CN103469349B - Fluorine-containing PTT random copolyester FDY fiber and preparation method thereof - Google Patents
Fluorine-containing PTT random copolyester FDY fiber and preparation method thereof Download PDFInfo
- Publication number
- CN103469349B CN103469349B CN201310445115.7A CN201310445115A CN103469349B CN 103469349 B CN103469349 B CN 103469349B CN 201310445115 A CN201310445115 A CN 201310445115A CN 103469349 B CN103469349 B CN 103469349B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- tpa
- terephthalic acid
- containing ptt
- fdy fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to fluorine-containing PTT random copolyester FDY fiber and a preparation method thereof. The preparation method comprises preparation of fluorine-containing PTT random copolyester melt and preparation of fluorine-containing PTT random copolyester FDY fiber. In the preparation technology of fluorine-containing PTT random copolyester melt, tetrafluoroterephthalic acid, terephthalic acid and 1, 3-propanediol are taken as raw materials, and an inhibitor is added for preparation of fluorine-containing PTT random copolyester melt; and melt is subjected to screw melt extrusion, cooling, oiling, stretching and reeling for preparation of fluorine-containing PTT random copolyester FDY fiber. The prepared fluorine-containing PTT random copolyester FDY fiber has breaking tenacity of 3-5 cN/dex and elongation at break of 18-45%. Due to the introduction of fluorine atoms, the copolyester FDY fiber is improved in superhydrophobicity, hydrophobicity, oleophobicity and antifouling performance, and has great application prospect in manufacture of waterproof garments, dirt-resistant working clothes and working clothes in certain special industries.
Description
Technical field
The present invention relates to a kind of fluorine-containing PTT random copolyester FDY fiber and preparation method thereof, particularly relate to fluorine-containing PTT random copolyester FDY fiber that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.
Background technology
Polyester (PET) is one of the most widely used synthetic high polymer of the current mankind; PET has just been synthesized the forties as far back as twentieth century; and find that it has excellent performance, and be widely used in the fields such as weaving, packaging, health care, automobile, electronic apparatus, security protection, environmental protection.In spinning process, introduce stretching action, the undrawn yarn with high-orientation and crystalline medium degree can be obtained, be called fullly drawn yarn (FDY), be i.e. FDY.FDY is mainly used as the warp thread of water jet looms fabric, and the conventional fullly drawn yarn (FDY) having terylene and polyamide fibre, all belongs to chemical-fibres filaments.The smooth softness of FDY fabric feel, is often used in and weaves silk-like fabric, has been widely used in clothes and family spin.
Polytrimethylene terephthalate (PTT) is a kind of new polyester macromolecular material having development prospect of new research and development after polyethylene terephthalate (PET) and mutual-phenenyl two acid bromide two alcohol ester (PBT), within 1998, is chosen as one of six large petrochemical industry new products by the U.S..Compared with PET, PBT, PTT has better elasticity, DIMENSIONAL STABILITY and dyeability etc.There is the multiple good characteristics such as uvioresistant, anti-internal stress, low water absorbable, low electrostatic and good biological degradability, reusable edible simultaneously, be therefore widely used in the fields such as carpet industry, dress materials, engineering plastics.
Along with the progress of society, the raising of living standards of the people, needs more and more higher to differential, the functionalization of polyester fiber.What therefore the modification of polyester also became particularly is important, and polyester modification object, except being optimized conventional polyester performance, mainly gives new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, antifouling deodorization etc.At present, the main new varieties of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity polyester, anti-soil polyester etc.
At present, by introducing fluorine atom in the polymer, thus improving the surface property of material, as hydro-oleophobicity and soil resistance etc., and giving polyester material various function.Because fluoropolymer has low-surface-energy, low-friction coefficient and non-adhesiveness usually, dust dirt is difficult to the characteristics such as attachment, and therefore the anti-soil ABRASION RESISTANCE of fluoropolymer is good.And current fluoropolymer is based on fluoroolefin base polymer (such as: polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, ethene ~ TFE copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. then relatively lags behind.
Many scholars are studied fluorochemical modified poly ester, and achieve certain achievement.The mode of current fluorochemical modified poly ester mainly by adding fluorine-containing end-capping reagent, or adds the fluorochemical such as Fluorinated dihydric alcohol, fluorine-containing binary acid and carrys out modified poly ester as Third monomer.Wang Zhong just waits (Wang Zhonggang, Li Wenjuan, by the industry that continues. fluorine-containing polyester with low-surface-energy and preparation method thereof: China, CN 101139434A, 2008.) adding of fluorine-containing end-capping reagent is adopted, dimethyl isophthalate and butanediol adopt ester-interchange method, add fluorine-containing end-capping reagent N ~ ethoxy perfluoro-octanoyl amine, have prepared the low and polyester material that contaminated resistance is good of fluorinated volume.Hu Juan (Hu Juan. the MOLECULE DESIGN of fluorine-containing polyester and photoresist waveguide material and performance study [D]. Master's thesis, Jilin: Jilin University, 2007.) principle of MOLECULE DESIGN is utilized, by adding the mode of Fluorinated dihydric alcohol copolymerization, paraphthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol ternary polymerization are synthesized the polyester of novel high fluorinated volume.This polyester has excellent performance and is applied to optical waveguide material.(the Q Z Zhu such as Qingzeng Zhu, C C Han.Synthesis andcrystalization behaviors of highly fluorinated aromatic polyesters [J] .Polymer 2007 (48): 3624 ~ 3631.) by adding the mode modified poly ester of fluorine-containing binary acid copolymerization, 2,3,4,5 ~ ptfe phthalate modification polyethylene glycol phthalate, the crystal property of polyester improves.
But the polyester these being contained fluorine element is applied in weaving and packaging material certain limitation, subject matter is that the molecular weight of polyesters containing fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art mainly gives its water proof anti-soil function by the fluorine-containing Final finishing mode of fabric at present, and the maximum shortcoming of these class methods is to be difficult to solve the problems such as ageing, durability and ABRASION RESISTANCE, and wastes time and energy.
Therefore, developing fluorine-containing polyester fiber for weaving and the modification of super-hydrophobic, hydrophobic and oil repellent, antifouling property of packaging material, important theory significance and using value will be had.
Summary of the invention
The invention provides a kind of fluorine-containing PTT random copolyester FDY fiber and preparation method thereof, fluorine-containing PTT random copolyester FDY fiber particularly providing a kind of benzene ring hydrogen to replaced by fluorine and preparation method thereof.Fluorine-containing PTT random copolyester FDY fiber of the present invention adopts the spinning of fluorine-containing PTT atactic polyester, described fluorine-containing PTT atactic polyester is by terephthalic acid (TPA), tetrafluoro terephthalic acid (TPA) and propylene glycol, through the fluorine-containing PTT atactic polyester that esterification and polycondensation reaction obtain.By copolymerization method, hydrophobic antifouling modification is carried out to polyester, fundamentally can solve ageing, the problem such as durability and ABRASION RESISTANCE of hydrophobic antifouling polyester, also can well solve this kind of problem that wastes time and energy.
The invention provides following technical scheme:
A kind of fluorine-containing PTT random copolyester FDY fiber directly extrudes or make section by fluorine-containing PTT atactic polyester melt to melt extrude through screw rod, cool, oil, stretch and reel obtained; Described fluorine-containing PTT atactic polyester is the fluorine-containing PTT atactic polyester obtained by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and 1,3-PD copolymerization; Described tetrafluoro terephthalic acid (TPA) has following structural formula:
The fluorine-containing PTT random copolyester FDY fiber of one as above, the fracture strength 3 ~ 5cN/dex of described fluorine-containing PTT random copolyester FDY fiber; Elongation at break is 18 ~ 45%.
Present invention also offers a kind of preparation method of fluorine-containing PTT random copolyester FDY fiber, is by fluorine-containing PTT atactic polyester melt-stoichiometry, obtained fluorine-containing PTT random copolyester FDY fiber of extruding, cool, oil, stretch and reel.
The described temperature extruded is 275 ~ 290 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 30 DEG C;
The described oil applying rate oiled is 0.42 ~ 1.5wt%;
The draft speed of the first hot-rolling of described stretching is 2000 ~ 2500m/min; The draft speed of the second hot-rolling is 4000 ~ 6000m/min, and its heat setting temperature is 135 ~ 155 DEG C;
The speed of described winding is 3950 ~ 5950m/min;
Described is cooled to lateral blowing or ring quenching, and temperature is 20 DEG C ~ 30 DEG C, and humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s.
The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight:
Component A: mineral oil 40-60 part;
B component: polyoxyethylene ether 20-35 part;
Component C: phosphate kalium salt 5-10 part;
Component D: cithrol 8-16 part;
Component E: sodium alkyl sulfonate 1-5 part;
Component F: perfluoroalkyl acrylate 1-5 part.
In described fluorine-containing polyester FDY fiber finish, component A mineral oil is smooth agent: this material is 9
#~ 17
#mineral oil in one.Mineral oil has good heat resistance, has good compatibility with other component, and it has and oils evenly, and the feature that film strength is high, effectively can also reduce the coefficient of friction of fiber and metal, and the cohesive force of increase fiber, is conducive to boundling.
In described fluorine-containing polyester FDY fiber finish, B component polyoxyethylene ether is emulsifying agent: this material is the one in isomery ten alcohol polyoxyethylene ether, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol, tridecanol polyoxyethylene ether, tetradecyl alchohol polyoxyethylene ether, hexadecanol polyoxyethylene ether and polyoxyethylene octadecanol.This component has good heat resistance, and its hydrophobic grouping and emulsified thing have good compatibility, can also keep larger hydrophily simultaneously, whole finish can be made to form uniform and stable emulsion.
In described fluorine-containing polyester FDY fiber finish, component C phosphate kalium salt is antistatic additive: this material is the one in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and isomerous tridecanol polyoxyethylene ether phosphate kalium salt.Adopt anionic antistatic agent, can surface hydrophilic be realized, be beneficial to the displacement of finish and slurry.The heat resistance of phosphate kalium salt is relatively good, good antistatic behaviour, can the antistatic effect of fortifying fibre, is conducive to the boundling of fiber.
In described fluorine-containing polyester FDY fiber finish, component D cithrol is collecting agent: this material is the one in polyethylene glycol stearate monoesters, polyethylene glycol stearate, polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester.Containing ester group in the large molecule of fluorine-containing polyester fiber, selected fatty acid ester, has better adhesive force with it.And its flatness is excellent, starching and heat resistance well, can meet the technological requirement of FDY finish.Collecting agent add the convergence and flatness that can improve finish, meanwhile, synergy can be played with phosphate kalium salt antistatic additive, the antistatic effect of fortifying fibre, the cohesive force of fiber be improved, is conducive to the boundling in fiber process.
In described fluorine-containing polyester FDY fiber finish, component E sodium alkyl sulfonate is additive: this material is the one in dodecyl sodium sulfate, pentadecyl sulfonic acid sodium and sodium cetanesulfonate.Sodium alkyl sulfonate add the penetrating power that can improve finish, make finish to be attached on tow in the short period of time uniformly, effectively can reduce the appearance of lousiness, broken end.
In described fluorine-containing polyester FDY fiber finish, component F perfluoroalkyl acrylate is additive: this material is the one in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethylmethyl acrylate and perfluorooctylethyl group methacrylate.Its objective is the surface tension in order to suitably reduce finish, being easy to form uniform continuous oil film.Perfluoroalkyl and acrylate have lower surface energy, and appropriate interpolation can lower the surface tension of finish, the wettability of finish and penetrability is greatly increased, is easy to the wetting and spreading at fiber, form uniform oil film.
The main implementation procedure of described fluorine-containing polyester FDY fiber finish: by B component, component C, component D, component E and the mixing of component F normal temperature, stir 20-30 minute, and then mixture is joined in component A, temperature controls as 40-55 DEG C, stir 0.5 ~ 2h, the FDY finish that described fluorine-containing polyester FDY fiber oil performance is excellent can be obtained, during use, be configured to the emulsion of 8 ~ 10% with pure water.
Described fluorine-containing PTT atactic polyester melt refers to the fluorine-containing PTT atactic polyester after melting, and the preparation method of described fluorine-containing PTT atactic polyester is divided into esterification and polycondensation reaction two step; Concrete steps are:
The esterification stage: employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out under normal pressure ~ 0.3MPa, and temperature controls at 250 ~ 270 DEG C, and the reaction time is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
The polycondensation reaction stage comprises polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The polycondensation reaction low vacuum stage:
In esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260 ~ 270 DEG C, and the reaction time is 30 ~ 50 minutes.
Polycondensation reaction high vacuum stage of Fig:
Above-mentioned material is after the low vacuum stage, continue to vacuumize, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 260 ~ 275 DEG C, in 3 ~ 4 hours reaction time, to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PTT atactic polyester as above, described starting monomer is terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO).Its mol ratio is: PTA:FPTA=1:0.02 ~ 1; (PTA+FPTA): PDO=1:1.3 ~ 2.
The preparation method of a kind of fluorine-containing PTT atactic polyester as above, described catalyst is selected from the one in butyl titanate-magnesium acetate, metatitanic acid four isopropyl esters-magnesium acetate, tetraethyl titanate-magnesium acetate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01% ~ 0.03% of tetrafluoro terephthalic acid (TPA) used and terephthalic acid (TPA) gross weight.
The preparation method of a kind of fluorine-containing PTT atactic polyester as above, described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate, Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.03% of tetrafluoro terephthalic acid (TPA) used and terephthalic acid (TPA) gross weight.
The preparation method of a kind of fluorine-containing PTT atactic polyester as above, when tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) mol ratio are 0.5 ~ 1:1, described esterification also adds the one in magnesia, silica, calcium oxide, zinc oxide and manganese oxide, as inhibitor, addition is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.There is fluorine atom in the phenyl ring due to dicarboxylic acids used, the electronegativity of fluorine atom is large, in the conjugation of esterification stage fluorine atom, the acidity of dicarboxylic acids is strengthened, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, reaction speed is accelerated, and reaction speed increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation reaction, particularly generate the end-cap product of alkene and aldehyde, constrain the increase of molecular weight of product; From experimental result, if do not add inhibitor, the molecular weight of polyesters of synthesis is on the low side, can not meet the demand of spinning and film forming; The speed added for controlling the esterification stage of inhibitor, decreases side reaction, improves the molecular weight of product, make to meet spinning requirement.
Usually, it is the hydrogen ion that ionized out by the dicarboxylic acids used catalyst as esterification in polyester esterification process, carry out self-catalyzed reaction, by regulating the temperature of esterification, pressure and the micromolecular speed ejecting its esterification of control, but the prerequisite of carrying out esterification under certain reaction temperature and pressure, just will can carry out esterification.When temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thus affect follow-up technique.If the Small molecular in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, due to the conjugation of fluorine, at esterification stage fluorine atom, the acidity of dicarboxylic acids is strengthened, cause the activity of carboxyl in dicarboxylic acids to increase, reaction speed is accelerated, and side reaction increases simultaneously, be difficult to control, and then affect the growth of molecular weight of product, therefore add inhibitor, namely by selecting metal oxide used to regulate.Described metal oxide can dissociate by the following two kinds mode:
Here M is metal ion, if the electronegativity of M is quite large, has stronger attraction, O-H key so just can be made to weaken to the duplet of oxonium ion, is conducive to reacting dissociation; On the contrary, if the electronegativity of M is little, so just alkali center will be generated.M-O-H is similar with amphoteric compound, when there being alkaline matter to exist, reacting and the mode by acid dissociation being carried out; And when acidic materials exist, then undertaken by the mode of alkali formula ionization.The M-O of back reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in O ion then relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, and intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and metal ion electronegativity is less, and negative charge density is larger.So, acidity and the alkalescence of metal oxide have just all connected with the electronegativity of metal ion, and the oxide that the electronegativity of metal ion is large is mainly acid, and what electronegativity was little is then alkalescence.
In the esterification stage of the present invention, reaction end reaches theoretical value more than 90% by the water quantity of distillate produced actual in esterification to be grasped.Theoretical value is the quantity of distillate by gained water during chemical equation complete reaction.Because esterification is originally as reversible reaction, moreover raw material has residual in conveyance conduit, and along with the carrying out reacted, the viscosity of system increases, and the shipwreck that esterification can be caused to produce is therefrom to discharge.
In polycondensation reaction high vacuum stage of Fig of the present invention, the numerical value that reaction end reaches setting by reactor beater motor power and in-line viscometer calculation value is grasped.The setting numerical value of its reactor beater motor power of different devices and in-line viscometer calculation value is not necessarily identical, and the determination of setting numerical value can by obtaining the analysis of polyester slice.
Fracture strength 3 ~ the 5cN/dex of the novel fluorine PTT random copolyester FDY fiber of gained of the present invention; Elongation at break is 18 ~ 45%.Due to the introducing of fluorine atom, improve super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, at waterproof garment, in the Work Clothes manufacture of the Work Clothes born dirty and some special industry, have huge prospect.
Beneficial effect:
1, gained novel fluorine PTT random copolyester FDY fiber contain fluorine atoms; due to the strong electronegativity of fluorine; high C ~ F bond energy and make final obtained copolyesters FDY fiber have well heat-resisting, ageing-resistant to the shielding protection effect of carbochain, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction, also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, extend range of application.
2, the smooth softness of gained novel fluorine PTT random copolyester FDY fiber feel, is applicable to weave silk-like fabric.
3, gained novel fluorine PTT random copolyester FDY fiber introduces fluorine atom by adopting, thus has hydrophobic antifouling characteristic.
4, gained novel fluorine PTT random copolyester FDY fiber is by adopting modification by copolymerization, fundamentally solves the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.
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.
A kind of fluorine-containing PTT random copolyester FDY fiber, be by fluorine-containing PTT atactic polyester melt-stoichiometry, extrude, cool, oil, stretch and reel obtained; Described fluorine-containing PTT atactic polyester is the fluorine-containing PTT atactic polyester obtained by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and 1,3-PD copolymerization; Described tetrafluoro terephthalic acid (TPA) has following structural formula:
The fluorine-containing PTT random copolyester FDY fiber of one as above, the fracture strength 3 ~ 5cN/dex of described fluorine-containing PTT random copolyester FDY fiber; Elongation at break is 18 ~ 45%.
Embodiment 1
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.02; (PTA+FPTA): PDO=1:1.3.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out under 0.3MPa, and temperature controls at 270 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst butyl titanate-magnesium acetate of 0.01% of dicarboxylic acids weight used and 0.01% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature controls at 270 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 4 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Directly measured by described fluorine polyester fondant to extrude, cool, oil, to stretch and coiling and molding obtains FDY fiber; The described temperature extruded is 275 DEG C; Described is cooled to lateral blowing cooling, and temperature is 20 DEG C DEG C, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 20 parts of poly-isomery ten alcohol polyoxyethylene ether, 10 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 16 parts of polyethylene glycol stearate monoesters, 4 parts of dodecyl sodium sulfates, 5 parts of perfluoro butyl ethyl propylene acid esters normal temperature mixing, stir 20min.Said mixture is joined 45 part 9
#in mineral oil, temperature controls at 55 DEG C, stirs 1h, can obtain the FDY finish of function admirable, and adding water when finish uses is made into the emulsion that solid content is 8wt%; The described oil applying rate oiled is 0.42wt%; The draft speed of the first hot-rolling of described stretching is 2000m/min; The draft speed of the second hot-rolling is 4000m/min, and its heat setting temperature is 135 DEG C; The speed of described winding is 3950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3cN/dex; Elongation at break is 45%.
Embodiment 2
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.06; (PTA+FPTA): PDO=1:1.4.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out under 0.3MPa, and temperature controls at 265 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst metatitanic acid four isopropyl esters-magnesium acetate of 0.02% of dicarboxylic acids weight used and 0.02% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature controls at 270 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 4 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
The preparation method of preparation FDY:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to lateral blowing cooling, and temperature is 25 DEG C, and humidity is 70%, and wind speed is 0.6m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 35 parts of isomerous tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 14 parts of polyethylene glycol stearates, 1 part of pentadecyl sulfonic acid sodium, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined 40 part 10
#in mineral oil, temperature controls at 40 DEG C, stirs 0.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2500m/min; The draft speed of the second hot-rolling is 6000m/min, and its heat setting temperature is 155 DEG C; The speed of described winding is 5950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 3
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.1; (PTA+FPTA): PDO=1:1.6.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at 0.2 mpa, and temperature controls at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the catalyst tetraethyl titanate-magnesium acetate of 0.03% of dicarboxylic acids weight used and 0.03% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature controls at 265 DEG C, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and reaction temperature controls at 270 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 280 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, and humidity is 60%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 25 parts of laurate polyoxyethylene ether, 7 part of ten tetracosanol phosphate kalium salt, 11 parts of polyethylene glycol lauric acid monoesters, 5 parts of sodium cetanesulfonates, 2 parts of perfluorooctylethyl group acrylate normal temperature mixing, stir 20min.Said mixture is joined 50 part 11
#in mineral oil, temperature controls at 55 DEG C, stirs 2h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.96%; The draft speed of the first hot-rolling of described stretching is 2200m/min; The draft speed of the second hot-rolling is 4500m/min, and its heat setting temperature is 140 DEG C; The speed of described winding is 4450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3.5cN/dex; Elongation at break is 40%.
Embodiment 4
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.2; (PTA+FPTA): PDO=1:1.8.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at 0.2 mpa, and temperature controls at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent Trimethyl phosphite of the sub-tin of catalyst acetic acid of 0.03% of dicarboxylic acids weight used and 0.03% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature controls at 260 DEG C, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and reaction temperature controls at 270 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 280 DEG C; Described is cooled to lateral blowing cooling, and temperature is 20 DEG C, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 23 parts of tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 8 parts of polyethylene glycol laurate dibasic acid esters, 3 parts of pentadecyl sulfonic acid sodium, 1 part of perfluoro butyl ethylmethyl acrylate normal temperature mixing, stir 30min.Said mixture is joined 60 part 12
#in mineral oil, temperature controls at 50 DEG C, stirs 1.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2300m/min; The draft speed of the second hot-rolling is 5000m/min, and its heat setting temperature is 145 DEG C; The speed of described winding is 4950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 4cN/dex; Elongation at break is 30%.
Embodiment 5
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.4; (PTA+FPTA): PDO=1:1.8.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at ambient pressure, and temperature controls at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst dibutyltin diacetate of 0.02% of dicarboxylic acids weight used and 0.02% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature controls at 270 DEG C, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 60Pa, and reaction temperature controls at 265 DEG C, 3 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, and humidity is 70%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 30 parts of polyoxyethylene octadecanols, 8 part of ten tetracosanol phosphate kalium salt, 12 parts of polyethylene glycol oleic acid monoesters, 2 parts of pentadecyl sulfonic acid sodium, 3 parts of perfluoro hexyl ethylmethyl acrylate normal temperature mixing, stir 30min.By said mixture and join 45 part 14
#in mineral oil, temperature controls at 55 DEG C, stirs 50 minutes, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling of described stretching is 2400m/min; The draft speed of the second hot-rolling is 5500m/min, and its heat setting temperature is 150 DEG C; The speed of described winding is 5450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 6
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA) (PTA), 1,3-PD (PDO) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.5; (PTA+FPTA): PDO=1:2.0.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at 0.2 mpa, and temperature controls at 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst butyl titanate-magnesium acetate of 0.03% of dicarboxylic acids weight used and 0.03% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 200Pa, temperature controls at 255 DEG C, and the reaction time is 30 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and reaction temperature controls at 260 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PTT atactic polyester section.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 275 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C DEG C, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 32 parts of hexadecanol polyoxyethylene ether, 6 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 14 parts of polyethylene glycol Glycol Oleic Acid Ester, 3 parts of sodium cetanesulfonates, 5 parts of perfluorooctylethyl group methacrylate normal temperature mixing, stir 20min.Said mixture is joined 40 part 15
#in mineral oil, temperature controls at 40 DEG C, stirs 1.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling stretched is 2400m/min; The draft speed of the second hot-rolling is 4000m/min, and its heat setting temperature is 135 DEG C; The speed of described winding is 3950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3cN/dex; Elongation at break is 45%.
Embodiment 7
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (TPA) (PTA), 1, ammediol (PDO) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the magnesia of 0.05% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.5; (PTA+FPTA): PDO=1:1.3.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out under 0.3MPa, and temperature controls at 270 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst butyl titanate-magnesium acetate of 0.01% of dicarboxylic acids weight used and 0.01% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature controls at 270 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 4 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PTT atactic polyester section.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 25 DEG C, and humidity is 70%, and wind speed is 0.6m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 28 parts of tetradecyl alchohol polyoxyethylene ether, 9 part of ten tetracosanol phosphate kalium salt, 13 parts of polyethylene glycol stearates, 4 parts of dodecyl sodium sulfates, 2 parts of perfluoro butyl ethylmethyl acrylate normal temperature mixing, stir 20min.Said mixture is joined 44 part 16
#in mineral oil, temperature controls at 45 DEG C, stirs 75 minutes, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2500m/min; The draft speed of the second hot-rolling is 6000m/min, and its heat setting temperature is 155 DEG C; The speed of described winding is 5950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 8
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (TPA) (PTA), 1, ammediol (PDO) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the silica of 0.02% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.6; (PTA+FPTA): PDO=1:1.4.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out under 0.3MPa, and temperature controls at 265 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst metatitanic acid four isopropyl esters-magnesium acetate of 0.02% of dicarboxylic acids weight used and 0.02% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature controls at 270 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 4 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PTT atactic polyester section.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 285 DEG C; Described is cooled to ring quenching, and temperature is 30 DEG C, and humidity is 60%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, getting 24 parts is ten tetracosanol polyoxyethylene ether, 5 parts of isomerous tridecanol phosphate kalium salts, 8 parts of polyethylene glycol laurate dibasic acid esters, 4 parts of sodium cetanesulfonates, 4 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stirs 20min.Said mixture is joined 55 part 17
#in mineral oil, temperature controls at 50 DEG C, stirs 1.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.96%; The draft speed of the first hot-rolling of described stretching is 2200m/min; The draft speed of the second hot-rolling is 4500m/min, and its heat setting temperature is 140 DEG C; The speed of described winding is 4450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3.5cN/dex; Elongation at break is 40%.
Embodiment 9
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (TPA) (PTA), 1, ammediol (PDO) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the calcium oxide of 0.03% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.7; (PTA+FPTA): PDO=1:1.6.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at 0.2 mpa, and temperature controls at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the catalyst tetraethyl titanate-magnesium acetate of 0.03% of dicarboxylic acids weight used and 0.03% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature controls at 265 DEG C, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and reaction temperature controls at 270 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PTT atactic polyester section.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 280 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 20 parts of poly-isomery ten alcohol polyoxyethylene ether, 10 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 16 parts of polyethylene glycol stearate monoesters, 4 parts of dodecyl sodium sulfates, 5 parts of perfluoro butyl ethyl propylene acid esters normal temperature mixing, stir 20min.Said mixture is joined 45 part 9
#in mineral oil, temperature controls at 55 DEG C, stirs 1h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2300m/min; The draft speed of the second hot-rolling is 5000m/min, and its heat setting temperature is 145 DEG C; The speed of described winding is 4950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 4cN/dex; Elongation at break is 30%.
Embodiment 10
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (TPA) (PTA), 1, ammediol (PDO) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the zinc oxide of 0.04% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:0.8; (PTA+FPTA): PDO=1:1.8.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at 0.2 mpa, and temperature controls at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent Trimethyl phosphite of the sub-tin of catalyst acetic acid of 0.03% of dicarboxylic acids weight used and 0.03% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature controls at 260 DEG C, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and reaction temperature controls at 270 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PTT atactic polyester section.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, and humidity is 65%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 35 parts of isomerous tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 14 parts of polyethylene glycol stearates, 1 part of pentadecyl sulfonic acid sodium, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined 40 part 10
#in mineral oil, temperature controls at 40 DEG C, stirs 0.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling of described stretching is 2400m/min; The draft speed of the second hot-rolling is 5500m/min, and its heat setting temperature is 150 DEG C; The speed of described winding is 5450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 11
A preparation method for fluorine-containing PTT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt terephthalic acid (TPA) (PTA), 1, ammediol (PDO) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the manganese oxide of 0.01% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), 1,3-PD (PDO) mol ratio are: PTA:FPTA=1:1; (PTA+FPTA): PDO=1:2.Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out at ambient pressure, and temperature controls at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst dibutyltin diacetate of 0.02% of dicarboxylic acids weight used and 0.02% of dicarboxylic acids weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature controls at 270 DEG C, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 60Pa, and reaction temperature controls at 265 DEG C, 3 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing PTT atactic polyester section.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, and humidity is 65%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 35 parts of isomerous tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 14 parts of polyethylene glycol stearates, 1 part of pentadecyl sulfonic acid sodium, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined 40 part 10
#in mineral oil, temperature controls at 40 DEG C, stirs 0.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling of described stretching is 2400m/min; The draft speed of the second hot-rolling is 5500m/min, and its heat setting temperature is 150 DEG C; The speed of described winding is 5450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Claims (10)
1. a fluorine-containing PTT random copolyester FDY fiber, is characterized in that: described fluorine-containing PTT random copolyester FDY fiber is through measuring, extruding, cool, oil, stretch and reel obtained by fluorine-containing PTT atactic polyester melt; Described fluorine-containing PTT atactic polyester is the fluorine-containing PTT atactic polyester obtained by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and 1,3-PD copolymerization; Described tetrafluoro terephthalic acid (TPA) has following structural formula:
2. the fluorine-containing PTT random copolyester FDY fiber of one according to claim 1, is characterized in that, the fracture strength 3 ~ 5cN/dex of described fluorine-containing PTT random copolyester FDY fiber; Elongation at break is 18 ~ 45%.
3. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber as claimed in claim 1, it is characterized in that: by fluorine-containing PTT atactic polyester melt through measuring, extruding, cool, oil, stretch and winding steps, obtained fluorine-containing PTT random copolyester FDY fiber;
The described temperature extruded is 275 ~ 290 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 30 DEG C;
The described oil applying rate oiled is 0.42 ~ 1.5wt%;
The draft speed of the first hot-rolling of described stretching is 2000 ~ 2500m/min; The draft speed of the second hot-rolling is 4000 ~ 6000m/min, and its heat setting temperature is 135 ~ 155 DEG C;
The speed of described winding is 3950 ~ 5950m/min;
The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight:
Component A: mineral oil 40-60 part;
B component: polyoxyethylene ether 20-35 part;
Component C: phosphate kalium salt 5-10 part;
Component D: cithrol 8-16 part;
Component E: sodium alkyl sulfonate 1-5 part;
Component F: perfluoroalkyl acrylate 1-5 part;
The preparation of finish:
By B component, component C, component D, component E and the mixing of component F normal temperature, stir 20-30 minute, and then mixture is joined in component A, temperature controls as 40-55 DEG C, stir 0.5 ~ 2h, can obtain fluorine-containing polyester FDY fiber finish, adding water when finish uses is made into the emulsion that solid content is 8 ~ 10wt%;
Described fluorine-containing PTT atactic polyester melt refers to the fluorine-containing PTT atactic polyester after melting, and the preparation method of described fluorine-containing PTT atactic polyester is divided into esterification and polycondensation reaction two step; Concrete steps are:
Described esterification:
Employing terephthalic acid (TPA), 1,3-PD are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) carries out esterification after being made into uniform sizing material as Third monomer; Without the need to extra catalyst in esterification, pressurize in nitrogen atmosphere, Stress control carries out under normal pressure ~ 0.3MPa, and temperature controls at 250 ~ 270 DEG C, and the reaction time is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, in described esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction time is 30 ~ 50 minutes;
Described polycondensation reaction high vacuum stage of Fig, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 260 ~ 275 DEG C, 3 ~ 4 hours reaction time.
4. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber 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 humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s.
5. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber according to claim 3, it is characterized in that, the mol ratio of terephthalic acid (TPA) and tetrafluoro terephthalic acid (TPA) is 1:0.02 ~ 1, and the total amount of terephthalic acid (TPA) and tetrafluoro terephthalic acid (TPA) and the mol ratio of 1.3-propylene glycol are 1:1.3 ~ 2.
6. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber according to claim 3, it is characterized in that, described catalyst is selected from the one in butyl titanate-magnesium acetate, tetraisopropyl titanate-magnesium acetate, tetraethyl titanate-magnesium acetate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01% ~ 0.03% of tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.
7. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber according to claim 3, it is characterized in that, described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate, Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.03% of tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.
8. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber according to claim 3, it is characterized in that, when tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) mol ratio are 0.5 ~ 1:1, described esterification also adds magnesia, silica, calcium oxide, zinc oxide or manganese oxide, and addition is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.
9. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber according to claim 3, is characterized in that, described fluorine-containing PTT atactic polyester melt is directly obtained by polymerization or cut into slices by fluorine-containing PTT atactic polyester to obtain through screw rod melting.
10. the preparation method of a kind of fluorine-containing PTT random copolyester FDY fiber according to claim 3, is characterized in that, described mineral oil is 9
#~ 17
#mineral oil in one; Described polyoxyethylene ether is the one in isomery ten alcohol polyoxyethylene ether, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol, tridecanol polyoxyethylene ether, tetradecyl alchohol polyoxyethylene ether, hexadecanol polyoxyethylene ether and polyoxyethylene octadecanol; Described phosphate kalium salt is the one in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and isomerous tridecanol polyoxyethylene ether phosphate kalium salt; Described cithrol is the one in polyethylene glycol stearate monoesters, polyethylene glycol stearate, polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester; Described sodium alkyl sulfonate is the one in dodecyl sodium sulfate, pentadecyl sulfonic acid sodium and sodium cetanesulfonate; Described perfluoroalkyl acrylate is the one in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethylmethyl acrylate and perfluorooctylethyl group methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310445115.7A CN103469349B (en) | 2013-09-26 | 2013-09-26 | Fluorine-containing PTT random copolyester FDY fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310445115.7A CN103469349B (en) | 2013-09-26 | 2013-09-26 | Fluorine-containing PTT random copolyester FDY fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103469349A CN103469349A (en) | 2013-12-25 |
| CN103469349B true CN103469349B (en) | 2015-07-01 |
Family
ID=49794382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310445115.7A Active CN103469349B (en) | 2013-09-26 | 2013-09-26 | Fluorine-containing PTT random copolyester FDY fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103469349B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725911B (en) * | 2020-12-22 | 2022-06-28 | 南通新帝克单丝科技股份有限公司 | High-dpf polyamide industrial yarn for electronic components and production method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257194A (en) * | 2008-10-17 | 2011-11-23 | 英威达技术有限公司 | Bicomponent spandex |
| CN103282569A (en) * | 2010-12-28 | 2013-09-04 | 纳幕尔杜邦公司 | A fabric prepared from fluorinated polyester blend yarns |
-
2013
- 2013-09-26 CN CN201310445115.7A patent/CN103469349B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257194A (en) * | 2008-10-17 | 2011-11-23 | 英威达技术有限公司 | Bicomponent spandex |
| CN103282569A (en) * | 2010-12-28 | 2013-09-04 | 纳幕尔杜邦公司 | A fabric prepared from fluorinated polyester blend yarns |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and crystallization behaviors of highly fluorinated aromatic polyesters;Qingzeng Zhu,et al.;《polymer》;20070424(第48期);3624-3631 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103469349A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103469335B (en) | Wear-resisting industrial yarn of a kind of fluorine polyester high-strength and preparation method thereof | |
| CN103469339B (en) | A kind of preparation method of fluorine polyester DTY fiber | |
| CN103526322B (en) | Fluorine-containing PET (polyethylene terephthalate)-PTT (polytrimethylene terephthalate) copolyester FDY (fully drawn yarn) fiber and preparation method thereof | |
| CN103469344B (en) | Fluorine-containing PTT-PBT copolyester POY fiber and preparation method thereof | |
| CN103469340B (en) | Fluorine-containing PBT random co-polyester DTY fiber and method for preparing same | |
| CN103510184B (en) | Fluorine-containing PET-PBT (polyethylene terephthalate- polybutylene terephthalate) copolyester DTY (draw texturing yarn) fiber and preparation method thereof | |
| CN103469360B (en) | A kind of preparation method of fluorine-containing PBT-PET core-skin composite fiber | |
| CN103524722B (en) | A kind of fluorine-containing PBT atactic polyester and preparation method thereof | |
| CN103524723A (en) | Fluorine polyester and preparation method thereof | |
| CN103469348B (en) | Fluorine-containing PBT polyester DTY fiber and preparation method thereof | |
| CN109853072A (en) | A kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament | |
| CN103510182B (en) | A kind of fluorine-containing PTT polyester FDY fiber and preparation method thereof | |
| CN103526335B (en) | A kind of preparation method of fluorine-containing PBT-PBT core-skin composite fiber | |
| CN103469338B (en) | A kind of preparation method of fluorine polyester POY fiber | |
| CN103469350B (en) | A kind of preparation method of fluorine polyester FDY fiber | |
| CN103469349B (en) | Fluorine-containing PTT random copolyester FDY fiber and preparation method thereof | |
| CN103469336B (en) | A kind of preparation method of fluorine-containing PTT polyester POY fiber | |
| CN103469334B (en) | A kind of preparation method of fluorine-containing PBT polyester POY fiber | |
| CN103469355B (en) | A kind of preparation method of fluorine-containing PET-PET blended fiber | |
| CN103588964B (en) | A kind of preparation method of fluorine-containing atactic polyester | |
| CN103469337B (en) | Preparation method of fluorine-containing random copolyester polyester pre-oriented yarn (POY) fibers | |
| CN103469356B (en) | A kind of preparation method of fluorine-containing PET-PET core-skin composite fiber | |
| CN103469358B (en) | A kind of preparation method of fluorine-containing PTT-PTT core-skin composite fiber | |
| CN103469361B (en) | A kind of preparation method of fluorine-containing PBT-PET blended fiber | |
| CN103469359B (en) | A kind of preparation method of fluorine-containing PTT-PET core-skin composite fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210527 Address after: No. 58, Yingbin Avenue, Xiadu community, Pingnan County, Guigang City, Guangxi Zhuang Autonomous Region, 537300 Patentee after: Li Weizhi Address before: 215228 industrial concentration area, Shengze Town, Wujiang City, Suzhou City, Jiangsu Province Patentee before: JIANGSU LIXIN CHEMICAL FIBER TECHNOLOGY Co.,Ltd. |