CN103789866B

CN103789866B - A kind of preparation method of polyhydroxy polycarboxylic ester fiber

Info

Publication number: CN103789866B
Application number: CN201410038072.5A
Authority: CN
Inventors: 王华平; 吉鹏; 王朝生; 陈向玲; 江振林; 汤廉; 刘红飞; 史原
Original assignee: Donghua University
Current assignee: Donghua University
Priority date: 2014-01-26
Filing date: 2014-01-26
Publication date: 2016-03-30
Anticipated expiration: 2034-01-26
Also published as: CN103789866A

Abstract

The present invention relates to a kind of preparation method of polyhydroxy polycarboxylic ester fiber.By dihydroxylic alcohols and polyhydroxy-alcohol according to certain mixed in molar ratio, utilize esterification stage by stage, the first Esterification Stage acid is micro-excessive, ensures that the monomer participating in esterification ability lower in polyalcohol fully reacts, is linked in polyester molecule chain.Supplement the end carboxyl of dihydroxylic alcohols to copolyesters in the second Esterification Stage to control, then prepare polyol polyester through polycondensation reaction.Utilizing polyhydroxy functional groups can introduce inorganic functional powder carries out function modified, and polyhydroxy can play package action, improves the performance that is uniformly dispersed of particle; Polyhydroxy avtive spot, can give fiber and carry out in a mild condition dyeing and having good dyeability.The polyol polyester of preparation, through melt spinning, finally prepares polyhydroxy polycarboxylic ester fiber and can be widely used in preparing moisture absorbing and sweat releasing, antistatic fibre, as close-fitting fabric, also may be used for high color fastness fiber product.

Description

A kind of preparation method of polyhydroxy polycarboxylic ester fiber

Technical field

The invention belongs to polyester technical field, relate to a kind of preparation method of polyhydroxy polycarboxylic ester fiber, particularly relate to the first esterification excessive acid and the second Esterification Stage alcohol is excessive, then through preparation method that is circular or the shaping polyhydroxy polycarboxylic ester fiber of shaped spinneret melt spinning.

Background technology

Polyester fiber is the kind be most widely used in current synthetic fiber, and polyester molecule structural arrangement is regular, and degree of crystallinity is high, this gives the good mechanical property of polyester fiber, wrinkle resistance etc.Polyester construction also also exists shortcoming while its excellent properties of imparting: strand arrangement closely, lacks polar functional group, result in its hygroscopicity very poor, and moisture is difficult to diffusion in the polyester.Under standard environment, polyester fiber regain is only 0.4%, and has a large amount of polar functional group hydroxyls in cotton fiber molecular structure, and fibre moisture regain rate reaches 7.5% ~ 8.0%.Method for this reason by chemical modification introduces polar functional group hydroxyl in the polyester to improve its moisture pick-up properties.But multistep esterification technique is all excessive with dihydroxylic alcohols in traditional polyester preparation process, intermediate product is all with hydroxy-end capped, the carboxyl that can react further is few, the modification by copolymerization monomer polyhydroxy-alcohol added for improving polyester moisture pick-up properties is difficult to participate in esterification, only exist in polyester system with micromolecular form, do not reach the effect introducing polyhydroxy modification.The standby method of this polyester constrains further developing of polyester technology in a lot of occasion.

Such as:

Hydrophilicity, lacks polar functional group in polyester fiber strand, and under standard environment (20 DEG C, relative humidity is 65%), regain is only 0.4%, and hygroscopicity is poor, wears use as the field of taking, and easily produces feeling of oppression and heat.And containing a large amount of hydroxy functional groups in natural fabric cotton fiber strand, under identical humiture, regain reaches 7.5 ~ 8%, has good hygroscopicity.

Antistatic property, lacks polar functional group in polyester fiber strand, easily produces the gathering of electrostatic, causes the suction-operated to dust, cause stain resistance to decline.

Dyeability, the arrangement of conventional polyester fiber strand is regular, and degree of crystallinity is high.Dye molecule is difficult to enter crystalline region, and the dyeing of fiber needs to carry out under high-temperature and high-pressure conditions, and lacks reactive functional groups in strand, and the dyeing of polyester fiber is more difficult reaches engrain effect, and COLOR FASTNESS also can constantly decline in time.In cotton fiber strand, reactive functionality hydroxyl can react with REACTIVE DYES, and dye molecule and hydroxyl form firmly covalent bond, has high color fastness Color.

Uvioresistant performance, it is the important content of chemical fibre area research that preparation has uvioresistant performance modified polyester fiber always.When cutting into slices for uvioresistant polyester by monomer in situ polymerization legal system, maximum difficult point how to make uvioresistant inorganic particle equably in dispersion polymerization systems.The polyalcohol introduced in polymerization improves system apparent viscosity, and inorganic particle can wrap up by a large amount of hydroxyls, prevents the agglomeration between the sedimentation of inorganic particle and powder, improves dispersing uniformity, thus strengthens uvioresistant performance.

Owing to lacking necessary polar functional group in polyester molecule as hydroxyl etc., the arrangement of polyester molecule chain structure is regular, and hygroscopicity is poor, easily produces sultry discomfort, easily produces electrostatic phenomenon, accumulate dust; Dyeing simultaneously needs to carry out at high temperature under high pressure, consumes a large amount of energy consumptions; Polyester apparent viscosity is low, and lacking hydroxyl cannot wrap up inorganic particle, easily reunites, thus affect polyester property between uvioresistant inorganic particle.

In existing copolymerization technique, the modification of the increase polar functional group of polyester is all to introduce polyhydroxy-alcohol as sorbierite, pentaerythrite, polyethylene glycol etc. in polymerization usually.First obtain polyol polyester through polycondensation again through over-churning, wherein system is that alcohol is excessive all the time, and in guarantee system, binary acid fully reacts.But it is inconsistent that esterification activity participated in by the multicomponent alcohol introduced, most of alcohol and binary acid are participated in the ability of reacting and are not so good as dihydroxylic alcohols, in system, dihydroxylic alcohols is excessive, after acid reaction terminates, the polyalcohol of non-complete reaction is there is in system, not only significantly do not increase the hydroxyl quantity of polyester, and these responseless polyalcohols cause serious adverse effect to copolyesters spinning moulding, also create the waste of raw material simultaneously.

Summary of the invention

The object of this invention is to provide a kind of preparation method of polyhydroxy polycarboxylic ester fiber, particularly provide a kind of first esterification acid micro-excessive and preparation method of the polyhydroxy polycarboxylic ester fiber that class alcohol is excessive.Inconsistent due to the activity of polyalcohol and acid reaction, the preparation method of a kind of polyhydroxy polycarboxylic ester fiber of the present invention, by the first Esterification Stage excessive acid, ensure that the monomer participating in esterification ability lower in polyalcohol fully reacts, be linked in polyester molecule chain, the copolyesters of formation sequence even structure distribution.First esterification stage carboxyl functional group is micro-excessive, provides the activation point of reaction.Can react with polyester modification monomer further, as two terminal hydroxy groups or amido functional group polyethylene glycols or the large molecule of polyetheramine; The dihydroxylic alcohols supplemented in the second Esterification Stage can regulate and control the end carboxyl of copolyesters, and the content of carboxyl end group of copolyesters is controlled in stable scope, then through circular or shaped spinneret melt spinning is shaping prepares polyhydroxy flexible polyester fiber.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber of the present invention, comprise the first esterification, the second esterification and polycondensation reaction successively, concrete steps are:

(1) first esterification:

Dihydroxylic alcohols and polyhydroxy-alcohol are configured to polyols blend according to mol ratio 98 ~ 99.5:0.5 ~ 2;

Glycol section polyalcohol total material amount more than 90% ensure that in the product prepared, polyester component accounts for major part, retain mechanical property, the stability of polyester excellence itself.The row that dihydroxylic alcohols and polyhydroxy-alcohol esterification advanced mixes, and can ensure that polyalcohol medium-high viscosity alcohol composition is dispersed in dihydroxylic alcohols.

Binary acid is added according to the hydroxy functional group mol ratio 1.02 ~ 1.10:1 of binary acid carboxyl functional group and described polyols blend;

The preparation of conventional polyol polyester is all excessive with alcohol, ensures acid fully reaction.But inconsistent due to the activity of dihydroxylic alcohols and other polyalcohol and acid reaction, most of alcohol and binary acid are participated in the ability of reacting and are not so good as dihydroxylic alcohols, and in system, dihydroxylic alcohols is excessive, after acid reaction terminates, there is the polyalcohol of non-complete reaction in system.The present invention, in the first esterification stage, utilizes binary acid carboxyl functional group micro-excessive, ensures that active inconsistent polyols blend can fully react.

Described polyols blend and described binary acid are added reaction kettle of the esterification and carries out the first esterification, the pressure of described first esterification is 0.01 ~ 0.5MPa, and the temperature of reaction is 230 ~ 260 DEG C, and the time of reaction is 0.5 ~ 3h; When the first esterification water yield reaches 90 ~ 95% of theoretical water yield, complete the first esterification;

First esterification controls can ensure that the composition that polyalcohol mid-boiling point is lower is avoided always at the top of reactor under stress at certain pressure, realizes contacting with material participating in reacting.Judge esterification yield with esterification water yield, simply can operate.Control that the first esterification water yield reaches theoretical 90 ~ 95%, the inconsistent polyalcohol of the activity now in system can fully react, and avoids there is free polyalcohol.

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary dihydroxylic alcohols, and the pressure of reaction is 0.1 ~ 0.5Mpa, and the temperature of reaction is 240 ~ 270 DEG C, and the time of reaction is 0.5 ~ 2h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The material amount of supplementing dihydroxylic alcohols is that 10.5% ~ 16.3% of polyol hydroxyls total mole number is added in the first esterification, makes the mol ratio of total alcoholic extract hydroxyl group and carboxylic acid functional in the first esterification and the second esterification be 1.10 ~ 1.30:1;

First esterification terminates supplementary dihydroxylic alcohols, is reacted completely by binary acid excessive for the first Esterification Stage, makes whole Esterification Stage alcohol and the mol ratio of acid maintain alcohol micro-excessive.The spinning of end carboxyl on rear road of polyester has important impact.Conventional polyester carboxyl value content is 20mol/T, and the first Esterification Stage terminates rear carboxylate with end carboxyl end-blocking, and the dihydroxylic alcohols that the second esterification supplements can continue to react with end carboxyl, thus at the end of the second esterification carboxylate with terminal hydroxy group end-blocking.

(3) finally the mixture of described second esterification is carried out polycondensation reaction, obtain polyester through polycondensation reaction;

The temperature of described polycondensation reaction remains on 260 ~ 280 DEG C, and described polycondensation reaction continues 2 ~ 4h, prepares polyol polyester.

Esterification terminates rear carboxylate and enters polycondensation phase, and polycondensation is divided into low vacuum stage and high vacuum stage of Fig.Low vacuum pressure controls at-50kPa, time 40 ~ 60min, and the low vacuum stage causes vacuum lead to block in order to avoid esterification directly enters high vacuum stage of Fig.Carry out high vacuum stage of Fig after the low vacuum stage terminates, high vacuum pressure controls at-101kPa, and time controling is at 1 ~ 3h.The whole polycondensation phase time is no more than 4.5h.The power of agitator value that polycondensation phase terminates to set with agitator is as discharging foundation.

(4) finally by the polyol polyester of described preparation through circular or shaped spinneret melt spinning is shaping prepares Multifunctional polyester fiber.

As preferred technical scheme:

Dihydroxylic alcohols described in the preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above is more than one in ethylene glycol, propylene glycol, butanediol or pentanediol.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, described polyhydroxy-alcohol is more than one in sorbierite, pentaerythrite or xylitol.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, described binary acid is terephthalic acid (TPA) or terephthalic acid (TPA) and the 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester mixture according to mol ratio 90 ~ 95:10 ~ 5.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, in described step (1): before the first esterification starts, first carries out stirring to pulp by described polyols blend and binary acid, makes fully blended in slurry kettle; And preheating reaction kettle of the esterification, imports material fully blended in slurry kettle when reaction kettle of the esterification internal temperature reaches 200 DEG C ~ 230 DEG C.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, in described step (1): before the first esterification starts, also add catalyst, heat stabilizer and antioxidant; The addition of described catalyst is 100 ~ 500ppm, and radix is the quality of described binary acid; The addition of described heat stabilizer is 0.001 ~ 0.02% of binary acid quality; The addition of described antioxidant is 0.001 ~ 0.03% of binary acid quality.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, described catalyst is Titanium series catalyst and/or antimony-based catalyst; Described Titanium series catalyst is butyl titanate and/or titanium ethylene glycolate; Described antimony-based catalyst is more than one in antimonous oxide, antimony acetate or antimony glycol.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, described heat stabilizer is one of them or its mixture of trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite ester.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, described antioxidant is antioxidant 1010, antioxidant 168 or antioxidant 616 one of them or its mixture.

The preparation method of a kind of polyhydroxy polycarboxylic ester fiber as above, described polyhydroxy polycarboxylic ester fiber is POY, FDY, DTY or staple fibre, and its spinning technique is respectively:

The polyol polyester that step (3) prepares is carried out melt spinning, its staple fiber spinning process is: spinning temperature is 270 ~ 300 DEG C, spinning speed is 800 ~ 1500m/min, and draft temperature is 60 ~ 80 DEG C, and predraft multiplying power is 1.02 ~ 1.10, one stretching ratio is 2.80 ~ 3.20, two road stretching ratios are 1.05 ~ 1.15, then through cutting off, and obtained polyol polyester staple fibre, the fiber number of staple fibre is 0.3 ~ 5dtex, and length is 38mm or 51mm.

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 270 ~ 300 DEG C, and spinning speed is 2000 ~ 3000m/min, and draft temperature is 60 ~ 80 DEG C, and total stretching ratio is 1.5 ~ 5.

Further, POY is after 8 h for equilibration, and respectively through first roller, the Ith hot case, coldplate, PU disc type false twister, the second roller, the nozzle of interlace, the IIth hot case, the 3rd roller, oil tanker, eventually passes Wound-up roller coiling and molding, can be made into polyol polyester DTY.

The wherein linear velocity 200-600m/min of first roller, the linear velocity 500-600m/min of the second roller, the linear velocity 300-600m/min of the 3rd roller, the linear velocity 400-700m/min of Wound-up roller, draw ratio 1.1-1.8, PU disc type false twisting D/Y is than being 1.2-2.5.

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning speed is 3500 ~ 4200m/min, the speed of hot-rolling GR1 is 1100 ~ 1500m/min, temperature is 80 ~ 110 DEG C, the speed of hot-rolling GR2 is 3550 ~ 4280m/min, temperature is 115 ~ 135 DEG C, obtained polyhydroxy flexible polyester FDY filament.

Profile spinneret as above is a kind of in trilobal spinnerets, platypelloid type spinnerets, hollow type spinnerets, cross spinnerets, Y type or " 8 " font spinnerets.

Beneficial effect:

(1) the present invention adopts esterification stage by stage: the first Esterification Stage is excessive acid, and the polyalcohol in guarantee system fully reacts.After completing 90 ~ 95% esterification yields, enter the second Esterification Stage, supplement dihydroxylic alcohols, the end group of regulation and control carboxylate.Esterification technique ensure that the polyalcohol of introducing can fully react stage by stage, the copolyesters of formation sequence even structure distribution.

(2) the present invention first esterification excessive acid system, can ensure that polyalcohol fully reacts, and the waste of minimizing raw material is avoided Small molecular to exist in system simultaneously and caused adverse influence to the spinning moulding of copolyesters.

(3) first stage carboxyl functional group of the present invention is micro-excessive, provides the activation point of reaction.Can react with polyester modification monomer further, as two terminal hydroxy groups or amido functional group polyethylene glycols or the large molecule of polyetheramine.

(4) comonomer polyalcohol of the present invention increases the apparent viscosity of slurry, and can carry out the even particulate dispersion of in-situ polymerization in system by utility inorganic particle, powder wraps up by polyhydroxy, reduces the reunion between inorganic particle.

(5) contain a large amount of polar functional group hydroxyls in the polyol polyester fiber molecule chain that the present invention synthesizes, can react with reactive dyestuff molecule, reaction condition is gentle, reduces energy consumption.The stock-dye degree of depth and COLOR FASTNESS are all significantly improved simultaneously.

Accompanying drawing explanation

Accompanying drawing is the FTIR figure of polyol polyester section

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.

Embodiment 1

A preparation method for polyhydroxy polycarboxylic ester fiber, comprise the first esterification, the second esterification, polycondensation reaction and melt spinning successively shaping, concrete steps are:

(1) first esterification:

Ethylene glycol and sorbierite are configured to polyols blend according to mol ratio 99.5:0.5;

Terephthalic acid (TPA) is added according to the hydroxy functional group mol ratio 1.02:1 of binary acid carboxyl functional group and described polyols blend;

Described polyols blend and described binary acid are added reaction kettle of the esterification and carries out the first esterification, the pressure of described first esterification is 0.01MPa, and the temperature of reaction is 230 DEG C, and the time of reaction is 4h; When the first esterification water yield reaches 95% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary ethylene glycol, and the pressure of reaction is 0.1Mpa, and the temperature of reaction is 240 DEG C, and the time of reaction is 2h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

Supplementary ethylene glycol is 10.5% of the first Esterification Stage polyol hydroxyls total mole number, makes alcohol total in the first esterification and the second esterification be 1.10 ~ 1.30:1 with the mol ratio of acid;

The temperature of described polycondensation reaction remains on 280 DEG C; Described polycondensation reaction continues 2h, prepares polyol polyester;

The Fourier's infrared tester (FTIR) adopting the NEXUS-670 model of Nicolet company of U.S. development is as shown in drawings 500-3500cm at wavelength ^-1test.The FTIR spectrogram of polyol polyester sample can be found out, 3430cm ^-1for-OH the vibration absorption peak introduced in polyalcohol; 2967cm ^-1the bimodal vibration absorption peak representing C-H in polyester at place; At 1716cm ^-1the strong absworption peak at place should be carbonyl (C=O) stretching vibration to be caused; 1400-1600cm ^-1the weak peak at place is the characteristic absorption band spectrum of phenyl ring; At 1246cm ^-1and 1100cm ^-12 wide by force and comparatively absworption peaks at place are that the asymmetric stretching vibration of the C-O-C key in ester causes; 1018cm ^-1and 872cm ^-1the peak at place, on corresponding Isosorbide-5-Nitrae-substituted benzene ring, C-H in-plane deformation vibrates and deformation vibration outside face respectively; At 725cm ^-1narrow and the strong absworption peak at place is that the C-H flexural vibrations in aromatic ring cause.The copolyesters prepared has the characteristic peak of target product.

(4) finally polyhydroxy polycarboxylic ester fiber is prepared by shaping for the polyol polyester melt spinning of described preparation;

Spinning temperature is 300 DEG C, and spinning speed is 1500m/min, and draft temperature is 80 DEG C, predraft multiplying power is 1.02, and one stretching ratio is 2.80, two road stretching ratios is 1.05, obtained polyol polyester staple fibre, the fiber number of staple fibre is 0.3dtex, and length is 38mm.The surface contact angle of fiber is 45 °, regain 2.0%, water absorption rate 250%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 2

(1) first esterification:

Propylene glycol and pentaerythrite are configured to polyols blend according to mol ratio 98:2;

Described polyols blend and described binary acid are added reaction kettle of the esterification and carries out the first esterification, the pressure of described first esterification is 0.01MPa, and the temperature of reaction is 230 DEG C, and the time of reaction is 4h; When the first esterification water yield reaches 90% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary propylene glycol, and the pressure of reaction is 0.1Mpa, and the temperature of reaction is 240 DEG C, and the time of reaction is 1h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

Supplementary propylene glycol is 10.5% of the first Esterification Stage polyol hydroxyls total mole number, makes alcohol total in the first esterification and the second esterification be 1.10 ~ 1.30:1 with the mol ratio of acid;

The temperature of described polycondensation reaction remains on 270 DEG C; Described polycondensation reaction continues 2h, prepares polyol polyester;

Fourier's infrared tester (FTIR) is utilized to be 500-3500cm at wavelength to prepared polyol polyester ^-1test.The FTIR spectrum analysis of polyol polyester sample obtains, 3430cm ^-1for-OH the vibration absorption peak introduced in polyalcohol.

(4) finally polyhydroxy polycarboxylic ester fiber is obtained by shaping for the polyol polyester melt spinning of preparation;

The polyol polyester that step (3) prepares is carried out melt spinning, its spinning technique is: spinning temperature is 290 DEG C, spinning speed is 1500m/min, draft temperature is 80 DEG C, and predraft multiplying power is 1.02, and one stretching ratio is 2.80, two road stretching ratios are 1.05, obtained polyol polyester staple fibre, the fiber number of staple fibre is 0.3dtex, and length is 38mm.The surface contact angle of fiber is 50 °, regain 2.2%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 3

(1) first esterification:

Butanediol and xylitol are configured to polyols blend according to mol ratio 99:1;

Terephthalic acid (TPA) and 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester is added according to the hydroxy functional group mol ratio 1.10:1 of binary acid carboxyl functional group and described polyols blend;

Described terephthalic acid (TPA) mixes according to mol ratio 90:10 with 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester;

Described polyols blend and described binary acid are added reaction kettle of the esterification and carries out the first esterification, the pressure of described first esterification is 0.5MPa, and the temperature of reaction is 260 DEG C, and the time of reaction is 2h; When the first esterification water yield reaches 90% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary butanediol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 270 DEG C, and the time of reaction is 1h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

Supplementary butanediol is 16.3% of the first Esterification Stage polyol hydroxyls total mole number, makes alcohol total in the first esterification and the second esterification be 1.10 ~ 1.30:1 with the mol ratio of acid;

The temperature of described polycondensation reaction remains on 265 DEG C; Described polycondensation reaction continues 2h, prepares polyol polyester;

(4) finally the polyol polyester of preparation is obtained polyhydroxy polycarboxylic ester fiber through hollow spinneret plate melt spinning is shaping;

The polyol polyester that step (3) prepares is carried out melt spinning, its spinning technique is: spinning temperature is 270 DEG C, spinning speed is 800m/min, draft temperature is 60 DEG C, and predraft multiplying power is 1.10, and one stretching ratio is 2.80, two road stretching ratios are 1.15, obtained polyol polyester staple fibre, the fiber number of staple fibre is 5dtex, and length is 38mm.The surface contact angle of fiber is 45 °, regain 2.5%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 4

(1) first esterification:

Ethylene glycol, pentanediol and xylitol are mixed into polyols blend, and wherein, the mol ratio of ethylene glycol and pentanediol is 90:10, and ethylene glycol and pentanediol and xylitol configure according to mol ratio 98:2;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 200 DEG C, material fully blended in slurry kettle is imported, and add the antioxidant 1010 of the butyl titanate of terephthalic acid (TPA) quality 100ppm, the trimethyl phosphate of terephthalic acid (TPA) quality 0.001% and terephthalic acid (TPA) quality 0.001%, carry out the first esterification, the pressure of described first esterification is 0.05MPa, the temperature of reaction is 245 DEG C, and the time of reaction is 3h; When the first esterification water yield reaches 95% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary ethylene glycol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 0.5h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

Supplementary ethylene glycol is 16.3% of the first Esterification Stage polyol hydroxyls total mole number, makes alcohol total in the first esterification and the second esterification be 1.10 ~ 1.30:1 with the mol ratio of acid;

The temperature of described polycondensation reaction remains on 280 DEG C; Described polycondensation reaction continues 4h, prepares polyol polyester;

The polyol polyester that step (3) prepares is carried out melt spinning, its spinning technique is: spinning temperature is 300 DEG C, spinning speed is 800m/min, draft temperature is 80 DEG C, and predraft multiplying power is 1.10, and one stretching ratio is 2.80, two road stretching ratios are 1.15, obtained polyol polyester staple fibre, the fiber number of staple fibre is 5dtex, and length is 51mm.The surface contact angle of fiber is 45 °, regain 2.5%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 5

(1) first esterification:

Ethylene glycol, propylene glycol and sorbierite are mixed into polyols blend, and wherein, the mol ratio of ethylene glycol and propylene glycol is 90:10, and ethylene glycol and propylene glycol and sorbierite configure according to mol ratio 99.5:0.5;

Terephthalic acid (TPA) is added according to the hydroxy functional group mol ratio 1.05:1 of binary acid carboxyl functional group and described polyols blend;

First described polyols blend and terephthalic acid (TPA) are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 200 DEG C, material fully blended in slurry kettle is imported, and add the antioxidant 168 of the titanium ethylene glycolate of terephthalic acid (TPA) quality 100ppm, the alkyl phosphoric acid diester of terephthalic acid (TPA) quality 0.005% and terephthalic acid (TPA) quality 0.005%, carry out the first esterification, the pressure of described first esterification is 0.01MPa, the temperature of reaction is 245 DEG C, and the time of reaction is 3h; When the first esterification water yield reaches 95% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary ethylene glycol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 255 DEG C, and the time of reaction is 0.5h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The temperature of described polycondensation reaction remains on 275 DEG C; Described polycondensation reaction continues 4h, prepares polyol polyester;

(4) finally the polyol polyester of preparation is obtained polyhydroxy polycarboxylic ester fiber through Y type spinneret melt spinning is shaping;

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 300 DEG C, and spinning speed is 2000m/min, and draft temperature is 80 DEG C, and total stretching ratio is 5.The surface contact angle of fiber is 48 °, regain 2.2%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 6

(1) first esterification:

Propylene glycol, butanediol and xylitol, pentaerythrite are mixed into polyols blend, and wherein, the mol ratio of propylene glycol and butanediol is 90:10, and dihydroxylic alcohols and sorbierite, pentaerythrite configure according to mol ratio 99:0.5:0.5;

Terephthalic acid (TPA) and 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester is added according to the hydroxy functional group mol ratio 1.05:1 of binary acid carboxyl functional group and described polyols blend;

Described terephthalic acid (TPA) mixes according to mol ratio 95:5 with 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 200 DEG C, material fully blended in slurry kettle is imported, and add titanium ethylene glycolate and 250ppm butyl titanate, three (nonyl phenyl) phosphite esters of terephthalic acid (TPA) quality 0.02% and the antioxidant 616 of terephthalic acid (TPA) quality 0.02% of terephthalic acid (TPA) quality 250ppm, carry out the first esterification, the pressure of described first esterification is 0.1MPa, the temperature of reaction is 240 DEG C, and the time of reaction is 3h; When the first esterification water yield reaches 92% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary propylene glycol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 0.5h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

Supplementary propylene glycol is 16.3% of the first Esterification Stage polyol hydroxyls total mole number, makes alcohol total in the first esterification and the second esterification be 1.10 ~ 1.30:1 with the mol ratio of acid;

(4) finally the polyol polyester of preparation is obtained polyhydroxy polycarboxylic ester fiber through flat spinneret melt spinning is shaping;

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 290 DEG C, and spinning speed is 2000m/min, and draft temperature is 80 DEG C, and total stretching ratio is 5.

The wherein linear velocity 200m/min of first roller, the linear velocity 600m/min of the second roller, the linear velocity 600m/min of the 3rd roller, the linear velocity 400m/min of Wound-up roller, draw ratio 1.1, PU disc type false twisting D/Y ratio is 1.2.

The surface contact angle of fiber is 45 °, regain 2.2%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 7

(1) first esterification:

Ethylene glycol, butanediol and xylitol, xylitol are mixed into polyols blend, and wherein, the mol ratio of ethylene glycol and butanediol is 95:5, and dihydroxylic alcohols and sorbierite alcohol and xylitol configure according to mol ratio 99:0.7:0.3;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimonous oxide of terephthalic acid (TPA) quality 500ppm, the trimethyl phosphate of terephthalic acid (TPA) quality 0.0005% and 0.0005% alkyl phosphoric acid diester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.0005% and 0.0005% antioxidant 168 and carry out the first esterification, the pressure of described first esterification is 0.02MPa, the temperature of reaction is 245 DEG C, and the time of reaction is 4h; When the first esterification water yield reaches 92% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary ethylene glycol, and the pressure of reaction is 0.3Mpa, and the temperature of reaction is 255 DEG C, and the time of reaction is 2h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The temperature of described polycondensation reaction remains on 275 DEG C; Described polycondensation reaction continues 2h, prepares polyol polyester;

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 300 DEG C, and spinning speed is 3000m/min, and draft temperature is 80 DEG C, and total stretching ratio is 1.5.

The wherein linear velocity 600m/min of first roller, the linear velocity 5000m/min of the second roller, the linear velocity 300m/min of the 3rd roller, the linear velocity 400m/min of Wound-up roller, draw ratio 1.8, PU disc type false twisting D/Y ratio is 2.5.

The surface contact angle of fiber is 50 °, regain 2.0%, water absorption rate 250%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 8

(1) first esterification:

Ethylene glycol, propylene glycol, butanediol and sorbierite, pentaerythrite, xylitol are mixed into polyols blend, wherein, the mol ratio of ethylene glycol and butanediol is 90:5:5, and dihydroxylic alcohols and sorbierite, pentaerythrite, xylitol configure according to mol ratio 98:0.6:0.6:0.8;

Terephthalic acid (TPA) and 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester is added according to the hydroxy functional group mol ratio 1.02:1 of binary acid carboxyl functional group and described polyols blend;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimony acetate of terephthalic acid (TPA) quality 200ppm, the trimethyl phosphate of terephthalic acid (TPA) quality 0.01% and 0.01% three (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.01% and the antioxidant 616 of 0.01% carry out the first esterification, the pressure of described first esterification is 0.3MPa, the temperature of reaction is 240 DEG C, and the time of reaction is 4h; When the first esterification water yield reaches 93% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary butanediol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 1h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The temperature of described polycondensation reaction remains on 275 DEG C; Described polycondensation reaction continues 3h, prepares polyol polyester;

(4) finally the polyol polyester of preparation is obtained polyhydroxy polycarboxylic ester fiber through cross spinneret melt spinning is shaping;

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 300 DEG C, and spinning speed is 2500m/min, and draft temperature is 75 DEG C, and total stretching ratio is 4.5.

The wherein linear velocity 400m/min of first roller, the linear velocity 500m/min of the second roller, the linear velocity 500m/min of the 3rd roller, the linear velocity 600m/min of Wound-up roller, draw ratio 1.2, PU disc type false twisting D/Y ratio is 1.6.

The surface contact angle of fiber is 50 °, regain 2.5%, water absorption rate 250%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 9

(1) first esterification:

Propylene glycol, butanediol and pentaerythrite, xylitol are mixed into polyols blend, and wherein, the mol ratio of propylene glycol and butanediol is 95:5, and dihydroxylic alcohols and pentaerythrite, xylitol configure according to mol ratio 99.5:03.:0.2;

Described terephthalic acid (TPA) mixes according to mol ratio 92:8 with 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimony glycol of terephthalic acid (TPA) quality 200ppm, terephthalic acid (TPA) quality 0.0005% alkyl phosphoric acid diester and 0.0005% 3 (nonyl phenyl) phosphite ester, the antioxidant 168 of terephthalic acid (TPA) quality 0.0005% and 0.0005% antioxidant 616, carry out the first esterification, the pressure of described first esterification is 0.05MPa, the temperature of reaction is 240 DEG C, and the time of reaction is 4h; When the first esterification water yield reaches 94% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The temperature of described polycondensation reaction remains on 270 DEG C; Described polycondensation reaction continues 3h, prepares polyol polyester;

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning temperature is 270 DEG C, spinning speed is 3500m/min, the speed of hot-rolling GR1 is 1500m/min, temperature is 80 DEG C, the speed of hot-rolling GR2 is 4280m/min, and temperature is 115 DEG C, obtained polyol polyester FDY filament.

The surface contact angle of fiber is 45 °, regain 2.5%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 10

(1) first esterification:

Propylene glycol, butanediol and pentaerythrite, xylitol are mixed into polyols blend, and wherein, the mol ratio of propylene glycol and butanediol is 95:5, and dihydroxylic alcohols and pentaerythrite, xylitol configure according to mol ratio 98.5:0.9:0.6;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended, and preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimonous oxide of terephthalic acid (TPA) quality 100ppm and the antimony acetate of 100ppm, terephthalic acid (TPA) quality 0.0005% alkyl phosphoric acid diester and 0.0005% 3 (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.001%, the antioxidant 168 of 0.001% and the antioxidant 616 of 0.001%, carry out the first esterification, the pressure of described first esterification is 0.3MPa, the temperature of reaction is 255 DEG C, the time of reaction is 3h, when the first esterification water yield reaches 91% of theoretical water yield, complete the first esterification,

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary butanediol, and the pressure of reaction is 0.4Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 1h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning temperature is 290 DEG C, spinning speed is 4200m/min, the speed of hot-rolling GR1 is 1100m/min, temperature is 110 DEG C, the speed of hot-rolling GR2 is 4280m/min, and temperature is 135 DEG C, obtained polyol polyester FDY filament.

The surface contact angle of fiber is 48 °, regain 2.2%, water absorption rate 260%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 11

(1) first esterification:

Propylene glycol, butanediol, pentanediol and pentaerythrite, xylitol are mixed into polyols blend, and wherein, the mol ratio of propylene glycol, butanediol and pentanediol is 90:5:5, and dihydroxylic alcohols and pentaerythrite, xylitol configure according to mol ratio 98.5:0.9:0.6;

Described terephthalic acid (TPA) mixes according to mol ratio 94:6 with 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended, and preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimonous oxide of terephthalic acid (TPA) quality 150ppm and the butyl titanate of 150ppm, terephthalic acid (TPA) quality 0.002% trimethyl phosphate, 0.002% alkyl phosphoric acid diester and 0.002% 3 (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.002%, the antioxidant 168 of 0.002% and the antioxidant 616 of 0.002%, carry out the first esterification, the pressure of described first esterification is 0.05MPa, the temperature of reaction is 245 DEG C, the time of reaction is 3h, when the first esterification water yield reaches 94% of theoretical water yield, complete the first esterification,

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary propylene glycol, and the pressure of reaction is 0.4Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 1.5h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The temperature of described polycondensation reaction remains on 265 DEG C; Described polycondensation reaction continues 3h, prepares polyol polyester;

(4) finally the polyol polyester of preparation is obtained polyhydroxy polycarboxylic ester fiber through " 8 " font spinneret melt spinning is shaping;

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning temperature is 300 DEG C, spinning speed is 3500m/min, the speed of hot-rolling GR1 is 1500m/min, temperature is 110 DEG C, the speed of hot-rolling GR2 is 3550m/min, and temperature is 135 DEG C, obtained polyol polyester FDY filament.

Embodiment 12

(1) first esterification:

Ethylene glycol, propylene glycol, butanediol, pentanediol and pentaerythrite, xylitol are mixed into polyols blend, wherein, the mol ratio of ethylene glycol, propylene glycol and butanediol is 85:5:5:5, and dihydroxylic alcohols and pentaerythrite, xylitol configure according to mol ratio 98.5:0.9:0.6;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended, and preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimony acetate of terephthalic acid (TPA) quality 250ppm and the titanium ethylene glycolate of 250ppm, terephthalic acid (TPA) quality 0.004% trimethyl phosphate, 0.004% alkyl phosphoric acid diester and 0.004% 3 (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.004%, the antioxidant 168 of 0.004% and the antioxidant 616 of 0.004%, carry out the first esterification, the pressure of described first esterification is 0.3MPa, the temperature of reaction is 255 DEG C, the time of reaction is 2h, when the first esterification water yield reaches 92% of theoretical water yield, complete the first esterification,

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary propylene glycol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 270 DEG C, and the time of reaction is 1.5h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning temperature is 300 DEG C, spinning speed is 4000m/min, the speed of hot-rolling GR1 is 1200m/min, temperature is 100 DEG C, the speed of hot-rolling GR2 is 4000m/min, and temperature is 120 DEG C, obtained polyol polyester FDY filament.

The surface contact angle of fiber is 50 °, regain 2.2%, water absorption rate 250%, and the resistance of fiber is 10 ⁹Ω cm.

Embodiment 13

(1) first esterification:

Ethylene glycol, propylene glycol, butanediol, pentanediol and sorbierite, pentaerythrite are mixed into polyols blend, wherein, ethylene glycol, propylene glycol, butanediol, pentanediol are according to mol ratio 85:5:5:5, and dihydroxylic alcohols and pentaerythrite, xylitol configure according to mol ratio 99:0.6:0.4;

Described terephthalic acid (TPA) mixes according to mol ratio 93:7 with 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended, and preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimony acetate of terephthalic acid (TPA) quality 100ppm, the antimonous oxide of 100ppm and the butyl titanate of 100ppm, terephthalic acid (TPA) quality 0.005% trimethyl phosphate, 0.005% alkyl phosphoric acid diester and 0.005% 3 (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.005%, the antioxidant 168 of 0.005% and the antioxidant 616 of 0.005%, carry out the first esterification, the pressure of described first esterification is 0.3MPa, the temperature of reaction is 255 DEG C, the time of reaction is 2h, when the first esterification water yield reaches 92% of theoretical water yield, complete the first esterification, the pressure of described first esterification is 0.25MPa, and the temperature of reaction is 255 DEG C, and the time of reaction is 2h, when the first esterification water yield reaches 95% of theoretical water yield, complete the first esterification,

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary ethylene glycol, and the pressure of reaction is 0.45Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 2h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning temperature is 295 DEG C, spinning speed is 4000m/min, the speed of hot-rolling GR1 is 1200m/min, temperature is 100 DEG C, the speed of hot-rolling GR2 is 4200m/min, and temperature is 125 DEG C, obtained polyol polyester FDY filament.

Embodiment 14

(1) first esterification:

Ethylene glycol, propylene glycol, butanediol, pentanediol and sorbierite, xylitol are mixed into polyols blend, wherein, ethylene glycol, propylene glycol, butanediol, pentanediol are according to mol ratio 85:5:5:5, and dihydroxylic alcohols and xylitol, xylitol configure according to mol ratio 99:0.6:0.4;

Described terephthalic acid (TPA) mixes according to mol ratio 91:9 with 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended, and preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimony acetate of terephthalic acid (TPA) quality 100ppm, the antimonous oxide of 100ppm, the titanium ethylene glycolate of 100ppm and the butyl titanate of 100ppm, the trimethyl phosphate of terephthalic acid (TPA) quality 0.005%, 0.005% alkyl phosphoric acid diester and 0.005% 3 (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.006%, the antioxidant 168 of 0.006% and the antioxidant 616 of 0.006%, carry out the first esterification, the pressure of described first esterification is 0.01MPa, the temperature of reaction is 240 DEG C, the time of reaction is 4h, when the first esterification water yield reaches 92% of theoretical water yield, complete the first esterification,

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary propylene glycol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 2h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 300 DEG C, and spinning speed is 2500m/min, and draft temperature is 70 DEG C, and total stretching ratio is 4.5.

The surface contact angle of fiber is 45 °, regain 2.2%, water absorption rate 260%, and the resistance of fiber is 10 ⁸Ω cm.

Embodiment 15

(1) first esterification:

Ethylene glycol, propylene glycol, butanediol, pentanediol and sorbierite, pentaerythrite, xylitol are mixed into polyols blend, wherein, ethylene glycol, propylene glycol, butanediol, pentanediol are according to mol ratio 85:5:5:5, and dihydroxylic alcohols and sorbierite, pentaerythrite, xylitol configure according to mol ratio 99:0.6:0.2:0.2;

First described polyols blend and terephthalic acid (TPA), 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester are carried out stirring to pulp in slurry kettle, make fully blended, and preheating reaction kettle of the esterification, when reaction kettle of the esterification internal temperature reaches 230 DEG C, material fully blended in slurry kettle is imported, and add the antimony acetate of terephthalic acid (TPA) quality 100ppm, the antimonous oxide of 100ppm, the titanium ethylene glycolate of antimony glycol 100ppm of 100ppm and the butyl titanate of 100ppm, the trimethyl phosphate of terephthalic acid (TPA) quality 0.005%, 0.005% alkyl phosphoric acid diester and 0.005% 3 (nonyl phenyl) phosphite ester, the antioxidant 1010 of terephthalic acid (TPA) quality 0.01%, the antioxidant 168 of 0.01% and the antioxidant 616 of 0.01%, carry out the first esterification, the pressure of described first esterification is 0.1MPa, the temperature of reaction is 245 DEG C, the time of reaction is 3h, when the first esterification water yield reaches 90% of theoretical water yield, complete the first esterification,

(2) second esterifications:

The material that described first esterification obtains is carried out the second esterification after supplementary ethylene glycol, and the pressure of reaction is 0.5Mpa, and the temperature of reaction is 265 DEG C, and the time of reaction is 2h; Second esterification is until esterification water yield reaches more than 98% termination of theoretical water yield;

The polyol polyester that step (3) prepares is carried out melt spinning, its spinning technique is: spinning temperature is 300 DEG C, spinning speed is 800m/min, draft temperature is 75 DEG C, and predraft multiplying power is 1.10, and one stretching ratio is 3.20, two road stretching ratios are 1.15, obtained polyol polyester staple fibre, the fiber number of staple fibre is 1.0dtex, and length is 38mm.

Claims

1. a preparation method for polyhydroxy polycarboxylic ester fiber, is characterized in that: comprise the first esterification, the second esterification and polycondensation reaction successively, concrete steps are:

(1) first esterification:

Described polyols blend and described binary acid are added reaction kettle of the esterification and carries out the first esterification, the pressure of described first esterification is 0.01 ~ 0.5MPa, and the temperature of reaction is 230 ~ 260 DEG C, and the time of reaction is 2 ~ 4h; When the first esterification water yield reaches 90 ~ 95% of theoretical water yield, complete the first esterification;

(2) second esterifications:

The temperature of described polycondensation reaction remains on 260 ~ 280 DEG C; Described polycondensation reaction continues 2 ~ 4h, prepares polyol polyester;

(4) described polyol polyester is prepared polyhydroxy polycarboxylic ester fiber through melt spinning is shaping;

Described dihydroxylic alcohols is more than one in ethylene glycol, propylene glycol, butanediol or pentanediol; Described polyhydroxy-alcohol is more than one in sorbierite, pentaerythrite or xylitol.

2. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 1, is characterized in that, described binary acid is terephthalic acid (TPA) or terephthalic acid (TPA) and the 5-sodium sulfonate-M-phthalic acid diethyl alcohol ester mixture according to mol ratio 9 ~ 9.5:1 ~ 0.5.

3. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 1, it is characterized in that, in described step (1): before the first esterification starts, first described polyols blend and binary acid are carried out stirring to pulp in slurry kettle, make fully blended; And preheating reaction kettle of the esterification, imports material fully blended in slurry kettle when reaction kettle of the esterification internal temperature reaches 200 DEG C ~ 230 DEG C.

4. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 1, is characterized in that, in described step (1): before the first esterification starts, also add catalyst, heat stabilizer and antioxidant; The addition of described catalyst is 100 ~ 500ppm, and radix is the quality of described binary acid; The addition of described heat stabilizer is 0.001 ~ 0.02% of binary acid quality; The addition of described antioxidant is 0.001 ~ 0.03% of binary acid quality.

5. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 4, is characterized in that, described catalyst is Titanium series catalyst and/or antimony-based catalyst; Described Titanium series catalyst is butyl titanate and/or titanium ethylene glycolate; Described antimony-based catalyst is more than one in antimonous oxide, antimony acetate or antimony glycol.

6. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 4, is characterized in that, described heat stabilizer is one of them or its mixture of trimethyl phosphate, alkyl phosphoric acid diester or three (nonyl phenyl) phosphite ester.

7. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 4, is characterized in that, described antioxidant is antioxidant 1010, antioxidant 168 or antioxidant 616 one of them or its mixture.

8. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 1, is characterized in that, described polyhydroxy polycarboxylic ester fiber is POY, FDY, DTY or staple fibre, and its spinning technique is respectively:

The polyol polyester that step (3) prepares is carried out melt spinning, its staple fiber spinning process is: spinning temperature is 270 ~ 300 DEG C, spinning speed is 800 ~ 1500m/min, and draft temperature is 60 ~ 80 DEG C, and predraft multiplying power is 1.02 ~ 1.10, one stretching ratio is 2.80 ~ 3.20, two road stretching ratios are 1.05 ~ 1.15, then through cutting off, and obtained polyol polyester staple fibre, the fiber number of staple fibre is 0.3 ~ 5dtex, and length is 38mm or 51mm; Fracture strength>=the 2.5cN/dtex of described polyol polyester staple fibre, fibrous fracture percentage elongation 20 ~ 30%, the surface contact angle of fiber is 45 ~ 50 °, regain>=2.0%, water absorption rate>=250%, and the resistance of fiber is 10 ⁹Ω cm;

The polyol polyester that step (3) prepares is carried out melt spinning, and its POY spinning technique is: spinning temperature is 270 ~ 300 DEG C, and spinning speed is 2000 ~ 3000m/min, and draft temperature is 60 ~ 80 DEG C, and total stretching ratio is 1.5 ~ 5; Fracture strength>=the 2.0cN/dtex of described polyol polyester POY, fibrous fracture percentage elongation>=100%, the surface contact angle of fiber is 45 ~ 50 °, regain>=2.0%, water absorption rate>=250%, and the resistance of fiber is 10 ⁹Ω cm;

Further, POY after 8 h for equilibration, respectively through first roller, the Ith hot case, coldplate, PU disc type false twister, the second roller, the nozzle of interlace, the IIth hot case, the 3rd roller, oil tanker, eventually passes Wound-up roller coiling and molding, makes polyol polyester DTY; The wherein linear velocity 200 ~ 600m/min of first roller, linear velocity 500 ~ the 600m/min of the second roller, the linear velocity 300 ~ 600m/min of the 3rd roller, the linear velocity 400 ~ 700m/min of Wound-up roller, draw ratio 1.1 ~ 1.8, PU disc type false twisting D/Y ratio is 1.2 ~ 2.5; Fracture strength>=the 3.0cN/dtex of described polyol polyester DTY, fibrous fracture percentage elongation 15 ~ 20%, the surface contact angle of fiber is 45 ~ 50 °, regain>=2.5%, water absorption rate>=250%, and the resistance of fiber is 10 ⁸Ω cm;

The polyol polyester that step (3) prepares is carried out melt spinning, FDY spinning technique is: spinning speed is 3500 ~ 4200m/min, the speed of hot-rolling GR1 is 1100 ~ 1500m/min, temperature is 80 ~ 110 DEG C, the speed of hot-rolling GR2 is 3550 ~ 4280m/min, temperature is 115 ~ 135 DEG C, obtained polyol polyester FDY filament; Fracture strength>=the 3.5cN/dtex of described polyol polyester FDY, fibrous fracture percentage elongation 20 ~ 25%, the surface contact angle of fiber is 45 ~ 50 °, regain>=2.0%, water absorption rate>=250%, and the resistance of fiber is 10 ⁹Ω cm;

9. the preparation method of a kind of polyhydroxy polycarboxylic ester fiber according to claim 1, it is characterized in that, described melt spinning shaping employing circular jetting filament plate or profile spinneret, described profile spinneret is a kind of in trilobal spinnerets, platypelloid type spinnerets, hollow type spinnerets, cross spinnerets, Y type spinnerets or " 8 " font spinnerets.