CN103556285B - Super low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof - Google Patents
Super low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof Download PDFInfo
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- CN103556285B CN103556285B CN201310478229.1A CN201310478229A CN103556285B CN 103556285 B CN103556285 B CN 103556285B CN 201310478229 A CN201310478229 A CN 201310478229A CN 103556285 B CN103556285 B CN 103556285B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 271
- 238000002360 preparation method Methods 0.000 title claims abstract description 75
- 238000002156 mixing Methods 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 38
- 239000007790 solid phase Substances 0.000 claims abstract description 38
- 238000004804 winding Methods 0.000 claims abstract description 36
- 238000009998 heat setting Methods 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 88
- 229910052731 fluorine Inorganic materials 0.000 claims description 88
- 239000011737 fluorine Substances 0.000 claims description 88
- 238000001816 cooling Methods 0.000 claims description 68
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 67
- 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 66
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 66
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 64
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 51
- 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 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 49
- 239000005977 Ethylene Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 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
- 230000009477 glass transition Effects 0.000 claims description 20
- 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 19
- 239000003054 catalyst Substances 0.000 claims description 18
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 18
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 238000001953 recrystallisation Methods 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 7
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 239000004744 fabric Substances 0.000 abstract description 5
- -1 fluoro epoxide Chemical class 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 230000008719 thickening Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000007664 blowing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 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
- 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
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process 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
- 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to super low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof, comprise the preparation of the sticky preparation of section of creep resistant polyester height and the super low shrinkage industrial yarn of creep resistant polyester; By polyester by solid phase polycondensation thickening, then carry out blending reaction with fluoro epoxide and obtain that described creep resistant polyester height is sticky cuts into slices; The sticky section of gained creep resistant polyester height through measuring, extruding, cool, oil, stretch, HEAT SETTING and winding obtain the super low shrinkage industrial yarn of creep resistant polyester.The super low shrinkage industrial yarn of gained creep resistant polyester has certain creep-resistant property, resistant to hydrolysis performance and stability, can be used in hot and humid environment for a long time, have huge prospect in fields such as plastics package, waterproof fabrics, rope, hawser and ocean fibers.
Description
Technical Field
The invention relates to an ultralow-shrinkage creep-resistant polyester industrial yarn and a preparation method thereof, in particular to an ultralow-shrinkage creep-resistant polyester industrial yarn modified by using a fluorine-containing epoxy compound as a 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 polyester industrial yarn is widely applied to different fields, and for the ultra-low shrinkage polyester industrial yarn, the PET molecules are regularly arranged, the crystallization density is high, the crystallinity is improved, and the shrinkage in size is reduced. It has the features of low dry heat shrinkage, high size stability, etc. and may be used widely in filter cloth, coated fabric, hose, conveying belt weft, etc.
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 polyester fibers.
Disclosure of Invention
The invention aims to provide a creep-resistant polyester ultralow-shrinkage industrial yarn and a preparation method thereof, and particularly relates to a creep-resistant polyester ultralow-shrinkage industrial yarn modified by using a fluorine-containing epoxy compound as a capping agent and a preparation method thereof. The creep-resistant polyester ultralow-shrinkage industrial yarn disclosed by the invention adopts creep-resistant polyester spinning, and the creep-resistant polyester is subjected to end-capping modification by using a 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 polyester ultralow-shrinkage industrial yarn 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:
a creep-resistant polyester ultralow-shrinkage industrial yarn is prepared by metering, extruding, cooling, oiling, stretching, heat setting and winding creep-resistant polyester high-viscosity chips; 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 is 10-20; the linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is less than or equal to 1.5%, the breaking strength is more than or equal to 7.0cN/dtex, the CV value of the breaking strength is less than or equal to 2.5%, the elongation at break is 20.0 +/-1.5%, the CV value of the elongation at break is less than or equal to 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 +/-0.25%.
The preparation method of the creep-resistant polyester ultralow-shrinkage industrial yarn is characterized in that the creep-resistant polyester ultralow-shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding;
the extrusion temperature is 290-320 ℃;
the cooling air temperature is 20-30 ℃;
the winding speed is 2600-3400 m/min;
the preparation method of the creep-resistant polyester hyperviscous slice is that polyester is tackified through solid phase polycondensation, and then the creep-resistant polyester hyperviscous slice is obtained through blending reaction with a fluorine-containing epoxy compound; 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 solid phase polycondensation method is that the polyester chip is heated to a temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the chip is improved, and the chip can be dried; when the polyester chip is a PET chip, increasing viscosity through solid phase polycondensation to enable the intrinsic viscosity of the PET chip to be increased to 0.9-1.2 dL/g; when the polyester chip is a PTT chip, increasing the intrinsic viscosity of the PTT chip to 0.9-1.3 dL/g through solid-phase polycondensation and tackifying; when the polyester chip is a PBT chip, the intrinsic viscosity of the PBT chip is increased to 0.9-1.3 dL/g through solid-phase polycondensation tackifying; when the polyester chip is a mixed polyester chip, increasing viscosity through solid-phase polycondensation to enable the intrinsic viscosity of the mixed polyester chip to be increased to 0.9-1.3 dL/g;
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 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 polyester is one or a mixture of more of PET, PTT and PBT or a copolymer of more of PET, PTT and PBT.
The intrinsic viscosity of PET in the polyester 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.
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 ultralow-shrinkage industrial yarn obtained by the invention has the advantages that the fluorine atoms have strong electronegativity, so that hydrogen bonds can be formed among polyester molecular chains, the acting force among molecules is increased, and the creep resistance effect can be realized to a certain extent.
2. The bisphenol A epoxy resin containing fluorine as the end capping agent of the creep-resistant polyester ultra-low shrinkage industrial yarn 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 ultralow-shrinkage industrial yarn 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 ultralow-shrinkage industrial yarn has huge prospects in the fields of plastic packaging, waterproof fabrics, ropes, cables, marine fibers and the like, and the application range 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 ultralow-shrinkage industrial yarn is prepared by metering, extruding, cooling, oiling, stretching, heat setting and winding creep-resistant polyester high-viscosity chips; 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。
the creep-resistant polyester ultralow-shrinkage industrial yarn has the linear density deviation rate of less than or equal to 1.5 percent, the breaking strength of more than or equal to 7.0cN/dtex, the breaking strength CV value of less than or equal to 2.5 percent, the elongation at break of 20.0 +/-1.5 percent, the elongation at break CV value of less than or equal to 7.0 percent and the dry heat shrinkage rate of 1.9 +/-0.25 percent under the test conditions of 177 ℃ and 0.05 cN/dtex.
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 5mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, 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.
Preparation of creep-resistant polyester hyperviscous slice:
tackifying PET polyester with the intrinsic viscosity of 0.6dL/g through solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester hyperviscous slice; 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 solid phase polycondensation method is that PET slices with the intrinsic viscosity of 0.6dL/g are heated to be higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PET slices is increased to be 0.9 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; 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 0.4 wt%; the winding speed was 2600 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0%, the elongation at break is 20.0%, the CV value of the elongation at break is 6.5%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
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 is 40 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring and reacting 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.
Preparation of creep-resistant polyester hyperviscous slice:
PTT polyester with the intrinsic viscosity of 0.7dL/g is tackified through solid phase polycondensation, and then the tackified PTT polyester is blended with bisphenol A epoxy resin containing fluorine to react to obtain the creep-resistant polyester high-viscosity slice; 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 solid phase polycondensation method is that PTT polyester chips with the intrinsic viscosity of 0.7dL/g are heated to be higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PTT chips is increased to 0.9 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 320 ℃; the cooling is cross air blow cooling, the temperature is 30 ℃, the relative humidity is 70%, and the wind speed is 0.8 m/s; the oiling rate of the oiling is 0.8 wt%; the winding speed was 3400 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultralow-shrinkage industrial yarn is 1.5%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 21.5%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 2.15%.
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 4mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 35 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, and stirring to react 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.
Preparation of creep-resistant polyester hyperviscous slice:
mixing PET polyester with the intrinsic viscosity of 0.6dL/g and PBT polyester with the intrinsic viscosity of 0.7dL/g according to the weight ratio of 1:1, tackifying by solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester hyperviscous slice; 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 solid phase polycondensation method is that PET and PBT polyester mixed slices are heated to a temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the mixed slices is improved to 0.9 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 300 ℃; the cooling is cross air blow cooling, the temperature is 25 ℃, the relative humidity is 65 percent, and the wind speed is 0.6 m/s; the oiling rate of the oiling is 0.6 wt%; the winding speed was 3000 m/min.
The linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 18.5%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.65%.
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 5mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, 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.
Preparation of creep-resistant polyester hyperviscous slice:
mixing PET polyester with the intrinsic viscosity of 0.65dL/g and PTT polyester with the intrinsic viscosity of 0.8dL/g according to the weight ratio of 1:1, tackifying by solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester high-viscosity slice; 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 4 wt% of the sum of the mass of the PET and the PTT polyesters; the solid phase polycondensation method is that PET and PTT polyester mixed slices are heated to a temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the mixed slices is increased to 1.1 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 300 ℃; the cooling is side-blown 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 0.4 wt%; the winding speed was 2800 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultra-low shrinkage industrial yarn is 1.3, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0 percent, the elongation at break is 20.0 percent, the CV value of the elongation at break is 6.5 percent, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 percent.
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 is 40 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring and reacting 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.
Preparation of creep-resistant polyester hyperviscous slice:
mixing PET polyester with the intrinsic viscosity of 0.7dL/g, PTT polyester with the intrinsic viscosity of 0.9dL/g and PBT polyester with the intrinsic viscosity of 0.9dL/g according to the weight ratio of 1:1:1, tackifying by solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester hyperviscous slice; blending reaction conditions are as follows: the temperature is 290 ℃, and the time is 3 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 solid phase polycondensation method comprises the steps of heating PET, PTT and PBT polyester mixed slices to a temperature higher than the glass transition temperature and lower than the melting point under a vacuum condition to improve the intrinsic viscosity of the mixed slices to 1.3 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 320 ℃; 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 0.4 wt%; the winding speed was 3400 m/min.
The linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 20.0%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
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 4mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 35 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, and stirring to react 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.
Preparation of creep-resistant polyester hyperviscous slice:
mixing PET polyester with the intrinsic viscosity of 0.6dL/g, PTT polyester with the intrinsic viscosity of 0.8dL/g and PBT polyester with the intrinsic viscosity of 0.8dL/g according to the weight ratio of 1:1:1, tackifying by solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester hyperviscous slice; 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 solid phase polycondensation method comprises the steps of heating PET, PTT and PBT polyester mixed slices to a temperature higher than the glass transition temperature and lower than the melting point under a vacuum condition to improve the intrinsic viscosity of the mixed slices to 0.9 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; 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 0.6 wt%; the winding speed is 3200 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultra-low shrinkage industrial yarn is 1.3, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0 percent, the elongation at break is 20.0 percent, the CV value of the elongation at break is 6.5 percent, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 percent.
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 5mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, 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.
Preparation of creep-resistant polyester hyperviscous slice:
mixing PET polyester with the intrinsic viscosity of 0.7dL/g and PBT polyester with the intrinsic viscosity of 0.7dL/g according to the weight ratio of 1:1, tackifying by solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester hyperviscous slice; 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 type epoxy resin is 4 wt% of the sum of the mass of the PET and the PTT polyesters; the solid phase polycondensation method is that PET and PTT polyester mixed slices are heated to a temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the mixed slices is increased to 0.9 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 320 ℃; the cooling is circular air blowing cooling, the temperature is 30 ℃, the relative humidity is 65%, and the wind speed is 0.4 m/s; the oiling rate of the oiling is 0.8 wt%; the winding speed was 2600 m/min.
The linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 20.0%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
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 is 40 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring and reacting 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.
Preparation of creep-resistant polyester hyperviscous slice:
tackifying PET polyester with the intrinsic viscosity of 0.7dL/g through solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin to obtain the creep-resistant polyester hyperviscous slice; 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 0.5 wt% of that of the PET polyester; the solid phase polycondensation method is that PET slices with the intrinsic viscosity of 0.7dL/g are heated to be higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PET slices is improved to be 1.3 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 300 ℃; the cooling is circular air blowing 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 0.6 wt%; the winding speed was 2800 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultra-low shrinkage industrial yarn is 1.3, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0 percent, the elongation at break is 20.0 percent, the CV value of the elongation at break is 6.5 percent, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 percent.
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 4mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 35 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, and stirring to react 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.
Preparation of creep-resistant polyester hyperviscous slice:
PTT polyester with the intrinsic viscosity of 0.9dL/g is tackified through solid phase polycondensation, and then the tackified PTT polyester is blended with bisphenol A epoxy resin containing fluorine to react to obtain the creep-resistant polyester high-viscosity slice; 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 5 wt% of the PTT polyester; the solid phase polycondensation method is that PTT polyester chips with the intrinsic viscosity of 0.9dL/g are heated to the temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PTT chips is improved to 1.3 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 310 ℃; 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 0.8 wt%; the winding speed was 3400 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultralow-shrinkage industrial yarn is 1.5%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 20.0%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
Example 10
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 5mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 30 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, 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.
Preparation of creep-resistant polyester hyperviscous slice:
tackifying PET polyester with the intrinsic viscosity of 0.65dL/g through solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A type epoxy resin and dicyclohexylcarbodiimide to obtain the creep-resistant polyester hyperviscous slice; 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 adding amount of the dicyclohexylcarbodiimide is 0.1 wt% of the PET polyester; the solid phase polycondensation method is that PET slices with the intrinsic viscosity of 0.65dL/g are heated to be higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PET slices is improved to be 1.0 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 300 ℃; the cooling is circular air blowing 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 0.6 wt%; the winding speed was 2800 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultra-low shrinkage industrial yarn is 1.3, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0 percent, the elongation at break is 20.0 percent, the CV value of the elongation at break is 6.5 percent, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 percent.
Example 11
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 is 40 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring and reacting 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.
Preparation of creep-resistant polyester hyperviscous slice:
PTT polyester with the intrinsic viscosity of 0.8dL/g is tackified through solid phase polycondensation, and then the tackified PTT polyester is mixed with fluorine-containing bisphenol A type epoxy resin and N, N' -diisopropylcarbodiimide to react to obtain the creep-resistant polyester hyperviscous slice; 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 creep-resistant polyester hyperviscous slice; the adding amount of the N, N' -diisopropylcarbodiimide is 1 wt% of the PTT polyester; the solid phase polycondensation method is that PTT polyester chips with the intrinsic viscosity of 0.8dL/g are heated to the temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PTT chips is improved to 1.1 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 300 ℃; the cooling is circular air blowing 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 0.6 wt%; the winding speed was 2800 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultra-low shrinkage industrial yarn is 1.3, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0 percent, the elongation at break is 20.0 percent, the CV value of the elongation at break is 6.5 percent, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 percent.
Example 12
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 is 40 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring and reacting 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.
Preparation of creep-resistant polyester hyperviscous slice:
the preparation method comprises the following steps of tackifying PBT polyester with the intrinsic viscosity of 0.7dL/g through solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin and N, N' -diisopropylcarbodiimide to obtain the creep-resistant polyester hyperviscous slice; 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 creep-resistant polyester hyperviscous slice; the adding amount of the N, N' -diisopropylcarbodiimide is 1 wt% of the PBT polyester; the solid phase polycondensation method is that PBT polyester chips with the intrinsic viscosity of 0.7dL/g are heated to be higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PBT chips is improved to be 0.9 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 320 ℃; 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 0.4 wt%; the winding speed was 3400 m/min.
The linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 20.0%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
Example 13
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 4mol/L sodium hydroxide solution which is saturated by anhydrous sodium carbonate and accounts for 35 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol, and stirring to react 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.
Preparation of creep-resistant polyester hyperviscous slice:
the preparation method comprises the following steps of tackifying PBT polyester with the intrinsic viscosity of 0.9dL/g through solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin and N, N' -diisopropylcarbodiimide to obtain the creep-resistant polyester hyperviscous slice; 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 5 wt% of the PBT polyester; the adding amount of the N, N' -diisopropylcarbodiimide is 1 wt% of the PBT polyester; the solid phase polycondensation method is that PBT polyester chips with the intrinsic viscosity of 0.9dL/g are heated to the temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PBT chips is improved to 1.3 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; the temperature of the extrusion is 320 ℃; 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 0.4 wt%; the winding speed was 3400 m/min.
The linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 2.5%, the elongation at break is 20.0%, the CV value of the elongation at break is 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
Example 14
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 is 40 percent of the mass of 4,4' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylidene ] diphenol and is saturated by anhydrous sodium carbonate, and stirring and reacting 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.
Preparation of creep-resistant polyester hyperviscous slice:
the preparation method comprises the following steps of tackifying PBT polyester with the intrinsic viscosity of 0.8dL/g through solid phase polycondensation, and then carrying out blending reaction with fluorine-containing bisphenol A epoxy resin and N, N' -diisopropylcarbodiimide to obtain the creep-resistant polyester hyperviscous slice; 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 creep-resistant polyester hyperviscous slice; the adding amount of the N, N' -diisopropylcarbodiimide is 1 wt% of the PBT polyester; the solid phase polycondensation method is that PBT polyester slices with the intrinsic viscosity of 0.8dL/g are heated to be higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the PBT slices is improved to be 1.1 dL/g; and the drying of the slices can be completed at the same time.
Preparation of creep-resistant polyester ultra-low shrinkage industrial yarn:
the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from a creep-resistant polyester high-viscosity slice through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding; 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 0.4 wt%; the winding speed was 2600 m/min.
The linear density deviation rate of the obtained creep-resistant polyester ultralow-shrinkage industrial yarn is 1.3%, the breaking strength is 7.2/dtex, the CV value of the breaking strength is 2.0%, the elongation at break is 20.0%, the CV value of the elongation at break is 6.5%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9%.
Claims (3)
1. A creep-resistant polyester ultralow-shrinkage industrial yarn is characterized in that: the creep-resistant polyester ultralow-shrinkage industrial yarn is prepared by metering, extruding, cooling, oiling, stretching, heat setting and winding creep-resistant polyester high-viscosity chips; 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 is 10-2; the linear density deviation rate of the creep-resistant polyester ultralow-shrinkage industrial yarn is less than or equal to 1.5%, the breaking strength is more than or equal to 7.0cN/dtex, the CV value of the breaking strength is less than or equal to 2.5%, the elongation at break is 20.0 +/-1.5%, the CV value of the elongation at break is less than or equal to 7.0%, and the dry heat shrinkage rate under the test conditions of 177 ℃ and 0.05cN/dtex is 1.9 +/-0.25%.
2. The process for preparing creep-resistant polyester ultra-low shrinkage industrial yarn as claimed in claim 1, wherein the creep-resistant polyester ultra-low shrinkage industrial yarn is prepared from creep-resistant polyester hyperviscous slices through the steps of metering, extruding, cooling, oiling, stretching, heat setting and winding;
the extrusion temperature is 290-320 ℃;
the cooling air temperature is 20-30 ℃;
the winding speed is 2600-3400 m/min;
the preparation method of the creep-resistant polyester hyperviscous slice is that polyester is tackified through solid phase polycondensation, and then the creep-resistant polyester hyperviscous slice is obtained through blending reaction with a fluorine-containing epoxy compound; 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 solid phase polycondensation method is that the polyester chip is heated to a temperature higher than the glass transition temperature and lower than the melting point under the vacuum condition, so that the intrinsic viscosity of the chip is improved, and the chip can be dried; when the polyester chip is a PET chip, increasing viscosity through solid phase polycondensation to enable the intrinsic viscosity of the PET chip to be increased to 0.9-1.2 dL/g;
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.
3. The method for preparing creep-resistant polyester ultralow-shrinkage industrial yarn according to claim 2, wherein the cooling is cross-blow or circular-blow cooling, the temperature is 20-30 ℃, the relative humidity is 65% ± 5%, and the wind speed is 0.4-0.8 m/s.
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| 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 |
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| CN102797056A (en) * | 2012-09-03 | 2012-11-28 | 江苏恒力化纤股份有限公司 | Manufacturing method for superlow shrinkage type PET industrial yarn |
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| 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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