CN103556291B - A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof - Google Patents
A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof Download PDFInfo
- Publication number
- CN103556291B CN103556291B CN201310480015.8A CN201310480015A CN103556291B CN 103556291 B CN103556291 B CN 103556291B CN 201310480015 A CN201310480015 A CN 201310480015A CN 103556291 B CN103556291 B CN 103556291B
- Authority
- CN
- China
- Prior art keywords
- resistant
- creep
- polyester
- hydrolysis
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 179
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 99
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 99
- 239000000835 fiber Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003381 stabilizer Substances 0.000 claims abstract description 22
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 72
- 229910052731 fluorine Inorganic materials 0.000 claims description 72
- 239000011737 fluorine Substances 0.000 claims description 72
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 47
- 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
- 238000001816 cooling Methods 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 43
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 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
- 238000003756 stirring Methods 0.000 claims description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 238000004804 winding Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 21
- 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 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 17
- 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
- 239000013078 crystal Substances 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000009998 heat setting Methods 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
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- -1 fluoro epoxide Chemical class 0.000 abstract description 8
- 239000004744 fabric Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 18
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance 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
- 229920006052 Chinlon® Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 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
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- 239000007789 gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof, comprise the preparation of creep resistant resistant to hydrolysis polyester fondant and the preparation of creep resistant resistant to hydrolysis polyester FDY fiber; By polyester and fluoro epoxide with Carbodiimides stabilizing agent is blended or add fluoro epoxide in the building-up process of polyester and namely Carbodiimides stabilizing agent obtains creep resistant resistant to hydrolysis polyester fondant; Gained creep resistant resistant to hydrolysis polyester fondant is through measuring, extruding, cool, oil, stretch and reel obtained creep resistant resistant to hydrolysis polyester FDY fiber.Gained creep resistant resistant to hydrolysis polyester FDY fiber has certain creep-resistant property, resistant to hydrolysis performance and stability, can be used in for a long time in field wet environment or hot and humid environment, have huge prospect in fields such as plastics package, waterproof fabrics, rope, hawser and ocean fibers.
Description
Technical Field
The invention relates to creep-resistant hydrolysis-resistant polyester FDY (fully drawn yarn) fibers and a preparation method thereof, in particular to creep-resistant hydrolysis-resistant polyester FDY fibers modified by using a fluorine-containing epoxy compound as a blocking agent and a carbodiimide stabilizer 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. By introducing a drawing action during spinning, a wound yarn having a high degree of orientation and a moderate degree of crystallinity, called fully drawn yarn, i.e., FDY, can be obtained. FDY is mainly used as warp of water-jet loom fabric, and conventional fully drawn yarns with terylene and chinlon belong to chemical fiber filaments. The FDY fabric has smooth and soft hand feeling, is often used for weaving the silk-like fabric, and has wide application in the aspects of clothing and home textiles.
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.
Hydrolysis also occurs when the polyester material is exposed to an environment above the glass transition temperature and in contact with water for a long time, and phenomena of random scission and depolymerization of the polymer chains occur. The depolymerization reaction of the polyester is carried out simultaneously at the inner part and the outer part of the polyester, which causes the aging of the polyester, leads the surface of the polyester product to lose luster, reduces the mechanical property and loses the use value. Not only wastes materials, but also pollutes the environment. The main factor influencing the hydrolysis of the polyester is the concentration of the terminal carboxyl, and the service life of the polyester material in a damp and hot environment can be prolonged by reducing the activity of the free terminal carboxyl in the polyester material and the concentration of the initial terminal carboxyl. In addition, the hydrolysis stabilizer can be added into the polyester material to consume the terminal carboxyl group generated in the hydrolysis process, so as to control the terminal carboxyl group concentration of the polyester material and further reduce the hydrolysis rate of the polyester material.
Related patents such as CN1312327A use a polymer containing epoxy and amino groups as a blocking agent to improve the hydrolysis resistance of polyester, but the preparation process of the blocking agent is complicated. Japanese patent JP9296097 adds specially prepared carbodiimide as a stabilizer to polyester plastics to endow the polyester plastics with better hydrolysis resistance, but carbodiimide compounds are expensive and have poor thermal stability, and gases harmful to human bodies are generated in the processing process. 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 relates to creep-resistant hydrolysis-resistant polyester FDY (fully drawn yarn) fibers and a preparation method thereof, in particular to creep-resistant hydrolysis-resistant polyester FDY fibers modified by using a fluorine-containing epoxy compound as a blocking agent and a carbodiimide stabilizer and a preparation method thereof. By using the carbodiimide stabilizer, the hydrolysis resistance of the polyester can be improved; 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 creep-resistant hydrolysis-resistant polyester FDY fiber 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 creep-resistant hydrolysis-resistant polyester FDY fiber is prepared by metering, extruding, cooling, oiling, stretching and winding creep-resistant hydrolysis-resistant polyester melt; the creep-resistant hydrolysis-resistant polyester is a polyester with a part of macromolecular chains blocked by fluorine-containing epoxy compounds and added with carbodiimide stabilizers, 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,
m＝80～100，
n＝10～20。
the filament number of the creep-resistant hydrolysis-resistant polyester FDY fiber is 0.5-3.0 dtex; the breaking strength is 1.6-2.5 cN/dtex; the elongation at break is 110 to 150%.
The carbodiimide stabilizer is one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
The creep-resistant hydrolysis-resistant polyester FDY fiber is prepared by metering, extruding, cooling, oiling, stretching and winding creep-resistant hydrolysis-resistant polyester melt;
the extrusion temperature is 260-290 ℃;
the cooling air temperature is 20-30 ℃;
the oiling rate of the oiling is 0.42-1.5 wt%;
the drawing speed of the first hot roller for drawing is 1000-1500 m/min; the drafting speed of the second hot roller is 4000-6000/min, and the heat setting temperature is 135-155 ℃;
the winding speed is 3950-5950 m/min;
the preparation method of the creep-resistant hydrolysis-resistant polyester comprises the following steps: carrying out blending reaction on polyester, a fluorine-containing epoxy compound and a carbodiimide stabilizer to obtain the creep-resistant hydrolysis-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 addition amount of the carbodiimide stabilizer is 0.1-1 wt% of the polyester;
or reacting with dibasic acid and dihydric alcohol as comonomers, adding a fluorine-containing epoxy compound and a carbodiimide stabilizer 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 hydrolysis-resistant polyester; the addition amount of the fluorine-containing epoxy compound is 0.8-8 wt% of the dibasic acid; the addition amount of the carbodiimide stabilizer is 0.2-2 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.
The dibasic acid is terephthalic acid; the dihydric alcohol is ethylene glycol.
The polyester is PET.
The intrinsic viscosity of the polyester PET is 0.6-0.7 dL/g.
The cooling is cross air blowing or circular air blowing, the temperature is 20-30 ℃, the relative humidity is 65% +/-5%, and the air speed is 0.4-0.8 m/s.
The creep-resistant hydrolysis-resistant polyester melt is directly obtained by polymerization or is obtained by melting creep-resistant hydrolysis-resistant polyester chips by a screw.
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:
10. according to the creep-resistant hydrolysis-resistant polyester FDY fiber, fluorine atoms have strong electronegativity, so that hydrogen bonds can be formed among polyester molecular chains, intermolecular acting force is increased, and the creep-resistant effect can be achieved to a certain extent.
11. According to the creep-resistant hydrolysis-resistant polyester FDY fiber, the bisphenol A epoxy resin containing fluorine as the end-capping reagent can play a role in chain extension, so that the relative molecular mass of the polyester can be increased, and the creep resistance of the polyester can be improved.
12. The creep-resistant hydrolysis-resistant polyester FDY fiber obtained by the invention is subjected to end-capping modification by using the fluorine-containing bisphenol A epoxy resin, so that the end carboxyl groups in the polyester molecules can be partially eliminated, and due to the introduction of silicon atoms and fluorine atoms, the polyester can be made hydrophobic and water repellent, and the hydrolysis resistance of the polyester is improved; the hydrolysis resistance of the polyester can also be improved by using a carbodiimide-based stabilizer.
13. The creep-resistant hydrolysis-resistant polyester FDY fiber has huge prospects in the fields of plastic packaging, waterproof fabrics, ropes, cables, marine fibers and the like, and expands the application range of polyester.
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 hydrolysis-resistant polyester FDY fiber is prepared by directly extruding creep-resistant hydrolysis-resistant polyester melt or preparing into slices, and performing screw melt extrusion, cooling, oiling, stretching and winding; the creep-resistant hydrolysis-resistant polyester is a polyester with a part of macromolecular chains blocked by fluorine-containing epoxy compounds and added with carbodiimide stabilizers, 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,
m＝80～100，
n＝10～20。
the creep-resistant hydrolysis-resistant polyester FDY fiber has the breaking strength of 3-5 cN/dex; the elongation at break is 18-45%.
The creep-resistant hydrolysis-resistant polyester FDY fiber is characterized in that the carbodiimide stabilizer is one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
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, fluorine-containing bisphenol A epoxy resin and dicyclohexylcarbodiimide to obtain the creep-resistant hydrolysis-resistant polyester; blending reaction conditions are as follows: the temperature is 270 ℃ and the time is 5 min; the addition amount of the fluorine-containing bisphenol A epoxy resin is 0.5 wt% of that of the PET polyester; the dicyclohexylcarbodiimide was added in an amount of 0.1 wt% of the PET polyester.
Method for making FDY fiber:
the FDY fiber is prepared by the creep-resistant hydrolysis-resistant polyester melt through metering, extrusion, cooling, oiling, first hot roller, second hot roller and winding molding; the temperature of the extrusion is 260 ℃; the cooling is cross air blow cooling, the temperature is 30 ℃, the relative humidity is 65%, and the wind speed is 0.8 m/s; the oiling rate of the oiling is 0.42 wt%; the drafting speed of the first hot roller is 1000 m/min; the drawing speed of the second hot roller is 4000m/min, and the heat setting temperature is 135 ℃; the winding speed is 3950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 3 cN/dex; the elongation at break was 45%.
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, fluorine-containing bisphenol A type epoxy resin and N, N' -diisopropylcarbodiimide to obtain the creep-resistant hydrolysis-resistant polyester; blending reaction conditions are as follows: the temperature is 290 ℃, and the time is 3 min; the addition amount of the fluorine-containing bisphenol A epoxy resin is 5 wt% of the PTT polyester; the amount of the N, N' -diisopropylcarbodiimide added is 1 wt% of the PTT polyester.
Preparation method of FDY:
directly extruding, cooling and oiling the creep-resistant hydrolysis-resistant polyester melt, and carrying out winding molding on the melt to obtain FDY fibers by using a first hot roller and a second hot roller; the temperature of the extrusion is 290 ℃; the cooling is side-blown cooling, the temperature is 20 ℃, the relative humidity is 60%, and the wind speed is 0.4 m/s; the oiling rate of the oiling is 1.5 wt%; the drawing speed of the first hot roller is 1500 m/min; the drafting speed of the second hot roller is 6000m/min, and the heat setting temperature is 155 ℃; the winding speed is 5950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 5 cN/dex; the elongation at break was 18%.
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 fluorine-containing bisphenol A epoxy resin and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride according to the weight ratio of 1:1 to react to obtain the creep-resistant hydrolysis-resistant polyester; blending reaction conditions are as follows: the temperature is 280 ℃ and the time is 4 min; the addition amount of the fluorine-containing bisphenol A type epoxy resin is 3 wt% of the sum of the PET and PBT polyesters; the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is added in an amount of 0.3 wt% of the sum of the qualities of the PET and PBT polyesters.
Method for making FDY fiber:
directly extruding, cooling and oiling the creep-resistant hydrolysis-resistant polyester melt, and carrying out winding molding on the melt to obtain FDY fibers by using a first hot roller and a second hot roller; the temperature of the extrusion is 270 ℃; the cooling is cross air blow cooling, the temperature is 25 ℃, the relative humidity is 70%, and the wind speed is 0.6 m/s; the oiling rate of the oiling is 0.96 wt%; the drawing speed of the first hot roller is 1200 m/min; the drafting speed of the second hot roller is 4500m/min, and the heat setting temperature is 140 ℃; the winding speed is 4450 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 3.5 cN/dex; the elongation at break was 40%.
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.
PET and PTT polyester are mixed with fluorine-containing bisphenol A type epoxy resin according to the weight ratio of 1:1 and the weight ratio of 1:1, performing blending reaction on dicyclohexylcarbodiimide and N, N' -diisopropylcarbodiimide to obtain the creep-resistant hydrolysis-resistant polyester; blending reaction conditions are as follows: the temperature is 275 ℃ and the time is 5 min; the addition amount of the fluorine-containing bisphenol A type epoxy resin is 4 wt% of the sum of the mass of the PET and the PTT polyesters; the adding amount of the dicyclohexylcarbodiimide and the N, N' -diisopropylcarbodiimide is 0.25 wt% of the sum of the mass of the PET and the mass of the PTT polyester.
Method for making FDY fiber:
directly extruding, cooling and oiling the creep-resistant hydrolysis-resistant polyester melt, and carrying out winding molding on the melt to obtain FDY fibers by using a first hot roller and a second hot roller; the temperature of the extrusion is 280 ℃; the cooling is cross air blowing or cooling, the temperature is 25 ℃, the relative humidity is 65%, and the wind speed is 0.6 m/s; the oiling rate of the oiling is 1.5 wt%; the drawing speed of the first hot roller is 1300 m/min; the drafting speed of the second hot roller is 5000m/min, and the heat setting temperature is 145 ℃; the winding speed is 4950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 4 cN/dex; the elongation at break was 30%.
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.
Mixing PET, PTT and PBT polyester with a fluorine-containing bisphenol A type epoxy resin according to a weight ratio of 1:1:1 and a weight ratio of 1: carrying out blending reaction on the N, N' -diisopropylcarbodiimide of 1 and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to obtain the creep-resistant hydrolysis-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; the addition amount of the N, N' -diisopropylcarbodiimide and the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 0.4 wt% of the sum of the PET, PTT and PBT polyesters.
Method for making FDY fiber:
directly extruding, cooling and oiling the creep-resistant hydrolysis-resistant polyester melt, and carrying out winding molding on the melt to obtain FDY fibers by using a first hot roller and a second hot roller; the temperature of the extrusion is 290 ℃; the cooling is cross-blow or circular-blow cooling, the temperature is 20 ℃, the relative humidity is 65%, and the wind speed is 0.4 m/s; the oiling rate of the oiling is 0.42 wt%; the drafting speed of the first hot roller is 1400 m/min; the drafting speed of the second hot roller is 5500m/min, and the heat setting temperature is 150 ℃; the winding speed is 5450 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 5 cN/dex; the elongation at break was 18%.
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 and dicyclohexylcarbodiimide 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 hydrolysis-resistant polyester; the addition amount of the fluorine-containing bisphenol A epoxy resin is 0.8 wt% of terephthalic acid; the amount of dicyclohexylcarbodiimide added was 0.2 wt% of terephthalic acid.
Method for making FDY fiber:
the FDY fiber is prepared by carrying out screw melt extrusion, cooling and oiling on the creep-resistant hydrolysis-resistant polyester chip, and carrying out winding molding on the creep-resistant hydrolysis-resistant polyester chip by a first hot roller and a second hot roller; the temperature of the extrusion is 260 ℃; the cooling is circular air blowing cooling, the temperature is 30 ℃, the relative humidity is 65%, and the air speed is 0.8 m/s; the oiling rate of the oiling is 0.42 wt%; the drafting speed of the first hot roller is 1000 m/min; the drawing speed of the second hot roller is 4000m/min, and the heat setting temperature is 135 ℃; the winding speed is 3950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 3 cN/dex; the elongation at break was 45%.
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 and N, N' -diisopropylcarbodiimide 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 hydrolysis-resistant polyester; the addition amount of the fluorine-containing bisphenol A epoxy resin is 8 wt% of terephthalic acid; the amount of N, N' -diisopropylcarbodiimide added was 2 wt% of terephthalic acid.
Method for making FDY fiber:
the FDY fiber is prepared by carrying out screw melt extrusion, cooling and oiling on the creep-resistant hydrolysis-resistant polyester chip, and carrying out winding molding on the creep-resistant hydrolysis-resistant polyester chip by a first hot roller and a second hot roller; the temperature of the extrusion is 290 ℃; the cooling is circular blowing cooling, the temperature is 20 ℃, the relative humidity is 65%, and the wind speed is 0.4 m/s; the oiling rate of the oiling is 1.5 wt%; the drawing speed of the first hot roller is 1500 m/min; the drafting speed of the second hot roller is 6000m/min, and the heat setting temperature is 155 ℃; the winding speed is 5950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 5 cN/dex; the elongation at break was 18%.
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.
Adding terephthalic acid, ethylene glycol and propylene glycol as comonomers in a molar ratio of 2:1:1, reacting, adding fluorine-containing bisphenol A epoxy resin and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride 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 hydrolysis-resistant polyester; the addition amount of the fluorine-containing bisphenol A epoxy resin is 2 wt% of terephthalic acid; the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride was added in an amount of 0.8 wt% based on the terephthalic acid.
Method for making FDY fiber:
the FDY fiber is prepared by carrying out screw melt extrusion, cooling and oiling on the creep-resistant hydrolysis-resistant polyester chip, and carrying out winding molding on the creep-resistant hydrolysis-resistant polyester chip by a first hot roller and a second hot roller; the temperature of the extrusion is 290 ℃; the cooling is cross-blow or circular-blow cooling, the temperature is 20 ℃, the relative humidity is 65%, and the wind speed is 0.4 m/s; the oiling rate of the oiling is 1.5 wt%; the drawing speed of the first hot roller is 1500 m/min; the drafting speed of the second hot roller is 6000m/min, and the heat setting temperature is 155 ℃; the winding speed is 5950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 5 cN/dex; the elongation at break was 18%.
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.
Terephthalic acid, ethylene glycol and butanediol are used as comonomers, feeding and reacting are carried out according to a molar ratio of 2:1:1, and when the intrinsic viscosity of a reaction product is more than 0.6dL/g, a fluorine-containing bisphenol A type epoxy resin and a weight ratio of 1:1, then stirring for 20min under a vacuum condition, and discharging to obtain the creep-resistant hydrolysis-resistant polyester; the addition amount of the fluorine-containing bisphenol A epoxy resin is 6 wt% of terephthalic acid; the addition amount of the dicyclohexylcarbodiimide and the N, N' -diisopropylcarbodiimide is 0.8 wt% of the terephthalic acid.
Method for making FDY fiber:
the FDY fiber is prepared by carrying out screw melt extrusion, cooling and oiling on the creep-resistant hydrolysis-resistant polyester chip, and carrying out winding molding on the creep-resistant hydrolysis-resistant polyester chip by a first hot roller and a second hot roller; the temperature of the extrusion is 280 ℃; the cooling is cross air blowing or circular air blowing, the temperature is 25 ℃, the relative humidity is 65 percent, and the wind speed is 0.8 m/s; the oiling rate of the oiling is 1.5 wt%; the drawing speed of the first hot roller is 1300 m/min; the drafting speed of the second hot roller is 5000m/min, and the heat setting temperature is 145 ℃; the winding speed is 4950 m/min; finally, creep-resistant hydrolysis-resistant polyester FDY fiber is prepared, and the breaking strength is 4 cN/dex; the elongation at break was 30%.
Claims (9)
1. A creep-resistant hydrolysis-resistant polyester FDY fiber is characterized in that: the creep-resistant hydrolysis-resistant polyester FDY fiber is prepared by metering, extruding, cooling, oiling, stretching and winding creep-resistant hydrolysis-resistant polyester melt; the creep-resistant hydrolysis-resistant polyester is a polyester with a part of macromolecular chains blocked by fluorine-containing epoxy compounds and added with carbodiimide stabilizers, 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,
m＝80～100，
n＝10～20。
2. the creep-resistant hydrolysis-resistant polyester FDY fiber according to claim 1, wherein the creep-resistant hydrolysis-resistant polyester FDY fiber has a breaking strength of 3 to 5 cN/dex; the elongation at break is 18-45%.
3. The creep-resistant hydrolysis-resistant polyester FDY fiber according to claim 1, wherein the carbodiimide stabilizer is one or more of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
4. The method of claim 1, wherein the creep-resistant hydrolysis-resistant polyester FDY fiber is prepared by the following steps: the creep-resistant hydrolysis-resistant polyester FDY fiber is prepared by metering, extruding, cooling, oiling, stretching and winding creep-resistant hydrolysis-resistant polyester melt;
the extrusion temperature is 260-290 ℃;
the cooling air temperature is 20-30 ℃;
the oiling rate of the oiling is 0.42-1.5 wt%;
the drawing speed of the first hot roller for drawing is 1000-1500 m/min; the drafting speed of the second hot roller is 4000-6000/min, and the heat setting temperature is 135-155 ℃;
the winding speed is 3950-5950 m/min;
the preparation method of the creep-resistant hydrolysis-resistant polyester comprises the following steps: carrying out blending reaction on polyester, a fluorine-containing epoxy compound and a carbodiimide stabilizer to obtain the creep-resistant hydrolysis-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 addition amount of the carbodiimide stabilizer is 0.1-1 wt% of the polyester;
or reacting with dibasic acid and dihydric alcohol as comonomers, adding a fluorine-containing epoxy compound and a carbodiimide stabilizer 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 hydrolysis-resistant polyester; the addition amount of the fluorine-containing epoxy compound is 0.8-8 wt% of the dibasic acid; the addition amount of the carbodiimide stabilizer is 0.2-2 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.
5. The method for preparing the creep-resistant hydrolysis-resistant polyester FDY fiber according to claim 4, wherein the dibasic acid is terephthalic acid; the dihydric alcohol is ethylene glycol.
6. The method as claimed in claim 4, wherein the polyester is PET.
7. The method of preparing the creep-resistant hydrolysis-resistant polyester FDY fiber according to claim 6, wherein the intrinsic viscosity of the polyester PET is 0.6 to 0.7 dL/g.
8. The preparation method of the creep-resistant hydrolysis-resistant polyester FDY fiber according to claim 4, wherein the cooling is cross-blown or circular-blown cooling, the temperature is 20-30 ℃, the relative humidity is 65% ± 5%, and the wind speed is 0.4-0.8 m/s.
9. The method as claimed in claim 4, wherein the creep-resistant hydrolysis-resistant polyester FDY fiber is prepared by directly polymerizing the creep-resistant hydrolysis-resistant polyester melt or by melting creep-resistant hydrolysis-resistant polyester chips by a screw.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310480015.8A CN103556291B (en) | 2013-10-14 | 2013-10-14 | A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310480015.8A CN103556291B (en) | 2013-10-14 | 2013-10-14 | A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103556291A CN103556291A (en) | 2014-02-05 |
| CN103556291B true CN103556291B (en) | 2015-08-05 |
Family
ID=50010629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310480015.8A Active CN103556291B (en) | 2013-10-14 | 2013-10-14 | A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103556291B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112746349B (en) * | 2020-12-29 | 2021-12-21 | 江苏恒力化纤股份有限公司 | High-strength creep-resistant polyester industrial yarn and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-10-14 CN CN201310480015.8A patent/CN103556291B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103556291A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103556293B (en) | High-strength flatness industrial yarn of a kind of ocean creep resistant polyester and preparation method thereof | |
| CN103526325B (en) | Water-repellent creep-resistant polyester fully drawn yarn (FDY) fiber and preparation method thereof | |
| CN103556294B (en) | A kind of creep resistant resistant to hydrolysis polyester and preparation method thereof | |
| CN103556285B (en) | Super low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN106400198A (en) | Manufacturing method of polyester fiber with anti-aging function | |
| CN113861411A (en) | High-stability nylon polymer and preparation method thereof | |
| CN103556289B (en) | Creep-resistant polyester and its preparation method | |
| CN103526327B (en) | High-modulus low-shrinkage creep-resistant polyester industrial yarn and preparation method thereof | |
| CN103541037B (en) | High-strength safety belt industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN103526326B (en) | High-modulus low-shrinkage creep-resistant activated polyester industrial yarn and preparation method thereof | |
| CN103774273B (en) | Anti-core suction type industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN103556291B (en) | A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof | |
| CN103541038B (en) | High intensity low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN103556292B (en) | Super high strength industrial filament of a kind of creep resistant polyester and preparation method thereof | |
| CN103556286B (en) | A kind of creep resistant resistant to hydrolysis polyester POY fiber and preparation method thereof | |
| CN103556287B (en) | Color silk of a kind of creep resistant polyester and preparation method thereof | |
| CN116695272A (en) | Breathable cationic dyeable polyester fiber and preparation method thereof | |
| CN115679469B (en) | Preparation method and application of P34HB fiber | |
| CN103526328B (en) | Supplementary restraint system industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN1974893A (en) | Prepn process of paraphthalic acid-butanediol succinate copolymer fiber | |
| CN103556288B (en) | High-strength car mould industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN103526324B (en) | High-strength low-elongation creep-resistant polyester industrial yarn and preparation method | |
| CN117646290B (en) | Flame-retardant antibacterial polyester industrial yarn and preparation method thereof | |
| JPH10168655A (en) | Polyester fiber and its production | |
| CN117624573B (en) | Flame-retardant polyester with homogeneously dispersed silicon dioxide, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |