
3. The high and low temperature resistant modified PET material of claim 1, wherein the compatibilizer is compatibilizer KO-311.
4. The high and low temperature resistant modified PET material of claim 1, wherein the lubricant is at least one of zinc stearate, ethylene glycol distearate.
5. The high and low temperature resistant modified PET material of claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076.
6. The modified PET material of claim 1, wherein the glass fibers are alkali-free glass fibers having an average diameter of 3-8 μm and an aspect ratio of (30-90): 1.
7. The modified PET material of claim 1, wherein the PET resin is at least one of Xiamen tenglong DSR TL-103, zhejiang wankai WK811, hainan Yishengsheng petrochemical YS-W01.
8. The high and low temperature resistant modified PET material of claim 1, wherein the preparation method of poly (1, 4-cyclohexanedimethanol) 2,3,5, 6-tetrafluoroterephthalic acid comprises the following steps: adding 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid and a catalyst into a high-boiling point solvent, stirring for 2-4 hours at 115-135 ℃ to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the reaction kettle with inert gas, stirring and reacting for 4-6 hours at 130-160 ℃ under normal pressure, reducing the pressure to 50-100Pa, heating to 280-300 ℃, keeping the temperature and the pressure, stirring and reacting for 10-16 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, performing rotary evaporation to remove the ethanol, and finally drying to constant weight at 85-95 ℃ in vacuum drying to obtain the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 1, 4-cyclohexanedimethanol ester.
9. The modified PET material with high and low temperature resistance according to claim 8, wherein the molar ratio of 1, 4-cyclohexanedimethanol, 2,3,5, 6-tetrafluoroterephthalic acid, catalyst and high boiling point solvent is 1:1 (0.5-1): 8-15; the catalyst is at least one of tetrabutyl titanate, p-toluenesulfonic acid and antimony acetate; the high boiling point solvent is dimethyl sulfoxide; the inert gas is any one of nitrogen, helium, neon and argon.
10. A method for preparing a modified PET material resistant to high and low temperatures according to any one of claims 1 to 9, comprising the steps of: uniformly mixing the raw materials in parts by weight to obtain a mixed material, and adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-low temperature resistant modified PET material; the extrusion molding temperature is 210-260 ℃, and the screw rotating speed of the double screw extruder is 280-350rpm.
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