CN103556285A - Creep-resistant polyester ultralow-shrinkage industrial yarn and its preparation method - Google Patents
Creep-resistant polyester ultralow-shrinkage industrial yarn and its preparation method Download PDFInfo
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- CN103556285A CN103556285A CN201310478229.1A CN201310478229A CN103556285A CN 103556285 A CN103556285 A CN 103556285A CN 201310478229 A CN201310478229 A CN 201310478229A CN 103556285 A CN103556285 A CN 103556285A
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- resistant polyester
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- 0 C=*C1=CC=CCC1 Chemical compound C=*C1=CC=CCC1 0.000 description 1
Abstract
The invention relates to a creep-resistant polyester ultralow-shrinkage industrial yarn and its preparation method. The preparation method includes preparation of a creep-resistant polyester hyperviscous slice and preparation of a creep-resistant polyester ultralow-shrinkage industrial yarn. According to the preparation method, polyester is tackified through solid phase polycondensation and then the tackified polyester is mixed with a fluorine-containing epoxy compound to react so as to obtain the creep-resistant polyester hyperviscous slice; and the creep-resistant polyester ultralow-shrinkage industrial yarn is prepared from the obtained creep-resistant polyester hyperviscous slice by metering, extrusion, cooling, oiling, stretching, thermoforming and coiling. The obtained creep-resistant polyester ultralow-shrinkage industrial yarn has a certain creep resistance, hydrolysis resistance and performance stability, can be used in a hot and humid environment for a long time, and has a huge prospect in the fields of plastic packing, waterproof fabric, ropes, cables, marine fiber and the like.
Description
Technical field
The present invention relates to super low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof, particularly relate to super low shrinkage industrial yarn of a kind of creep resistant polyester that carries out modification with fluoro epoxide as end-capping reagent and preparation method thereof.
Background technology
Polyester (PET) is one of the most widely used synthetic high polymer of the current mankind, there is high strength, high-modulus and good heat resistance, be linear thermoplastic's polymer of realizing the earliest industrial applications, it is widely used in the fields such as plastics package, film and chemical fibre.Polyester industrial yarn is widely used in different fields, and for ultralow shrinkage type polyester industrial yarn, to be that PET molecule is regular arrange its architectural feature, and crystal density is larger, and degree of crystallinity improves and contraction in size reduces.It has compared with low dry-hot shrinkage and the good feature such as DIMENSIONAL STABILITY and be widely used in filter cloth, coated fabric, the aspects such as flexible pipe and conveyer belt parallel.
The molecular chain structure of polyester is the linear macromolecule that contains benzene ring structure, the functional group's marshalling on strand, and unbranched, the flexibility of macromolecular chain is poor.Compare with other macromolecular materials, the strand generation slippage of polyester is difficulty comparatively, has certain DIMENSIONAL STABILITY.But can there is creep while using for a long time in polyester material more than vitrification point.Creep is the trend of the slow permanent movement of solid material or distortion under stress influence, it be the result due to long duration of action under the stress lower than material yield intensity.When material is during for a long time in heated condition or near temperature fusing point, creep meeting is more violent.The temperature range that the deformation of creep occurs is because of material difference difference, relevant with its molecular structure.If there is larger creep in polyester material in the process of using, will cause the unstable of its size, form, this will seriously limit polyester material particularly application in high-strength rope field in a lot of fields.
Improving polyester material creep-resistant property can be by following several mode: (1) is used below the vitrification point of material; (2) take various method of modifying, large molecule is occurred crosslinked; (3) improve macromolecular relative molecular mass; (4) improve active force between macromolecular chain, comprise that chain linked to owner introduces fragrant heterocycle, polar group or form inierpeneirating network structure etc.
Patents as the patent CN200680017951.3 of U.S. Avery Dennison Corp discloses a kind of take contain the creep resistant pressure sensitive adhesive product that aromatic hydrocarbon that vinyl replaces and conjugated diene block copolymer are main component.Patents is if CN200910097866.8 is by adding photosensitizer to polyethylene fiber preliminary treatment, then process ultraviolet irradiation improves the creep-resistant property of fiber.CN201110434278.6 adopts photosensitizer and thermal initiator to be cross-linked common initiation of polyethylene fiber, thereby increases the creep-resistant property of fiber.But there be limited evidence currently of has for polyester fiber about creep resisting research.
Summary of the invention
The object of this invention is to provide super low shrinkage industrial yarn of a kind of creep resistant polyester and preparation method thereof, particularly relate to super low shrinkage industrial yarn of a kind of creep resistant polyester that carries out modification with fluoro epoxide as end-capping reagent and preparation method thereof.The super low shrinkage industrial yarn of creep resistant polyester of the present invention adopts creep resistant Direct-spinning of PET Fiber, described creep resistant polyester is by being used fluoro epoxide to carry out blocking modification to polyester, the creep-resistant property of polyester can be improved to a certain extent, resistant to hydrolysis performance and the stability of polyester can be improved simultaneously.The super low shrinkage industrial yarn of a kind of creep resistant polyester of the present invention, can be used in hot and humid environment for a long time, in plastics package, waterproof fabrics, rope, hawser and ocean, with fields such as fibers, has huge prospect.
The invention provides following technical scheme:
A super low shrinkage industrial yarn for creep resistant polyester, be by the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling make; Described creep resistant polyester refers to the polyester of fluoro epoxide end-blocking gained for the part macromolecular chain of polyester, and described end-blocking refers to one end end-blocking and/or the two ends sealed to macromolecular chain, and its molecular structural formula is respectively:
One end end-blocking,
Two ends sealed,
Wherein,
m=80～100，
n=10～20。
The super low shrinkage industrial yarn of a kind of creep resistant polyester as above, line density deviation ratio≤1.5% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength >=7.0cN/dtex, fracture strength CV value≤2.5%, extension at break is 20.0 ± 1.5%, extension at break CV value≤7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05 cN/dtex is 1.9 ± 0.25%.
The preparation method of the super low shrinkage industrial yarn of described creep resistant polyester, be by the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester;
The described temperature of extruding is 290～320 ℃;
Described cooling wind-warm syndrome is 20～30 ℃;
The speed of described coiling is 2600～3400m/min;
The preparation method of the high sticky section of described creep resistant polyester refers to polyester is passed through to solid phase polycondensation tackify, then carries out blending reaction with fluoro epoxide and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 270～290 ℃, the time is 3～5min; Described fluoro epoxide addition is 0.5～5wt% of described polyester; The method of described solid phase polycondensation is by described polyester slice, more than being heated to vitrification point, below fusing point, the inherent viscosity of section is improved under vacuum condition, can complete chip drying simultaneously; When described polyester slice is PET section, by solid phase polycondensation tackify, make the inherent viscosity of PET section bring up to 0.9～1.2dL/g; When described polyester slice is PTT section, by solid phase polycondensation tackify, make the inherent viscosity of PTT section bring up to 0.9～1.3dL/g; When described polyester slice is PBT section, by solid phase polycondensation tackify, make the inherent viscosity of PBT section bring up to 0.9～1.3dL/g; When described polyester slice is mixed polyester section, by solid phase polycondensation tackify, make the inherent viscosity of mixed polyester section bring up to 0.9～1.3dL/g;
Described fluoro epoxide refers to fluorine-containing bisphenol A type epoxy resin, and its molecular structural formula is:
N=10～20 wherein;
Described fluorine-containing bisphenol A type epoxy resin is by diphenyl silanediol and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is raw material, adopts stannic chloride to carry out blending reaction as catalyst and makes; Concrete steps are:
Described 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 10～15mol/L sodium hydroxide solution of 1.5～2.0% of biphenol quality, at ambient temperature stirring reaction 16～18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3～5mol/L sodium hydroxide solution of 30～40% use natrium carbonicum calcinatums of biphenol quality, at ambient temperature stirring reaction 10～15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of described fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.06～0.10% is as catalyst, in temperature, is to carry out blending reaction under 150～180 ℃ and the mixing time condition that is 30～40min, obtains described fluorine-containing bisphenol A type epoxy resin.
Described is cooled to lateral blowing or encircles quenching, and temperature is 20 ℃～30 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.
Described polyester refer in PET, PTT and PBT one or more mixture or several copolymers.
In described polyester, the inherent viscosity of PET is 0.6～0.7dL/g; The inherent viscosity of PTT is 0.7～0.9dL/g; The inherent viscosity of PBT is 0.7～0.9dL/g.
Fluorine-containing bisphenol A type epoxy resin described in the present invention is by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol reaction obtains 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether, gained 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether reacts and makes with diphenyl silanediol.In described fluorine-containing bisphenol A type epoxy resin, contain
structure, but this structure space steric hindrance is larger, is difficult to obtain the bisphenol A epoxide resin of certain molecular weight.In described fluorine-containing bisphenol A type epoxy resin
structure, can reduce the sterically hindered of macromolecular chain, and Chain Flexibility is strengthened to some extent, can greatly promote the polymerisation of bisphenol A type epoxy resin, effectively improves its relative molecular mass.
Described fluorine-containing bisphenol A type epoxy resin has certain degree of polymerization, strand is longer, there is certain modulus, with polyester blend, can increase the ratio of benzene ring structure in polyester molecule chain, make the functional group on strand arrange more neatly, effectively improve stretch modulus and the TENSILE STRENGTH of polyester.
Described fluorine-containing bisphenol A type epoxy resin, because fluorine atom has strong electronegativity, can form a large amount of and uniform hydrogen bond with polyester blend, gives full play to the effect of fluorine atom, effectively increases intermolecular active force.Polyester after described fluorine-containing bisphenol A type epoxy resin blocking modification, even if there is in use External Force Acting, its strand is also difficult to occur slippage, the deformation of creep is little, DIMENSIONAL STABILITY is fine, can play to a certain extent creep resisting effect, improves better the creep-resistant property of polyester.
Described fluorine-containing bisphenol A type epoxy resin carries out modification as end-capping reagent to polyester, and its epoxy construction containing can partly be eliminated the end carboxyl in polyester molecule, controls the growth rate of carboxylic end group concentration, and the degree that effectively controlled hydrolysis speed is accelerated.This has just been avoided its phenomenon that hydrolysis occurs and occur macromolecule random chain scission and depolymerization during long-time exposure more than vitrification point, in the environment of contact water; Again because end-capping reagent has been introduced silicon atom, fluorine atom in macromolecular chain, the performance that can give polyester hydrophobic, refuse water, has improved the hydrolytic resistance of polyester to a certain extent, has improved the service life of polyester material in hygrothermal environment.In addition, fluorine-containing bisphenol A type epoxy resin has special epoxy construction, reacts, but do not have little molecule as the generation of water with polyester blend, has avoided polyester to occur in process of production, from degraded, to make gained polyester have good heat endurance.
Beneficial effect:
1, the super low shrinkage industrial yarn of the creep resistant polyester of gained of the present invention because fluorine atom has strong electronegativity, can form hydrogen bond between polyester molecule chain, increases intermolecular active force, can play to a certain extent creep resisting effect.
2, the super low shrinkage industrial yarn of the creep resistant polyester of gained of the present invention, the fluorine-containing bisphenol A type epoxy resin of its end-capping reagent can play the effect of a chain extension simultaneously, can increase the relative molecular mass of polyester, improves the creep-resistant property of polyester.
3, the super low shrinkage industrial yarn of the creep resistant polyester of gained of the present invention, by fluorine-containing bisphenol A type epoxy resin, carry out blocking modification, can partly eliminate the end carboxyl in polyester molecule, again due to the introducing of silicon atom, fluorine atom, can make polyester hydrophobic, refuse water, improve the hydrolytic resistance of polyester.
4, the super low shrinkage industrial yarn of the creep resistant polyester of gained of the present invention, has huge prospect in plastics package, waterproof fabrics, rope, hawser and ocean with fields such as fibers, has expanded range of application.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The super low shrinkage industrial yarn of a kind of creep resistant polyester of the present invention, be by the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling make; Described creep resistant polyester refers to the polyester of fluoro epoxide end-blocking gained for the part macromolecular chain of polyester, and described end-blocking refers to one end end-blocking and/or the two ends sealed to macromolecular chain, and its molecular structural formula is respectively:
One end end-blocking,
Two ends sealed,
Wherein,
m=80～100，
n=10～20。
The super low shrinkage industrial yarn of a kind of creep resistant polyester as above, line density deviation ratio≤1.5% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength >=7.0cN/dtex, fracture strength CV value≤2.5%, extension at break is 20.0 ± 1.5%, extension at break CV value≤7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9 ± 0.25%.
Embodiment 1
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.5% 15mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 16h; Then cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 5mol/L sodium hydroxide solution of 30% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 10h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.06% is as catalyst, in temperature, is to carry out blending reaction under 180 ℃ and the mixing time condition that is 30min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PET polyester that is 0.6dL/g by inherent viscosity is by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 270 ℃, the time is 5min; Described fluorine-containing bisphenol A type epoxy resin addition is the 0.5wt% of PET polyester; The PET polyester slice that the method for described solid phase polycondensation is is 0.6dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PET section bring up to 0.9dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 290 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; The described oil applying rate oiling is 0.4wt%; The speed of described coiling is 2600m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 2
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 2.0% 10mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3mol/L sodium hydroxide solution of 40% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.10% is as catalyst, in temperature, is to carry out blending reaction under 150 ℃ and the mixing time condition that is 40min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PTT polyester that is 0.7dL/g by inherent viscosity is by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 290 ℃, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of PTT polyester; The PTT polyester slice that the method for described solid phase polycondensation is is 0.7dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PTT section bring up to 0.9dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 320 ℃; Described to be cooled to lateral blowing cooling, and temperature is 30 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; The described oil applying rate oiling is 0.8wt%; The speed of described coiling is 3400m/min.
The line density deviation ratio 1.5% of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 21.5%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 2.15%.
Embodiment 3
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.8% 12mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 17h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 4mol/L sodium hydroxide solution of 35% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 13h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.08% is as catalyst, in temperature, is to carry out blending reaction under 170 ℃ and the mixing time condition that is 35min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that the PET polyester that is 0.6dL/g by inherent viscosity and inherent viscosity are 0.7dL/g mixes by the weight ratio of 1:1, by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 280 ℃, the time is 4min; The addition of described fluorine-containing bisphenol A type epoxy resin is the 3wt% of described PET, PBT polyester quality sum; The method of described solid phase polycondensation is by PET, PBT polyester hybrid slicing, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 0.9dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 300 ℃; Described to be cooled to lateral blowing cooling, and temperature is 25 ℃, and relative humidity is 65%%, and wind speed is 0.6m/s; The described oil applying rate oiling is 0.6wt%; The speed of described coiling is 3000m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 18.5%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.65%.
Embodiment 4
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.5% 15mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 16h; Then cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 5mol/L sodium hydroxide solution of 30% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 10h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.06% is as catalyst, in temperature, is to carry out blending reaction under 180 ℃ and the mixing time condition that is 30min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PTT polyester that the PET polyester that is 0.65dL/g by inherent viscosity and inherent viscosity are 0.8dL/g mixes by the weight ratio of 1:1, by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 280 ℃, the time is 4min; The addition of described fluorine-containing bisphenol A type epoxy resin is the 4wt% of described PET, PTT polyester quality sum; The method of described solid phase polycondensation is by PET, PTT polyester hybrid slicing, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 1.1dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 300 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiling is 0.4wt%; The speed of described coiling is 2800m/min.
The line density deviation ratio 1.3 of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 5
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 2.0% 10mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3mol/L sodium hydroxide solution of 40% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.10% is as catalyst, in temperature, is to carry out blending reaction under 150 ℃ and the mixing time condition that is 40min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that the PTT polyester that the PET polyester that is 0.7dL/g by inherent viscosity, inherent viscosity are 0.9dL/g and inherent viscosity are 0.9dL/g mixes by the weight ratio of 1:1:1, by solid phase polycondensation tackify, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 290 ℃, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin is the 1.5wt% of described PET, PTT, PBT polyester quality sum; The method of described solid phase polycondensation is by PET, PTT, PBT polyester hybrid slicing, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 1.3dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 320 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiling is 0.4wt%; The speed of described coiling is 3400m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 20.0%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 6
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.8% 12mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 17h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 4mol/L sodium hydroxide solution of 35% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 13h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.08% is as catalyst, in temperature, is to carry out blending reaction under 170 ℃ and the mixing time condition that is 35min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that the PTT polyester that the PET polyester that is 0.6dL/g by inherent viscosity, inherent viscosity are 0.8dL/g and inherent viscosity are 0.8dL/g mixes by the weight ratio of 1:1:1, by solid phase polycondensation tackify, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 285 ℃, the time is 4min; Described fluorine-containing bisphenol A type epoxy resin is the 1.5wt% of described PET, PTT, PBT polyester quality sum; The method of described solid phase polycondensation is by PET, PTT, PBT polyester hybrid slicing, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 0.9dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 290 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiling is 0.6wt%; The speed of described coiling is 3200m/min.
The line density deviation ratio 1.3 of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 7
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.5% 15mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 16h; Then cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 5mol/L sodium hydroxide solution of 30% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 10h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.06% is as catalyst, in temperature, is to carry out blending reaction under 180 ℃ and the mixing time condition that is 30min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that the PET polyester that is 0.7dL/g by inherent viscosity and inherent viscosity are 0.7dL/g mixes by the weight ratio of 1:1, by solid phase polycondensation tackify, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain the high sticky section of creep resistant polyester described in described creep resistant; Blending reaction condition: temperature is 270 ℃, the time is 5min; The addition of described fluorine-containing bisphenol A type epoxy resin is the 4wt% of described PET, PTT polyester quality sum; The method of described solid phase polycondensation is by PET, PTT polyester hybrid slicing, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 0.9dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 320 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiling is 0.8wt%; The speed of described coiling is 2600m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 20.0%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 8
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 2.0% 10mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3mol/L sodium hydroxide solution of 40% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.10% is as catalyst, in temperature, is to carry out blending reaction under 150 ℃ and the mixing time condition that is 40min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PET polyester that is 0.7dL/g by inherent viscosity is by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 290 ℃, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 0.5wt% of PET polyester; The PET polyester slice that the method for described solid phase polycondensation is is 0.7dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PET section bring up to 1.3dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 300 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; The described oil applying rate oiling is 0.6wt%; The speed of described coiling is 2800m/min.
The line density deviation ratio 1.3 of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 9
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.8% 12mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 17h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 4mol/L sodium hydroxide solution of 35% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 13h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.08% is as catalyst, in temperature, is to carry out blending reaction under 170 ℃ and the mixing time condition that is 35min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PTT polyester that is 0.9dL/g by inherent viscosity is by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 270 ℃, the time is 5min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of PTT polyester; The PTT polyester slice that the method for described solid phase polycondensation is is 0.9dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PTT section bring up to 1.3dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 310 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiling is 0.8wt%; The speed of described coiling is 3400m/min.
The line density deviation ratio 1.5% of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 20.0%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 10
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.5% 15mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 16h; Then cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 5mol/L sodium hydroxide solution of 30% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 10h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.06% is as catalyst, in temperature, is to carry out blending reaction under 180 ℃ and the mixing time condition that is 30min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PET polyester that is 0.65dL/g by inherent viscosity is by solid phase polycondensation tackify, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and dicyclohexylcarbodiimide and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 270 ℃, the time is 5min; Described fluorine-containing bisphenol A type epoxy resin addition is the 0.5wt% of PET polyester; The addition of described dicyclohexylcarbodiimide is the 0.1wt% of PET polyester; The PET polyester slice that the method for described solid phase polycondensation is is 0.65dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PET section bring up to 1.0dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 300 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; The described oil applying rate oiling is 0.6wt%; The speed of described coiling is 2800m/min.
The line density deviation ratio 1.3 of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 11
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 2.0% 10mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3mol/L sodium hydroxide solution of 40% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.10% is as catalyst, in temperature, is to carry out blending reaction under 150 ℃ and the mixing time condition that is 40min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PTT polyester that is 0.8dL/g by inherent viscosity is by solid phase polycondensation tackify, and then, with fluorine-containing bisphenol A type epoxy resin and N, N'-DIC carries out blending reaction and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 290 ℃, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of the high sticky section of described creep resistant polyester; Described N, N'-DIC addition is the 1wt% of PTT polyester; The PTT polyester slice that the method for described solid phase polycondensation is is 0.8dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PTT section bring up to 1.1dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 300 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; The described oil applying rate oiling is 0.6wt%; The speed of described coiling is 2800m/min.
The line density deviation ratio 1.3 of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 12
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 2.0% 10mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3mol/L sodium hydroxide solution of 40% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.10% is as catalyst, in temperature, is to carry out blending reaction under 150 ℃ and the mixing time condition that is 40min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that is 0.7dL/g by inherent viscosity is by solid phase polycondensation tackify, and then, with fluorine-containing bisphenol A type epoxy resin, N, N'-DIC carries out blending reaction and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 290 ℃, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of the high sticky section of described creep resistant polyester; Described N, N'-DIC addition is the 1wt% of PBT polyester; The PBT polyester slice that the method for described solid phase polycondensation is is 0.7dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PBT section bring up to 0.9dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 320 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiling is 0.4wt%; The speed of described coiling is 3400m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 20.0%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 13
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 1.8% 12mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 17h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 4mol/L sodium hydroxide solution of 35% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 13h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.08% is as catalyst, in temperature, is to carry out blending reaction under 170 ℃ and the mixing time condition that is 35min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that is 0.9dL/g by inherent viscosity is by solid phase polycondensation tackify, and then, with fluorine-containing bisphenol A type epoxy resin, N, N'-DIC carries out blending reaction and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 270 ℃, the time is 5min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of PBT polyester; Described N, N'-DIC addition is the 1wt% of PBT polyester; The PBT polyester slice that the method for described solid phase polycondensation is is 0.9dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PBT section bring up to 1.3dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 320 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiling is 0.4wt%; The speed of described coiling is 3400m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, extension at break is 20.0%, extension at break CV value 7.0%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Embodiment 14
4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 2.0% 10mol/L sodium hydroxide solution of biphenol quality, at ambient temperature stirring reaction 18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3mol/L sodium hydroxide solution of 40% use natrium carbonicum calcinatum of biphenol quality, at ambient temperature stirring reaction 15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.10% is as catalyst, in temperature, is to carry out blending reaction under 150 ℃ and the mixing time condition that is 40min, obtains described fluorine-containing bisphenol A type epoxy resin.
The preparation of the high sticky section of creep resistant polyester:
The PBT polyester that is 0.8dL/g by inherent viscosity is by solid phase polycondensation tackify, and then, with fluorine-containing bisphenol A type epoxy resin, N, N'-DIC carries out blending reaction and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 290 ℃, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of the high sticky section of described creep resistant polyester; Described N, N'-DIC addition is the 1wt% of PBT polyester; The PBT polyester slice that the method for described solid phase polycondensation is is 0.8dL/g by inherent viscosity, more than being heated to vitrification point, below fusing point, makes the inherent viscosity of PBT section bring up to 1.1dL/g under vacuum condition; Can complete chip drying simultaneously.
The preparation of the super low shrinkage industrial yarn of creep resistant polyester:
By the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester; The described temperature of extruding is 290 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; The described oil applying rate oiling is 0.4wt%; The speed of described coiling is 2600m/min.
The line density deviation ratio 1.3% of the super low shrinkage industrial yarn of gained creep resistant polyester, fracture strength 7.2/dtex, fracture strength CV value 2.0%, extension at break is 20.0%, extension at break CV value 6.5%, the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9%.
Claims (6)
1. a super low shrinkage industrial yarn for creep resistant polyester, is characterized in that: the super low shrinkage industrial yarn of described creep resistant polyester be by the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling make; Described creep resistant polyester refers to the polyester of fluoro epoxide end-blocking gained for the part macromolecular chain of polyester, and described end-blocking refers to one end end-blocking and/or the two ends sealed to macromolecular chain, and its molecular structural formula is respectively:
One end end-blocking,
Two ends sealed,
Wherein,
m=80～100，
n=10～20。
2. the super low shrinkage industrial yarn of a kind of creep resistant polyester according to claim 1, it is characterized in that, line density deviation ratio≤1.5% of the super low shrinkage industrial yarn of described creep resistant polyester, fracture strength >=7.0cN/dtex, fracture strength CV value≤2.5%, extension at break is 20.0 ± 1.5%, extension at break CV value≤7.0%, and the dry-hot shrinkage under the test condition of 177 ℃ and 0.05cN/dtex is 1.9 ± 0.25%.
3. the preparation method of the super low shrinkage industrial yarn of a kind of creep resistant polyester as claimed in claim 1, it is characterized in that by the high sticky section of creep resistant polyester through measuring, extrude, cooling, oil, stretching, HEAT SETTING and coiling step, make the super low shrinkage industrial yarn of creep resistant polyester;
The described temperature of extruding is 290～320 ℃;
Described cooling wind-warm syndrome is 20～30 ℃;
The speed of described coiling is 2600～3400m/min;
The preparation method of the high sticky section of described creep resistant polyester refers to polyester is passed through to solid phase polycondensation tackify, then carries out blending reaction with fluoro epoxide and obtains the high sticky section of described creep resistant polyester; Blending reaction condition: temperature is 270～290 ℃, the time is 3～5min; Described fluoro epoxide addition is 0.5～5wt% of described polyester; The method of described solid phase polycondensation is by described polyester slice, more than being heated to vitrification point, below fusing point, the inherent viscosity of section is improved under vacuum condition, can complete chip drying simultaneously; When described polyester slice is PET section, by solid phase polycondensation tackify, make the inherent viscosity of PET section bring up to 0.9～1.2dL/g; When described polyester slice is PTT section, by solid phase polycondensation tackify, make the inherent viscosity of PTT section bring up to 0.9～1.3dL/g; When described polyester slice is PBT section, by solid phase polycondensation tackify, make the inherent viscosity of PBT section bring up to 0.9～1.3dL/g; When described polyester slice is mixed polyester section, by solid phase polycondensation tackify, make the inherent viscosity of mixed polyester section bring up to 0.9～1.3dL/g;
Described fluoro epoxide refers to fluorine-containing bisphenol A type epoxy resin, and its molecular structural formula is:
N=10～20 wherein;
Described fluorine-containing bisphenol A type epoxy resin is by diphenyl silanediol and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is raw material, adopts stannic chloride to carry out blending reaction as catalyst and makes; Concrete steps are:
Described 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] preparation of biphenol diepoxy propyl ether:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol is with the mixed in molar ratio of 4:1, adds 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] 10～15mol/L sodium hydroxide solution of 1.5～2.0% of biphenol quality, at ambient temperature stirring reaction 16～18h; Cool to room temperature, then add 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] the saturated 3～5mol/L sodium hydroxide solution of 30～40% use natrium carbonicum calcinatums of biphenol quality, at ambient temperature stirring reaction 10～15h; Then use chloroform extraction, gained organic phase is removed to chloroform by steaming and excessive epoxychloropropane obtains thick liquid, joined in absolute ethyl alcohol and be recrystallized, obtain 4,4'-[2,2,2-, tri-fluoro-1-(three fluoro methyl) ethylidene] crystal of biphenol diepoxy propyl ether;
The preparation of described fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] biphenol diepoxy propyl ether is with the mixed in molar ratio of 1:2, adds 4,4'-[2,2,2-tri-fluoro-1-(three fluoro methyl) ethylidene] stannic chloride of biphenol diepoxy propyl ether quality 0.06～0.10% is as catalyst, in temperature, is to carry out blending reaction under 150～180 ℃ and the mixing time condition that is 30～40min, obtains described fluorine-containing bisphenol A type epoxy resin.
4. according to the preparation method of the super low shrinkage industrial yarn of a kind of creep resistant polyester claimed in claim 3, it is characterized in that, described lateral blowing or the ring quenching of being cooled to, temperature is 20 ℃～30 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.
5. according to the preparation method of the super low shrinkage industrial yarn of a kind of creep resistant polyester claimed in claim 3, it is characterized in that, described polyester refer in PET, PTT and PBT one or more mixture or several copolymers.
6. according to the preparation method of the super low shrinkage industrial yarn of a kind of creep resistant polyester described in claim 3 or 5, it is characterized in that, in described polyester, the inherent viscosity of PET is 0.6～0.7dL/g; The inherent viscosity of PTT is 0.7～0.9dL/g; The inherent viscosity of PBT is 0.7～0.9dL/g.
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