CN103526324B - High-strength low-elongation creep-resistant polyester industrial yarn and preparation method - Google Patents
High-strength low-elongation creep-resistant polyester industrial yarn and preparation method Download PDFInfo
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- CN103526324B CN103526324B CN201310478960.4A CN201310478960A CN103526324B CN 103526324 B CN103526324 B CN 103526324B CN 201310478960 A CN201310478960 A CN 201310478960A CN 103526324 B CN103526324 B CN 103526324B
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Abstract
The invention relates to a high-strength low-elongation creep-resistant polyester industrial yarn and a preparation method thereof. The preparation method comprises the preparation of a high-viscosity creep-resistant polyester chip and the preparation of the high-strength low-elongation creep-resistant polyester industrial yarn; polyester is subjected to solid phase polycondensation for viscosifying and then is blended and reacted with a fluorine-containing epoxy compound to obtain the high-viscosity creep-resistant polyester chip; then the high-viscosity creep-resistant polyester chip is subjected to metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength low-elongation creep-resistant polyester industrial yarn. The high-strength low-elongation creep-resistant polyester industrial yarn has certain creep resistance, hydrolysis resistance and performance stability, can be used in a high-temperature high-humidity environment for a long time, and has great prospect in the fields of plastic packaging, waterproof fabrics, ropes, mooring ropes, marine fibers and the like.
Description
Technical field
The present invention relates to industrial yarn of a kind of creep resistant polyester and preparation method thereof, particularly relate to a kind of fluoro epoxide and carry out industrial yarn of the creep resistant polyester of modification and preparation method thereof as end-capping reagent.
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 the linear thermoplastic's polymer realizing industrial applications the earliest, it is widely used in the fields such as plastics package, film and chemical fibre.High-strength low-elongation polyester industrial filament, also known as common standard type polyester industrial yarn, is the large kind of one in polyester industrial yarn.There is high strength, low elongation, high-modulus, dry-hot shrinkage comparatively high.Its good combination property, of many uses, be at present mainly used as tire cord and conveyer belt, the warp of canvas and safety belt for vehicle, conveyer belt.
The molecular chain structure of polyester is the linear macromolecule containing benzene ring structure, the functional group's marshalling on strand, and unbranched, the flexibility of macromolecular chain is poor.Compared with other macromolecular materials, the strand generation slippage of polyester is comparatively difficult, has certain DIMENSIONAL STABILITY.But can creep be there is during long-time use 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 due to the result of long duration of action under lower than the stress of material yield strength.When material over time is in heated condition or the temperature near fusing point, creep can be more violent.The temperature range that the deformation of creep occurs is different because material is different, relevant with its molecular structure.If polyester material, in the process used, larger creep occurs, will cause the instability of its size, form, this will seriously limit the application of polyester material in a lot of field particularly high-strength field of rope.
Improving polyester material creep-resistant property can by following several mode: (1) uses below the vitrification point of material; (2) take various method of modifying, large molecule is occurred crosslinked; (3) macromolecular relative molecular mass is improved; (4) improve macromolecular chain intermolecular forces, comprise chain linked to owner and introduce fragrant heterocycle, polar group or form inierpeneirating network structure etc.
The patent CN200680017951.3 of Patents as Avery Dennison Corp of the U.S. discloses a kind of creep resistant pressure sensitive adhesive product being main component with the aromatic hydrocarbon replaced containing vinyl and conjugated diene block copolymer.Patents if CN200910097866.8 is by adding photosensitizer to polyethylene fiber preliminary treatment, then improves the creep-resistant property of fiber through ultraviolet irradiation.CN201110434278.6 adopts photosensitizer and thermal initiator jointly to cause crosslinked to polyethylene fiber, thus 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 industrial yarn of a kind of creep resistant polyester and preparation method thereof, particularly relate to a kind of fluoro epoxide and carry out industrial yarn of the creep resistant polyester of modification and preparation method thereof as end-capping reagent.The industrial yarn of creep resistant polyester of the present invention adopts creep resistant polyester spinning, described creep resistant polyester carries out blocking modification by using fluoro epoxide 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 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, has huge prospect in fields such as plastics package, waterproof fabrics, rope, hawser and ocean fibers.
The invention provides following technical scheme:
A kind of industrial yarn of creep resistant polyester, be by the sticky section of creep resistant polyester height through measuring, extruding, cool, oil, stretch, HEAT SETTING and winding obtain, the preparation method of the sticky section of described creep resistant polyester height refers to by polyester by solid phase polycondensation thickening, then carries out blending reaction with fluoro epoxide and obtains that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 ~ 290 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity of section is improved, and can complete chip drying simultaneously; When described polyester slice is PET section, by solid phase polycondensation thickening, the inherent viscosity that PET is cut into slices brings up to 0.9 ~ 1.2dL/g; Described creep resistant polyester refers to the polyester of the part macromolecular chain fluoro epoxide end-blocking gained of polyester, and described end-blocking refers to one end end-blocking to macromolecular chain and/or two ends sealed, and its molecular structural formula is respectively:
One end end-blocking,
Two ends sealed,
Wherein,
m＝80～100，
n＝10～20。
The industrial yarn of a kind of creep resistant polyester as above, line density deviation ratio≤1.5% of the industrial yarn of described creep resistant polyester, fracture strength >=8.3cN/dtex, fracture strength value for coefficient of variation≤2.5%, extension at break is 10.0 ± 1.5%, extension at break value for coefficient of variation≤7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0 ± 0.5%.
Described polyester refers to the mixture of one or more in PET, PTT and PBT 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.
The preparation method of the industrial yarn of described creep resistant polyester, be by the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester;
The described temperature extruded is 290 ~ 320 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 30 DEG C;
The described oil applying rate oiled is 0.4 ~ 0.8wt%;
The speed of described winding is 2600 ~ 3200m/min;
Described fluoro epoxide refers to fluorine-containing bisphenol A type epoxy resin, and its molecular structural formula is:
Wherein n=10 ~ 20;
Described fluorine-containing bisphenol A type epoxy resin is raw material by diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers, adopts stannic chloride to carry out blending reaction as catalyst and obtain; Concrete steps are:
The preparation of described 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.5 ~ 2.0% 10 ~ 15mol/L sodium hydroxide solution, stirring reaction 16 ~ 18h at ambient temperature; Cool to room temperature, add 4 again, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 30 ~ 40% the sodium hydroxide solution of 3 ~ 5mol/L, described sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 10 ~ 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of described fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers is with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.06 ~ 0.10% is as catalyst, under temperature is 150 ~ 180 DEG C and mixing time is the condition of 30 ~ 40min, carries out blending reaction, namely obtains described fluorine-containing bisphenol A type epoxy resin.
Described is cooled to lateral blowing or ring quenching, and temperature is 20 DEG C ~ 30 DEG C, and relative humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s.
Bisphenol A type epoxy resin fluorine-containing described in the present invention is by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol is obtained by reacting 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers, gained 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers and diphenyl silanediol react obtained.Contain in described fluorine-containing bisphenol A type epoxy resin
structure, but this structure space steric hindrance is comparatively large, is difficult to the bisphenol A epoxide resin obtaining 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, greatly can 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, the ratio of benzene ring structure in polyester molecule chain can be increased, functional group on strand is arranged more neat, 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, give full play to the effect of fluorine atom, effectively increase intermolecular active force.Polyester after described fluorine-containing bisphenol A type epoxy resin blocking modification, even if having External Force Acting in use, its strand is also difficult to slippage occurs, the deformation of creep is little, DIMENSIONAL STABILITY is fine, can play creep resisting effect to a certain extent, improve the creep-resistant property of polyester better.
Described fluorine-containing bisphenol A type epoxy resin carries out modification as end-capping reagent to polyester, and its epoxy construction contained partly can eliminate the end carboxyl in polyester molecule, controls the growth rate of carboxylic end group concentration, and the degree of effectively controlled hydrolysis speed acceleration.Avoiding problems its long-time phenomenon hydrolysis occurring and occurs macromolecule random chain scission and depolymerization when exposing more than vitrification point, in the environment of contact water; Again because end-capping reagent introduces silicon atom, fluorine atom in macromolecular chain, polyester hydrophobic can be given, refuse the performance of water, improve the hydrolytic resistance of polyester to a certain extent, improve the service life of polyester material in hygrothermal environment.In addition, fluorine-containing bisphenol A type epoxy resin has special epoxy construction, reacts with polyester blend, but does not have the generation of Small molecular as water, avoids polyester and occurs in process of production, from degraded, to make gained polyester have good heat endurance.
Beneficial effect:
1, the industrial yarn of the creep resistant polyester of gained of the present invention, because fluorine atom has strong electronegativity, can form hydrogen bond, increase intermolecular active force between polyester molecule chain, can play creep resisting effect to a certain extent.
2, the 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, improve the creep-resistant property of polyester.
3, the industrial yarn of the creep resistant polyester of gained of the present invention, carry out blocking modification by fluorine-containing bisphenol A type epoxy resin, partly can eliminate the end carboxyl in polyester molecule, again due to the introducing of silicon atom, fluorine atom, polyester hydrophobic can be made, refuse water, improve the hydrolytic resistance of polyester.
4, the industrial yarn of the creep resistant polyester of gained of the present invention, has huge prospect in fields such as plastics package, waterproof fabrics, rope, hawser and ocean fibers, extends range of application.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The industrial yarn of a kind of creep resistant polyester of the present invention, be by the sticky section of creep resistant polyester height through measuring, extruding, cool, oil, stretch, HEAT SETTING and winding obtain; Described creep resistant polyester refers to the polyester of the part macromolecular chain fluoro epoxide end-blocking gained of polyester, and described end-blocking refers to one end end-blocking to macromolecular chain and/or two ends sealed, and its molecular structural formula is respectively:
One end end-blocking,
Two ends sealed,
Wherein,
m＝80～100，
n＝10～20。
The industrial yarn of a kind of creep resistant polyester as above, line density deviation ratio≤1.5% of the industrial yarn of described creep resistant polyester, fracture strength >=8.3cN/dtex, fracture strength value for coefficient of variation≤2.5%, extension at break is 10.0 ± 1.5%, extension at break value for coefficient of variation≤7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0 ± 0.5%.
Embodiment 1
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.5% 15mol/L sodium hydroxide solution, stirring reaction 16h at ambient temperature; Then cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 30% the sodium hydroxide solution of 5mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 10h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.06% as catalyst, under temperature be 180 DEG C and mixing time is the condition of 30min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PET polyester of 0.6dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 DEG C, the time is 5min; Described fluorine-containing bisphenol A type epoxy resin addition is the 0.5wt% of PET polyester; The method of described solid phase polycondensation is the PET polyester slice of 0.6dL/g by inherent viscosity, and be heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity that PET is cut into slices brings up to 0.9dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 290 DEG C; Described is cooled to lateral blowing cooling, and temperature is 20 DEG C, and relative humidity is 70%, and wind speed is 0.4m/s; The described oil applying rate oiled is 0.4wt%; The speed of described winding is 2600m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 2
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 2.0% 10mol/L sodium hydroxide solution, stirring reaction 18h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 40% the sodium hydroxide solution of 3mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.10% as catalyst, under temperature be 150 DEG C and mixing time is the condition of 40min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PTT polyester of 0.7dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 290 DEG C, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of PTT polyester; The method of described solid phase polycondensation is the PTT polyester slice of 0.7dL/g by inherent viscosity, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of PTT slice bring up to 0.9dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 320 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.8m/s; The described oil applying rate oiled is 0.8wt%; The speed of described winding is 3200m/min.
The line density deviation ratio 1.3% of the industrial yarn of gained creep resistant polyester, fracture strength 8.5cN/dtex, fracture strength value for coefficient of variation 2.3%, extension at break is 11.5%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.5%.
Embodiment 3
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.8% 12mol/L sodium hydroxide solution, stirring reaction 17h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 35% the sodium hydroxide solution of 4mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 13h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.08% as catalyst, under temperature be 170 DEG C and mixing time is the condition of 35min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
The PBT polyester of to be the PET polyester of 0.6dL/g and inherent viscosity by inherent viscosity be 0.7dL/g mixes by the weight ratio of 1:1, by solid phase polycondensation thickening, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 280 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 0.9dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 300 DEG C; Described is cooled to lateral blowing cooling, and temperature is 25 DEG C, and relative humidity is 65%, and wind speed is 0.6m/s; The described oil applying rate oiled is 0.6wt%; The speed of described winding is 3000m/min.
The line density deviation ratio 1.5% of the industrial yarn of described creep resistant polyester, fracture strength 8.5cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 8.5%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 9.5%.
Embodiment 4
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.5% 15mol/L sodium hydroxide solution, stirring reaction 16h at ambient temperature; Then cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 30% the sodium hydroxide solution of 5mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 10h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.06% as catalyst, under temperature be 180 DEG C and mixing time is the condition of 30min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
The PTT polyester of to be the PET polyester of 0.65dL/g and inherent viscosity by inherent viscosity be 0.8dL/g mixes by the weight ratio of 1:1, by solid phase polycondensation thickening, then carries out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtains that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 280 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 1.1dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 300 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiled is 0.4wt%; The speed of described winding is 2800m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.3%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.5%.
Embodiment 5
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 2.0% 10mol/L sodium hydroxide solution, stirring reaction 18h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 40% the sodium hydroxide solution of 3mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.10% as catalyst, under temperature be 150 DEG C and mixing time is the condition of 40min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
Be the PET polyester of 0.7dL/g by inherent viscosity, the PBT polyester of inherent viscosity to be the PTT polyester of 0.9dL/g and inherent viscosity be 0.9dL/g mixes by the weight ratio of 1:1:1, by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 290 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 1.3dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 320 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C DEG C, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiled is 0.4wt%; The speed of described winding is 3200m/min.
The line density deviation ratio 1.5% of the industrial yarn of described creep resistant polyester, fracture strength 8.5cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 9.5%.
Embodiment 6
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.8% 12mol/L sodium hydroxide solution, stirring reaction 17h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 35% the sodium hydroxide solution of 4mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 13h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.08% as catalyst, under temperature be 170 DEG C and mixing time is the condition of 35min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
Be the PET polyester of 0.6dL/g by inherent viscosity, the PBT polyester of inherent viscosity to be the PTT polyester of 0.8dL/g and inherent viscosity be 0.8dL/g mixes by the weight ratio of 1:1:1, by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 285 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 0.9dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiled is 0.6wt%; The speed of described winding is 3200m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 7
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.5% 15mol/L sodium hydroxide solution, stirring reaction 16h at ambient temperature; Then cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 30% the sodium hydroxide solution of 5mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 10h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.06% as catalyst, under temperature be 180 DEG C and mixing time is the condition of 30min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
The PBT polyester of to be the PET polyester of 0.7dL/g and inherent viscosity by inherent viscosity be 0.7dL/g mixes by the weight ratio of 1:1, by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and to obtain described in described creep resistant that creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of hybrid slicing bring up to 0.9dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 320 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiled is 0.8wt%; The speed of described winding is 2600m/min.
The line density deviation ratio 1.5% of the industrial yarn of described creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 8
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 2.0% 10mol/L sodium hydroxide solution, stirring reaction 18h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 40% the sodium hydroxide solution of 3mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.10% as catalyst, under temperature be 150 DEG C and mixing time is the condition of 40min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PET polyester of 0.7dL/g by solid phase polycondensation thickening, then with fluorine-containing bisphenol A type epoxy resin
Carry out blending reaction and obtain the sticky section of described creep resistant polyester height; Blending reaction condition: temperature is 290 DEG C, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 0.5wt% of PET polyester; The method of described solid phase polycondensation is the PET polyester slice of 0.7dL/g by inherent viscosity, and be heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity that PET is cut into slices brings up to 1.3dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 300 DEG C; Described is cooled to ring quenching, and temperature is 25 DEG C, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiled is 0.6wt%; The speed of described winding is 2800m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 9
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.8% 12mol/L sodium hydroxide solution, stirring reaction 17h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 35% the sodium hydroxide solution of 4mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 13h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.08% as catalyst, under temperature be 170 DEG C and mixing time is the condition of 35min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PTT polyester of 0.9dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 DEG C, the time is 5min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of PTT polyester; The method of described solid phase polycondensation is the PTT polyester slice of 0.9dL/g by inherent viscosity, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of PTT slice bring up to 1.3dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 310 DEG C; Described is cooled to ring quenching, and temperature is 30 DEG C, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiled is 0.8wt%; The speed of described winding is 3200m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 10
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.5% 15mol/L sodium hydroxide solution, stirring reaction 16h at ambient temperature; Then cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 30% the sodium hydroxide solution of 5mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 10h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.06% as catalyst, under temperature be 180 DEG C and mixing time is the condition of 30min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PET polyester of 0.65dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and dicyclohexylcarbodiimide and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 DEG C, 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 method of described solid phase polycondensation is the PET polyester slice of 0.65dL/g by inherent viscosity, and be heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity that PET is cut into slices brings up to 1.0dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 290 DEG C; Described is cooled to lateral blowing cooling, and temperature is 20 DEG C, and relative humidity is 70%, and wind speed is 0.4m/s; The described oil applying rate oiled is 0.4wt%; The speed of described winding is 2600m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 11
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 2.0% 10mol/L sodium hydroxide solution, stirring reaction 18h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 40% the sodium hydroxide solution of 3mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.10% as catalyst, under temperature be 150 DEG C and mixing time is the condition of 40min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PTT polyester of 0.8dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin and N, N'-DIC and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 290 DEG C, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of the sticky section of described creep resistant polyester height; Described N, N'-DIC addition is the 1wt% of PTT polyester; The method of described solid phase polycondensation is the PTT polyester slice of 0.8dL/g by inherent viscosity, is heated to more than vitrification point under vacuum, below fusing point, makes the inherent viscosity of PTT slice bring up to 1.1dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 320 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.8m/s; The described oil applying rate oiled is 0.8wt%; The speed of described winding is 3200m/min.
The line density deviation ratio 1.3% of the industrial yarn of gained creep resistant polyester, fracture strength 8.5cN/dtex, fracture strength value for coefficient of variation 2.3%, extension at break is 11.5%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.5%.
Embodiment 12
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 2.0% 10mol/L sodium hydroxide solution, stirring reaction 18h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 40% the sodium hydroxide solution of 3mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.10% as catalyst, under temperature be 150 DEG C and mixing time is the condition of 40min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PBT polyester of 0.7dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin, N, N'-DIC and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 290 DEG C, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of the sticky section of described creep resistant polyester height; Described N, N'-DIC addition is the 1wt% of PBT polyester; The method of described solid phase polycondensation be by inherent viscosity be 0.7dL/g PBT polyester section, be heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity that PBT is cut into slices brings up to 0.9dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 300 DEG C; Described is cooled to lateral blowing cooling, and temperature is 25 DEG C, and relative humidity is 65%, and wind speed is 0.6m/s; The described oil applying rate oiled is 0.6wt%; The speed of described winding is 3000m/min.
The line density deviation ratio 1.5% of the industrial yarn of described creep resistant polyester, fracture strength 8.5cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 8.5%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 9.5%.
Embodiment 13
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.8% 12mol/L sodium hydroxide solution, stirring reaction 17h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 35% the sodium hydroxide solution of 4mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 13h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.08% as catalyst, under temperature be 170 DEG C and mixing time is the condition of 35min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PBT polyester of 0.9dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin, N, N'-DIC and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 DEG C, 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 method of described solid phase polycondensation be by inherent viscosity be 0.9dL/g PBT polyester section, be heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity that PBT is cut into slices brings up to 1.3dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 300 DEG C; Described is cooled to ring quenching, and temperature is 25 DEG C, and relative humidity is 65%, and wind speed is 0.4m/s; The described oil applying rate oiled is 0.6wt%; The speed of described winding is 2800m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Embodiment 14
The preparation of 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 2.0% 10mol/L sodium hydroxide solution, stirring reaction 18h at ambient temperature; Cool to room temperature, then add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 40% the sodium hydroxide solution of 3mol/L, sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.10% as catalyst, under temperature be 150 DEG C and mixing time is the condition of 40min, carry out blending reaction, namely obtain described fluorine-containing bisphenol A type epoxy resin.
The preparation of the sticky section of creep resistant polyester height:
By inherent viscosity be the PBT polyester of 0.8dL/g by solid phase polycondensation thickening, then carry out blending reaction with fluorine-containing bisphenol A type epoxy resin, N, N'-DIC and obtain that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 290 DEG C, the time is 3min; Described fluorine-containing bisphenol A type epoxy resin addition is the 5wt% of the sticky section of described creep resistant polyester height; Described N, N'-DIC addition is the 1wt% of PBT polyester; The method of described solid phase polycondensation be by inherent viscosity be 0.8dL/g PBT polyester section, be heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity that PBT is cut into slices brings up to 1.1dL/g; Chip drying can be completed simultaneously.
The preparation of the industrial yarn of creep resistant polyester:
By the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtain the industrial yarn of creep resistant polyester; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, and relative humidity is 65%, and wind speed is 0.8m/s; The described oil applying rate oiled is 0.6wt%; The speed of described winding is 3200m/min.
The line density deviation ratio 1.5% of the industrial yarn of gained creep resistant polyester, fracture strength 8.3cN/dtex, fracture strength value for coefficient of variation 2.5%, extension at break is 10.0%, extension at break value for coefficient of variation 7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0%.
Claims (4)
1. the industrial yarn of a creep resistant polyester, it is characterized in that: the industrial yarn of described creep resistant polyester be by the sticky section of creep resistant polyester height through measuring, extruding, cool, oil, stretch, HEAT SETTING and winding obtain, the preparation method of the sticky section of described creep resistant polyester height refers to by polyester by solid phase polycondensation thickening, then carries out blending reaction with fluoro epoxide and obtains that described creep resistant polyester height is sticky cuts into slices; Blending reaction condition: temperature is 270 ~ 290 DEG C, 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, is heated to more than vitrification point under vacuum, below fusing point, the inherent viscosity of section is improved, and can complete chip drying simultaneously; When described polyester slice is PET section, by solid phase polycondensation thickening, the inherent viscosity that PET is cut into slices brings up to 0.9 ~ 1.2dL/g; Described creep resistant polyester refers to the polyester of the part macromolecular chain fluoro epoxide end-blocking gained of polyester, and described end-blocking refers to one end end-blocking to macromolecular chain and/or two ends sealed, and its molecular structural formula is respectively:
One end end-blocking,
Two ends sealed,
Wherein,
m＝80～100，
n＝10～20；
Line density deviation ratio≤1.5% of the industrial yarn of described creep resistant polyester, fracture strength >=8.3cN/dtex, fracture strength value for coefficient of variation≤2.5%, extension at break is 10.0 ± 1.5%, extension at break value for coefficient of variation≤7.0%, the dry-hot shrinkage at 177 DEG C and under the test condition of 0.05cN/dtex is 10.0 ± 0.5%.
2. the industrial yarn of a kind of creep resistant polyester according to claim 1, is characterized in that, in described polyester, the inherent viscosity of PET is 0.6 ~ 0.7dL/g.
3. the preparation method of the industrial yarn of a kind of creep resistant polyester according to claim 1, to is characterized in that by the sticky section of creep resistant polyester height through measure, extruding, cool, oil, stretch, HEAT SETTING and winding steps, obtains the industrial yarn of creep resistant polyester;
The described temperature extruded is 290 ~ 320 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 30 DEG C;
The described oil applying rate oiled is 0.4 ~ 0.8wt%;
The speed of described winding is 2600 ~ 3200m/min;
Described fluoro epoxide refers to fluorine-containing bisphenol A type epoxy resin, and its molecular structural formula is:
Wherein n=10 ~ 20;
Described fluorine-containing bisphenol A type epoxy resin is raw material by diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers, adopts stannic chloride to carry out blending reaction as catalyst and obtain; Concrete steps are:
The preparation of described 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers:
In nitrogen atmosphere, by epoxychloropropane and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol with the mixed in molar ratio of 4:1, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 1.5 ~ 2.0% 10 ~ 15mol/L sodium hydroxide solution, stirring reaction 16 ~ 18h at ambient temperature; Cool to room temperature, add 4 again, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol quality 30 ~ 40% the sodium hydroxide solution of 3 ~ 5mol/L, described sodium hydroxide solution is with the saturated solution of natrium carbonicum calcinatum, stirring reaction 10 ~ 15h at ambient temperature; Then chloroform extraction is used, by gained organic phase by steaming except chloroform and excessive epoxychloropropane obtain thick liquid, joined in absolute ethyl alcohol and be recrystallized, namely 4 are obtained, 4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] crystal of biphenol bisglycidyl ethers;
The preparation of described fluorine-containing bisphenol A type epoxy resin:
By diphenyl silanediol and 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] biphenol bisglycidyl ethers is with the mixed in molar ratio of 1:2, add 4,4'-[2,2,2-tri-fluoro-1-(trifluoromethy) ethylidene] stannic chloride of biphenol bisglycidyl ethers quality 0.06 ~ 0.10% is as catalyst, under temperature is 150 ~ 180 DEG C and mixing time is the condition of 30 ~ 40min, carries out blending reaction, namely obtains described fluorine-containing bisphenol A type epoxy resin.
4. the preparation method of the industrial yarn of a kind of creep resistant polyester according to claim 3, is characterized in that, described is cooled to lateral blowing or ring quenching, and temperature is 20 DEG C ~ 30 DEG C, and relative humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s.
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| CN102336898A (en) * | 2010-07-16 | 2012-02-01 | 东丽纤维研究所（中国）有限公司 | Copolyester, its production method and application |
| CN102498156A (en) * | 2009-09-16 | 2012-06-13 | 3M创新有限公司 | Epoxy-functionalized perfluoropolyether polyurethanes |
| CN102787378A (en) * | 2012-09-03 | 2012-11-21 | 江苏恒力化纤股份有限公司 | Manufacturing method for high-strength low-elongation type dacron industrial yarn |
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| JP2005325504A (en) * | 2004-04-13 | 2005-11-24 | Kaneka Corp | Flame-retardant polyester artificial hair |
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| CN102498156A (en) * | 2009-09-16 | 2012-06-13 | 3M创新有限公司 | Epoxy-functionalized perfluoropolyether polyurethanes |
| CN102336898A (en) * | 2010-07-16 | 2012-02-01 | 东丽纤维研究所（中国）有限公司 | Copolyester, its production method and application |
| CN102787378A (en) * | 2012-09-03 | 2012-11-21 | 江苏恒力化纤股份有限公司 | Manufacturing method for high-strength low-elongation type dacron industrial yarn |
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