CN103556289B - Creep-resistant polyester and its preparation method - Google Patents
Creep-resistant polyester and its preparation method Download PDFInfo
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- CN103556289B CN103556289B CN201310479658.0A CN201310479658A CN103556289B CN 103556289 B CN103556289 B CN 103556289B CN 201310479658 A CN201310479658 A CN 201310479658A CN 103556289 B CN103556289 B CN 103556289B
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- trifluoromethyl
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- 229920000728 polyester Polymers 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 76
- 239000011737 fluorine Substances 0.000 claims abstract description 76
- 239000004593 Epoxy Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 230000000903 blocking effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 53
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 47
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 46
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 42
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 35
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 12
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 238000001953 recrystallisation Methods 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The invention relates to creep-resistant polyester and its preparation method. According to the preparation method, polyester is mixed with a fluorine-containing epoxy compound or a fluorine-containing epoxy compound is added during the synthesis process of polyester. Then, the creep-resistant polyester can be obtained. By the use of the fluorine-containing epoxy compound for blocking modification of the polyester, creep-resistant performance of the polyester can be improved to some extent, and hydrolysis resistance and performance stability of the polyester can be raised. Fiber prepared from the creep-resistant polyester can be used in a hot and humid environment for a long time, and has a huge prospect in the fields of plastic packing, waterproof fabric, ropes, cables, marine fiber and the like.
Description
Technical Field
The invention relates to creep-resistant polyester and a preparation method thereof, in particular to creep-resistant polyester modified by using a fluorine-containing epoxy compound as an end capping agent and a preparation method thereof.
Background
Polyester (PET) is one of the most widely used synthetic polymers currently used by human beings, has high strength, high modulus and good heat resistance, is a linear thermoplastic polymer which is the earliest to realize industrial application, and is widely applied to the fields of plastic packaging, films, chemical fibers and the like.
The molecular chain structure of the polyester is a linear macromolecule containing a benzene ring structure, functional groups on the molecular chain are arranged orderly, no branched chain exists, and the flexibility of the macromolecular chain is poor. Compared with other high polymer materials, the molecular chain of the polyester is difficult to slip, and has certain dimensional stability. However, polyester materials creep when used for extended periods above the glass transition temperature. Creep is the tendency of a solid material to slowly and permanently move or deform under the influence of stress, which occurs as a result of prolonged action at stresses below the yield strength of the material. Creep can be more severe when the material is heated for extended periods of time or at temperatures near the melting point. The temperature range in which creep deformation occurs differs from material to material, depending on the molecular structure. If the polyester material undergoes large creep in the using process, the dimensional and form of the polyester material are unstable, which seriously limits the application of the polyester material in many fields, in particular the field of high-strength ropes.
The creep resistance of the polyester material can be improved by the following methods: (1) use below the glass transition temperature of the material; (2) adopting various modification methods to crosslink macromolecules; (3) improving the relative molecular mass of macromolecules; (4) the method for improving the acting force between macromolecular chains comprises the steps of introducing aromatic heterocyclic rings and polar groups into a main chain or forming an interpenetrating network structure and the like.
Related patents such as patent CN200680017951.3 by allidanesen discloses a creep-resistant pressure-sensitive adhesive product based on a block copolymer containing vinyl-substituted aromatic hydrocarbon and conjugated diene. Related patents such as CN200910097866.8 improve the creep resistance of the fibers by adding a photosensitizer to the polyethylene fibers for pretreatment and then uv irradiation. CN201110434278.6 uses photosensitizer and thermal initiator to initiate crosslinking for polyethylene fiber, thereby increasing creep resistance of fiber. However, there is currently little research on creep resistance for polyesters.
Disclosure of Invention
The invention aims to provide creep-resistant polyester and a preparation method thereof, and particularly relates to creep-resistant polyester modified by using a fluorine-containing epoxy compound as an end capping agent and a preparation method thereof. The polyester is subjected to end capping modification by using the fluorine-containing epoxy compound, so that the creep resistance of the polyester can be improved to a certain extent, and the hydrolysis resistance and the performance stability of the polyester can be improved; the fiber prepared from the creep-resistant polyester can be used in high-temperature and high-humidity environments for a long time, and has great prospects in the fields of plastic packaging, waterproof fabrics, ropes, cables, marine fibers and the like.
The invention provides the following technical scheme:
the invention relates to a preparation method of creep-resistant polyester, which comprises the steps of carrying out blending reaction on polyester and a fluorine-containing epoxy compound to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 270-290 ℃, and the time is 3-5 min; the addition amount of the fluorine-containing epoxy compound is 0.5-5 wt% of the polyester; the polyester is one or a mixture of more of PET, PTT and PBT or a copolymer of more of PET, PTT and PBT; in the polyester, the intrinsic viscosity of PET is 0.6-0.7 dL/g; the intrinsic viscosity of the PTT is 0.7-0.9 dL/g; the PBT has an intrinsic viscosity of 0.7-0.9 dL/g.
Or reacting with dibasic acid and dihydric alcohol as comonomers, adding a fluorine-containing epoxy compound when the intrinsic viscosity of a reaction product is more than 0.6dL/g, stirring for 10-30 min under a vacuum condition, and discharging to obtain the creep-resistant polyester; the addition amount of the fluorine-containing epoxy compound is 0.8-8 wt% of the dibasic acid; the dibasic acid is terephthalic acid; the dihydric alcohol is one or more of ethylene glycol, propylene glycol and butanediol.
The creep-resistant polyester is obtained by blocking partial macromolecular chains of polyester by using a fluorine-containing epoxy compound, wherein the blocking is performed on one end and/or two ends of the macromolecular chains, and the molecular formulas are as follows:
one end of the tube is sealed and the other end is sealed,
the two ends are sealed and the end is closed,
wherein,
Rf＝
m＝80～100，
n＝10～20。
the fluorine-containing epoxy compound is fluorine-containing bisphenol A epoxy resin, and the molecular structural formula of the fluorine-containing epoxy compound is as follows:
wherein n is 10 to 20.
The fluorine-containing bisphenol A type epoxy resin is prepared by blending diphenyl silanediol and 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether serving as raw materials by using tin chloride as a catalyst; the method comprises the following specific steps:
preparation of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding 8-10 mol/L sodium hydroxide solution which is 1.5-2.0% of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in mass, and stirring to react for 16-18 h at room temperature; cooling to room temperature, adding 3-5 mol/L sodium hydroxide solution which is 30-40% of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, wherein the sodium hydroxide solution is saturated by anhydrous sodium carbonate, and stirring and reacting for 10-15 h at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
the preparation of the fluorine-containing bisphenol A epoxy resin comprises the following steps:
mixing diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether according to a molar ratio of 1:2, adding tin chloride accounting for 0.06-0.10% of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether as a catalyst, and carrying out blending reaction at the temperature of 150-180 ℃ for 30-40 min to obtain the fluorine-containing bisphenol A epoxy resin.
The fluorine-containing bisphenol A epoxy resin is prepared from epichlorohydrin and 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene]Reacting diphenol to obtain 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene]Bisphenol diglycidyl ether, 4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene]The bisphenol diglycidyl ether and diphenyl silanediol react to obtain the product. The fluorine-containing bisphenol A epoxy resin containsHowever, the structure has large steric hindrance, and bisphenol A epoxy resin with a certain molecular weight is difficult to obtain. Among the fluorine-containing bisphenol A type epoxy resinsThe structure can reduce the steric hindrance of a macromolecular chain, enhance the flexibility of the molecular chain, greatly promote the polymerization reaction of the bisphenol A epoxy resin and effectively improve the relative molecular mass of the bisphenol A epoxy resin.
The fluorine-containing bisphenol A epoxy resin has a certain degree of polymerization, longer molecular chain and a certain modulus, and can increase the proportion of benzene ring structures in the molecular chain of polyester by blending with the polyester, so that functional groups on the molecular chain are arranged more orderly, and the tensile modulus and tensile strength of the polyester are effectively improved.
The fluorine-containing bisphenol A epoxy resin has strong electronegativity, so that a large amount of uniform hydrogen bonds can be formed by blending the fluorine atoms with polyester, the function of the fluorine atoms is fully exerted, and the intermolecular acting force is effectively increased. Even if the polyester modified by the fluorine-containing bisphenol A epoxy resin in a blocking way has an external force effect when in use, the molecular chain of the polyester is difficult to slip, the creep deformation is small, the dimensional stability is good, the creep resistance can be realized to a certain extent, and the creep resistance of the polyester is better improved.
The fluorine-containing bisphenol A epoxy resin is used as an end-capping agent to modify polyester, and the epoxy structure of the epoxy resin can partially eliminate terminal carboxyl in polyester molecules, control the growth rate of the concentration of the terminal carboxyl and effectively control the acceleration degree of the hydrolysis rate. The phenomena of hydrolysis and random breakage and depolymerization of a high molecular chain when the glass transition temperature is higher and the glass transition temperature is exposed to water for a long time are avoided; and because the end capping agent introduces silicon atoms and fluorine atoms into a macromolecular chain, the polyester can be endowed with hydrophobic and water repellent performance, the hydrolysis resistance of the polyester is improved to a certain extent, and the service life of the polyester material in a damp and hot environment is prolonged. In addition, the fluorine-containing bisphenol A epoxy resin has a special epoxy structure, is mixed with polyester to react, but does not generate small molecules such as water, so that the polyester is prevented from being self-degraded in the production process, and the obtained polyester has good thermal stability.
Has the advantages that:
1. the creep-resistant polyester obtained by the invention has strong electronegativity of fluorine atoms, so that hydrogen bonds can be formed among polyester molecular chains, intermolecular acting force is increased, and the creep-resistant polyester can play a role to a certain extent.
2. The bisphenol A epoxy resin containing fluorine as the end-capping reagent of the creep-resistant polyester obtained by the invention can play a role of chain extension at the same time, can increase the relative molecular mass of the polyester and improve the creep resistance of the polyester.
3. The creep-resistant polyester obtained by the invention can partially eliminate terminal carboxyl in polyester molecules by carrying out end-capping modification on the fluorine-containing bisphenol A epoxy resin, and can make the polyester hydrophobic and water repellent and improve the hydrolysis resistance of the polyester due to the introduction of silicon atoms and fluorine atoms.
4. The creep-resistant polyester obtained by the invention has great prospect in the fields of plastic packaging, waterproof fabrics, ropes, cables, marine fibers and the like, and the application range of the polyester is expanded.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The creep-resistant polyester is obtained by blocking part of macromolecular chains of polyester by a fluorine-containing epoxy compound, wherein the blocking refers to blocking one end and/or two ends of the macromolecular chains, and the molecular structural formulas are respectively as follows:
one end of the tube is sealed and the other end is sealed,
the two ends are sealed and the end is closed,
wherein,
Rf＝
m＝80～100，
n＝10～20。
the creep-resistant polyester is prepared from the fluorine-containing epoxy compound in an amount of 0.5-5 wt% of the polyester, or 0.8-8 wt% of the dibasic acid.
Example 1
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding 15mol/L sodium hydroxide solution accounting for 1.5 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol, and stirring for reaction for 16 hours at room temperature; then cooling to room temperature, adding a sodium hydroxide solution which is 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is 5mol/L, wherein the sodium hydroxide solution is a solution saturated by anhydrous sodium carbonate, and stirring and reacting for 10 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.06 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction at the temperature of 180 ℃ for 30min to obtain the fluorine-containing bisphenol A epoxy resin.
Carrying out blending reaction on PET polyester and fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 270 ℃ and the time is 5 min; the amount of the fluorine-containing bisphenol A epoxy resin added was 0.5 wt% of the PET polyester.
Example 2
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in the molar ratio of 4 to 1 in nitrogen atmosphere, adding 10mol/L sodium hydroxide solution of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in 2.0 wt%, and stirring at room temperature for 18 hr; cooling to room temperature, adding 3mol/L sodium hydroxide solution which accounts for 40 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring for reaction for 15 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.10 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction under the conditions that the temperature is 150 ℃ and the stirring time is 40min, so that the fluorine-containing bisphenol A epoxy resin is obtained.
Carrying out blending reaction on PTT polyester and fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 290 ℃, and the time is 3 min; the amount of the fluorine-containing bisphenol A epoxy resin added was 5 wt% of the PTT polyester.
Example 3
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding a 12mol/L sodium hydroxide solution accounting for 1.8 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol, and stirring for reaction at room temperature for 17 hours; cooling to room temperature, adding a 4mol/L sodium hydroxide solution accounting for 35 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, wherein the sodium hydroxide solution is a solution saturated by anhydrous sodium carbonate, and stirring for reaction for 13 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.08 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction at the temperature of 170 ℃ for 35min to obtain the fluorine-containing bisphenol A epoxy resin.
Blending PET (polyethylene terephthalate) and PBT (polybutylene terephthalate) polyester with a fluorine-containing bisphenol A epoxy resin according to the weight ratio of 1:1 to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 280 ℃ and the time is 4 min; the fluorine-containing bisphenol A epoxy resin accounts for 3 wt% of the sum of the PET and PBT polyesters.
Example 4
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding 15mol/L sodium hydroxide solution accounting for 1.5 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol, and stirring for reaction for 16 hours at room temperature; then cooling to room temperature, adding a sodium hydroxide solution which is 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is 5mol/L, wherein the sodium hydroxide solution is a solution saturated by anhydrous sodium carbonate, and stirring and reacting for 10 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.06 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction at the temperature of 180 ℃ for 30min to obtain the fluorine-containing bisphenol A epoxy resin.
Blending PET and PTT polyester with fluorine-containing bisphenol A epoxy resin according to the weight ratio of 1:1 to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 275 ℃ and the time is 5 min; the fluorine-containing bisphenol A epoxy resin accounts for 4 wt% of the total mass of the PET and the PTT polyesters.
Example 5
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in the molar ratio of 4 to 1 in nitrogen atmosphere, adding 10mol/L sodium hydroxide solution of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in 2.0 wt%, and stirring at room temperature for 18 hr; cooling to room temperature, adding 3mol/L sodium hydroxide solution which accounts for 40 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring for reaction for 15 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.10 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction under the conditions that the temperature is 150 ℃ and the stirring time is 40min, so that the fluorine-containing bisphenol A epoxy resin is obtained.
Blending PET, PTT and PBT polyester with fluorine-containing bisphenol A epoxy resin according to the weight ratio of 1:1:1 to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 285 ℃, and the time is 4 min; the fluorine-containing bisphenol A type epoxy resin accounts for 1.5 wt% of the sum of the PET, PTT and PBT polyesters.
Example 6
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding a 12mol/L sodium hydroxide solution accounting for 1.8 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol, and stirring for reaction at room temperature for 17 hours; cooling to room temperature, adding a 4mol/L sodium hydroxide solution accounting for 35 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, wherein the sodium hydroxide solution is a solution saturated by anhydrous sodium carbonate, and stirring for reaction for 13 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.08 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction at the temperature of 170 ℃ for 35min to obtain the fluorine-containing bisphenol A epoxy resin.
Adding terephthalic acid and ethylene glycol as comonomers in a molar ratio of 1:1, reacting, adding fluorine-containing bisphenol A epoxy resin when the intrinsic viscosity of a reaction product is more than 0.6dL/g, stirring for 10min under a vacuum condition, and discharging to obtain the creep-resistant polyester; the amount of the fluorine-containing bisphenol A epoxy resin added was 0.8 wt% based on the weight of terephthalic acid.
Example 7
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding 15mol/L sodium hydroxide solution accounting for 1.5 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol, and stirring for reaction for 16 hours at room temperature; then cooling to room temperature, adding a sodium hydroxide solution which is 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is 5mol/L, wherein the sodium hydroxide solution is a solution saturated by anhydrous sodium carbonate, and stirring and reacting for 10 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.06 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction at the temperature of 180 ℃ for 30min to obtain the fluorine-containing bisphenol A epoxy resin.
Taking terephthalic acid and butanediol as comonomers, feeding and reacting according to a molar ratio of 1:1, adding fluorine-containing bisphenol A epoxy resin when the intrinsic viscosity of a reaction product is more than 0.6dL/g, stirring for 130min under a vacuum condition, and discharging to obtain the creep-resistant polyester; the amount of the fluorine-containing bisphenol A epoxy resin added was 8 wt% of terephthalic acid.
Example 8
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in the molar ratio of 4 to 1 in nitrogen atmosphere, adding 10mol/L sodium hydroxide solution of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in 2.0 wt%, and stirring at room temperature for 18 hr; cooling to room temperature, adding 3mol/L sodium hydroxide solution which accounts for 40 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring for reaction for 15 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.10 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction under the conditions that the temperature is 150 ℃ and the stirring time is 40min, so that the fluorine-containing bisphenol A epoxy resin is obtained.
Taking terephthalic acid, ethylene glycol and propylene glycol as comonomers, feeding and reacting at a molar ratio of 2:1:1, adding fluorine-containing bisphenol A epoxy resin when the intrinsic viscosity of a reaction product is more than 0.6dL/g, stirring for 15min under a vacuum condition, and discharging to obtain the creep-resistant polyester; the amount of the fluorine-containing bisphenol A epoxy resin added was 2 wt% of terephthalic acid.
Example 9
Preparation of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding a 12mol/L sodium hydroxide solution accounting for 1.8 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol, and stirring for reaction at room temperature for 17 hours; cooling to room temperature, adding a 4mol/L sodium hydroxide solution accounting for 35 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, wherein the sodium hydroxide solution is a solution saturated by anhydrous sodium carbonate, and stirring for reaction for 13 hours at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
preparation of fluorine-containing bisphenol A epoxy resin:
diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether are mixed according to the molar ratio of 1:2, tin chloride accounting for 0.08 percent of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether is added as a catalyst, and the mixture is subjected to blending reaction at the temperature of 170 ℃ for 35min to obtain the fluorine-containing bisphenol A epoxy resin.
Taking terephthalic acid, ethylene glycol and butanediol as comonomers, feeding and reacting at a molar ratio of 2:1:1, adding fluorine-containing bisphenol A epoxy resin when the intrinsic viscosity of a reaction product is more than 0.6dL/g, stirring for 20min under a vacuum condition, and discharging to obtain the creep-resistant polyester; the amount of the fluorine-containing bisphenol A epoxy resin added was 6 wt% of terephthalic acid.
Claims (5)
1. A preparation method of creep-resistant polyester is characterized by comprising the following steps: carrying out blending reaction on polyester and a fluorine-containing epoxy compound to obtain the creep-resistant polyester; blending reaction conditions are as follows: the temperature is 270-290 ℃, and the time is 3-5 min; the addition amount of the fluorine-containing epoxy compound is 0.5-5 wt% of the polyester;
or reacting with dibasic acid and dihydric alcohol as comonomers, adding a fluorine-containing epoxy compound when the intrinsic viscosity of a reaction product is more than 0.6dL/g, stirring for 10-30 min under a vacuum condition, and discharging to obtain the creep-resistant polyester; the addition amount of the fluorine-containing epoxy compound is 0.8-8 wt% of the dibasic acid;
the fluorine-containing epoxy compound is fluorine-containing bisphenol A epoxy resin, and the molecular structural formula of the fluorine-containing epoxy compound is as follows:
wherein n is 10-20;
the fluorine-containing bisphenol A type epoxy resin is prepared by blending diphenyl silanediol and 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether serving as raw materials by using tin chloride as a catalyst; the method comprises the following specific steps:
preparation of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol diglycidyl ether:
mixing epoxy chloropropane and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in a molar ratio of 4:1 in a nitrogen atmosphere, adding 10-15 mol/L sodium hydroxide solution which is 1.5-2.0% of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] diphenol in mass, and stirring to react for 16-18 h at room temperature; cooling to room temperature, adding 3-5 mol/L sodium hydroxide solution which is 30-40% of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, wherein the sodium hydroxide solution is saturated by anhydrous sodium carbonate, and stirring and reacting for 10-15 h at room temperature; then extracting with chloroform, evaporating the obtained organic phase to remove chloroform and excessive epichlorohydrin to obtain a thick liquid, adding the thick liquid into absolute ethyl alcohol for recrystallization to obtain crystals of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether;
the preparation of the fluorine-containing bisphenol A epoxy resin comprises the following steps:
mixing diphenyl silanediol and 4,4'- [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether according to a molar ratio of 1:2, adding tin chloride accounting for 0.06-0.10% of the mass of the 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol diglycidyl ether as a catalyst, and carrying out blending reaction at the temperature of 150-180 ℃ for 30-40 min to obtain the fluorine-containing bisphenol A epoxy resin.
2. The method of claim 1, wherein the dibasic acid is terephthalic acid; the dihydric alcohol is one or more of ethylene glycol, propylene glycol and butanediol.
3. The method for preparing the creep-resistant polyester according to claim 1, wherein the polyester is one or a mixture of PET, PTT and PBT or a copolymer of PET, PTT and PBT.
4. The method for preparing a creep-resistant polyester according to claim 3, wherein the intrinsic viscosity of PET in the polyester is 0.6 to 0.7 dL/g; the intrinsic viscosity of the PTT is 0.7-0.9 dL/g; the PBT has an intrinsic viscosity of 0.7-0.9 dL/g.
5. The creep-resistant polyester according to claim 1, wherein: the creep-resistant polyester is obtained by blocking partial macromolecular chains of polyester by using a fluorine-containing epoxy compound, wherein the blocking is performed on one end and/or two ends of the macromolecular chains, and the molecular structural formulas are respectively as follows:
one end of the tube is sealed and the other end is sealed,
the two ends are sealed and the end is closed,
wherein,
m＝80～100，
n＝10～20。
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| JPS56100877A (en) * | 1980-01-18 | 1981-08-13 | Furukawa Electric Co Ltd:The | Hot melt sticking composition |
| JP2002029019A (en) * | 2000-05-09 | 2002-01-29 | Toray Ind Inc | Biaxially oriented laminated polyester film and method for manufacturing the same |
| CN101180377A (en) * | 2005-04-20 | 2008-05-14 | 艾利丹尼森公司 | Creep resistant adhesives and tapes made therewith |
| CN101538793A (en) * | 2009-04-20 | 2009-09-23 | 浙江理工大学 | Method for improving creep-resistant property of ultra-high molecular weight polyethylene fiber |
| CN102493168A (en) * | 2011-12-22 | 2012-06-13 | 北京服装学院 | Method for improving creep resistant performance of ultra-high molecular weight polyethylene fiber |
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| JPS56100877A (en) * | 1980-01-18 | 1981-08-13 | Furukawa Electric Co Ltd:The | Hot melt sticking composition |
| JP2002029019A (en) * | 2000-05-09 | 2002-01-29 | Toray Ind Inc | Biaxially oriented laminated polyester film and method for manufacturing the same |
| CN101180377A (en) * | 2005-04-20 | 2008-05-14 | 艾利丹尼森公司 | Creep resistant adhesives and tapes made therewith |
| CN101538793A (en) * | 2009-04-20 | 2009-09-23 | 浙江理工大学 | Method for improving creep-resistant property of ultra-high molecular weight polyethylene fiber |
| CN102493168A (en) * | 2011-12-22 | 2012-06-13 | 北京服装学院 | Method for improving creep resistant performance of ultra-high molecular weight polyethylene fiber |
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