CN109735939A - Fused mass directly spinning adds coloured polyester fiber and preparation method thereof online - Google Patents

Fused mass directly spinning adds coloured polyester fiber and preparation method thereof online Download PDF

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CN109735939A
CN109735939A CN201811615722.2A CN201811615722A CN109735939A CN 109735939 A CN109735939 A CN 109735939A CN 201811615722 A CN201811615722 A CN 201811615722A CN 109735939 A CN109735939 A CN 109735939A
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fused mass
acid
butyl
mass directly
polyester fiber
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CN109735939B (en
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杨超明
尹立新
王丽丽
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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Abstract

The present invention relates to a kind of fused mass directly spinnings to add coloured polyester fiber and preparation method thereof online, the preparation method comprises the following steps: fused mass directly spinning is made by modified poly ester melt by the technique after combination and adds coloured polyester fiber online by fused mass directly spinning after line adding technology is in conjunction with FDY technique；Masterbatch is added online into modified poly ester melt during fused mass directly spinning；It is modified poly ester FDY that fused mass directly spinning obtained adds coloured polyester fiber online, the strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, the binary acid segment with tert-butyl side group, fluorine-containing binary acid segment and 2,5,6,6- tetramethyl -2,5- heptandiol segment.Preparation method of the present invention is simple, passes through fluorine-containing binary acid, the binary acid with tert-butyl side group and 2,5,6,6- tetramethyl -2,5- heptandiols are modified polyester, the hydrolysis rate for improving polyester, improves the natural degradation performance of polyester fiber and product mechanical property obtained is excellent.

Description

Fused mass directly spinning adds coloured polyester fiber and preparation method thereof online
Technical field
The invention belongs to polyester fiber technical field, it is related to a kind of fused mass directly spinning and adds coloured polyester fiber and its system online Preparation Method.
Background technique
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, and PET is high with modulus, strong because of it The advantages that degree is high, conformality is good and barrier property is good is widely used in the fields such as fiber, bottle packaging, film and sheet material, yield Cumulative year after year, position in industry are obviously improved.
Textile industry fibre staining at present is mainly using the final finishing dyeing for first knitting after stain.Conventional polyester staple fiber can be used Disperse dyes dyeing, but need just to can be carried out in the presence of high temperature and pressure or carrier, the solarization jail of dyeing big to fibre damage Degree, washing and every fastness such as ironing are poor, and energy consumption is high, low efficiency, seriously polluted.By polyester fondant and Masterbatch (color Powder) the coloured polyester fiber filament that is obtained using fused mass directly spinning, have it is resistance to soap, the preferable fastness ability such as solarization and rub resistance, And the coloured polyester fiber filament of various colors enriches the selectivity of textile enterprise, becomes the preferred silk by consumers Wire material.
With the fast development of PET industry, although PET will not directly cause damages to environment, after its use Waste product huge amount and very strong to the repellence of atmosphere and microorganism reagent, PET waste oneself become global environmental pollution Organic matter.Currently, the common processing method to PET waste has landfill, burning and recycling, although landfill and burning are Simplest method will also cause certain pollution to environment, and degradation recycling is to handle PET waste effectively and the way of science Diameter, but due to PET construction densification, crystallinity is high, and natural degradation time is very long, the ratio recycled at present also very little.It is based on The enhancing of environmental consciousness, resource-effective and sustainability demand, take polyester fiber natural degradation oneself become China science and technology Worker's problem in the urgent need to address.
Therefore, it studies and a kind of improves the side of polyester degradation rate and degradation effect problem by being modified to polyester Method, and the fused mass directly spinning that mechanical property is good, inherent viscosity is low is prepared using the modified poly ester and adds coloured polyester fiber online Great realistic meaning.
Summary of the invention
The purpose of the present invention is overcome to take that coloured polyester fiber degradation rate is slow, degradation effect is poor lacks in the prior art It falls into, provides a kind of method by being modified polyester to improve polyester degradation rate and degradation effect, and use the modification Polyester adds coloured polyester fiber to prepare the fused mass directly spinning that mechanical property is good, inherent viscosity is low online.
In order to achieve the above object, the present invention adopts the following technical scheme that:
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, by the online adding technology of fused mass directly spinning and FDY work After skill combines, modified poly ester FDY is made by modified poly ester melt by the technique after combination and is added with online to get fused mass directly spinning Color polyester fiber；
Masterbatch is added online into modified poly ester melt during fused mass directly spinning；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group, containing Fluorine binary acid and 2,5,6,6- tetramethyl -2,5- heptandiol successively carry out esterification and polycondensation reaction after mixing；
Binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, 3- The own dioctyl phthalate of tert-butyl -1,6- or the own dioctyl phthalate of 2,5- di-t-butyl -1,6-；The present invention uses 5- tert-butyl -1,3- benzene diformazan Acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- or the own dioctyl phthalate of 2,5- di-t-butyl -1,6- are to poly- Ester is modified, and easily causes the variation of main chain activity, so that the interaction force between chain element is changed, molecule chain element Between distance can also occur to change accordingly, increase modified poly ester cavity free volume, the increase of empty free volume can drop Low moisture penetrates into the difficulty inside modified poly ester, improves the natural degradation rate of modified poly ester；
Fluorine-containing binary acid is the fluoro- 1,3- malonic acid of 2,2- bis-, the fluoro- 1,4- succinic acid of 2,2- bis-, the fluoro- 1,5- penta 2 of 2,2- bis- Acid or the fluoro- 1,4- succinic acid of 2,2,3,3- tetra-；The fluorine-containing binary acid that the present invention passes through the introducing special construction in polyester molecule chain The degradation rate of polyester is significantly improved, fluorine-containing binary acid is characterized in that fluorine atom on α carbon, when in hydrolytic process When introducing the fluorine-containing binary acid, since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that the electron cloud in polyester on C-O key Density reduces, and the stability decline of tetrahedral anion is conducive to the progress of nucleophilic addition, simultaneously because containing on α carbon The steric hindrance of fluorine binary acid is less than terephthalic acid (TPA), further promotes the progress of nucleophilic addition, thus significantly improves Degradation rate.
The structural formula of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:
The present invention passes through the mutual cooperation pair of 2,5,6,6- tetramethyl -2,5- heptandiol and the binary acid with tert-butyl side group Polyester is modified, and has been obviously improved the degradation rate of polyester, 2,5,6,6- tetramethyl -2,5- heptandiols and with tert-butyl side group Binary acid in the presence of tert-butyl can cause the variation of main chain activity, to change the interaction force between chain element, Distance between molecule chain element can also occur to change accordingly, lead to the increase of modified poly ester cavity free volume.With short-chain branch Substituent group (such as methyl, ethyl group) is compared, and tert-butyl occupies biggish spatial position, in the mode of strand arrangement Bigger free volume will be obtained；Compared with chain substituent of drawing money on credit, what one side tert-butyl increased is empty free volume, and is grown What branched alkyl substituent increased is slit free volume, and the rigidity of another aspect tert-butyl is greater than chain substituent of drawing money on credit, and is reduced point Entanglement between subchain, thus tert-butyl has more free bodies compared with chain substituent of drawing money on credit in the mode that strand arranges Product.The introducing of 2,5,6,6- tetramethyl -2,5- heptandiol and the binary acid with tert-butyl side group so that modified poly ester cavity from Increased by volume, so that water or other molecules etc. are easier to penetrate into modified poly ester macromolecule internal, the degradation to modified poly ester Deng generation active influence.
As a preferred technical scheme:
Fused mass directly spinning as described above adds the preparation method of coloured polyester fiber online, the Masterbatch by 20~ The mass ratio of the pigment of 30wt% and the polyester composition of 70~80wt%, the Masterbatch and modified poly ester melt is 1~3:97 ~99, the color of the pigment is red, yellow, blue, green, purple or black；
The own dioctyl phthalate of the 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and 2,5- di-t-butyl -1,6- oneself The synthetic method of dioctyl phthalate are as follows:
Wolframic acid and hydrogen peroxide are mixed first, 10~15min is stirred at room temperature, be then added raw alcohol first 80~ 1~2h is reacted under the conditions of 85 DEG C of temperature, then is warming up to 90~95 DEG C of 2~3h of reaction, and in reaction process, reactant is in always Reflux state finally carries out crystallisation by cooling, washing and purification；
When reaction starts, the molar ratio of wolframic acid, raw alcohol and hydrogen peroxide is 1:30~40:120~150；
The own dioctyl phthalate of the 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and 2,5- di-t-butyl -1,6- oneself The corresponding raw alcohol of dioctyl phthalate is respectively 2- tert. butyl cyclohexanol, the pure and mild 2,4- di-t-butyl cyclohexanol of 4- t-butylcyclohexyl；
The synthesis step of the 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:
(1) by 1~1.2:1:1.2~1.3:2.0~3.0 molar ratio by KOH powder, 3- methyl -3- hydroxyl butine, 3, 3- dimethyl-2-butanone and isopropyl ether mixing, react 2~4h under condition of ice bath, carry out crystallisation by cooling, centrifugation after reaction Separate, wash, refine and be dried to obtain octyne glycol；
(2) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2~3:10:0.01~0.03,40~50 DEG C temperature under the conditions of react 50~60min, be continually fed into hydrogen in reaction process, separated and purified after reaction To 2,5,6,6- tetramethyl -2,5- heptandiol.
Fused mass directly spinning as described above adds the preparation method of coloured polyester fiber, the preparation step of the modified poly ester online It is rapid as follows:
(1) esterification；
By terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group, fluorine-containing binary acid and 2,5,6,6- tetramethyl- 2,5- heptandiols are made into slurry, and catalyst, delustering agent and stabilizer is added after mixing, and pressurization carries out ester in nitrogen atmosphere Change reaction, moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching 90% of theoretical value or more；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 250~260 DEG C, the reaction time is 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 270~282 DEG C, the reaction time is 50~90min.
Fused mass directly spinning as described above adds the preparation method of coloured polyester fiber, the terephthalic acid (TPA) and second two online The molar ratio of alcohol be 1:1.2~2.0, the binary acid with tert-butyl side group, fluorine-containing binary acid and 2,5,6,6- tetramethyl -2, The sum of additional amount of 5- heptandiol is 3~5mol% (molar percentage) of terephthalic acid (TPA) additional amount, band tert-butyl side The binary acid of base, fluorine-containing binary acid and 2, the molar ratio of 5,6,6- tetramethyl -2,5- heptandiols is 1~2:2~4:3~5, described The additional amount of catalyst, delustering agent and stabilizer be respectively 0.03~0.05wt% of terephthalic acid (TPA) additional amount, 0.20~ 0.25wt% and 0.01~0.05wt% (mass percent).Binary acid of the present invention with tert-butyl side group, fluorine-containing binary acid and The additional amount of 2,5,6,6- tetramethyl -2,5- heptandiols is not limited to this, those skilled in the art can actual conditions be adjusted, But adjustment amplitude should not be too large, and the excessive regularity destruction to polyester macromolecule structure of additive amount is too big, to the crystallinity of fiber And Effect on Mechanical Properties is excessive, is unfavorable for the production and application of fiber, additive amount is too low, then effect is unobvious.
Fused mass directly spinning as described above adds the preparation method of coloured polyester fiber online, and the catalyst is three oxidations two Antimony, antimony glycol or antimony acetate, the delustering agent be titanium dioxide, the stabilizer be triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
Fused mass directly spinning as described above adds the preparation method of coloured polyester fiber, the number-average molecular weight of modified poly ester online It is 25000~30000, molecular weight distributing index is 1.8~2.2
Fused mass directly spinning as described above adds the preparation method of coloured polyester fiber online, and the fused mass directly spinning adds online The process of technique are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, and it is molten Body after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly together；
The process of the FDY technique are as follows: metering, spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding；
The parameter of the FDY technique are as follows: 285~295 DEG C of spinning temperature, 19~23 DEG C of cooling temperature, network pressure 0.20 ~0.30MPa, a 1800~2500m/min of roller speed, 75~90 DEG C of a roll temperature, two roller speed 3600~4000m/min, two 105~125 DEG C of roll temperature, 3560~3920m/min of winding speed.
The present invention also provides the preparation methods for adding coloured polyester fiber online using fused mass directly spinning as described above to be made Fused mass directly spinning add coloured polyester fiber online, be modified poly ester FDY；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, the binary with tert-butyl side group Sour segment, fluorine-containing binary acid segment and 2,5,6,6- tetramethyl -2,5- heptandiol segment.
As a preferred technical scheme:
Fused mass directly spinning as described above adds coloured polyester fiber online, and fused mass directly spinning adds coloured polyester fiber online Filament number is 1.0~3.0dtex, and breaking strength >=3.8cN/dtex, breaking strength CV value≤5.0%, elongation at break is 35 ± 4%, extension at break CV value≤9.0%, boiling water shrinkage is 7.0 ± 0.5%, strip dry CV value≤1.5%, and oil content is 1.00 ± 0.20wt%, internet pricing are 20 ± 4/m.The present invention by the binary acid with tert-butyl side group, fluorine-containing binary acid with And 2, the introducing of 5,6,6- tetramethyl -2,5- heptandiols is modified polyester, and the above-mentioned mechanical property of obtained fiber is simultaneously Do not decline, it is suitable with the prior art.
Fused mass directly spinning as described above adds coloured polyester fiber online, and fused mass directly spinning adds coloured polyester fiber online and exists After 25 DEG C and relative humidity are placed 60 months under conditions of being 65%, inherent viscosity declines 15~20%.Conventional coloured polyester In the same circumstances, inherent viscosity descends below 5% to fiber.Of the invention introduces fluorine-containing binary acid in polyester macromolecule chain When, since fluorine atom is on α carbon, electron-withdrawing ability is stronger, promotes the progress of nucleophilic addition, makes in polyester macromolecule chain Ester linkage breaking, thus significantly improve degradation rate.
Invention mechanism:
The present invention passes through the binary acid with tert-butyl side group, fluorine-containing binary acid and 2,5,6,6- tetramethyl -2,5- heptandiol Polyester is modified, and by fused mass directly spinning after line adding technology is in conjunction with FDY technique, fused mass directly spinning obtained adds online The degradation property and degradation effect of coloured polyester fiber are greatly promoted.Due to the binary acid with tert-butyl side group and 2,5, The mutual cooperation of 6,6- tetramethyl -2,5- heptandiols is modified polyester, increases modified poly ester cavity free volume, cavity is certainly Hydrone can reduce by the increase of volume and penetrate into difficulty inside modified poly ester, improve the degradation rate of modified poly ester； In addition, the modification due to fluorine-containing binary acid to polyester again, can promote the progress of nucleophilic addition in hydrolytic process, and significantly mention High degradation rate.
Binary acid with tert-butyl side group and 2,5,6,6- tetramethyl -2,5- heptandiol improve polyester fiber to polyester modification Degradation property the specific mechanism of action it is as follows:
Macromolecular chain in polymer is not closely to pile up completely, always with the presence of gap between macromolecular chain, this Portion void volume is free volume.It penetrates into small molecule inside macromolecule, to have foot in macromolecule or between macromolecule Enough big gaps, so pore size (the i.e. ruler of free volume in the permeability and diffusivity of small molecule and macromolecular structure It is very little) it is related, in a certain range, the size of free volume is bigger, and the permeability of small molecule is higher, and diffusivity is better.Free body Product is divided into empty free volume and slit free volume again, and empty free volume has bigger space ruler compared with slit free volume It is brighter compared with effect when increasing slit free volume to increase empty free volume for very little, for the permeability of small molecule promotion It is aobvious.
The size and type of free volume depend primarily on the structure of polymer, and the principal element for influencing polymer architecture is Steric hindrance, side group size and side group structure etc..When position a certain on main polymer chain is replaced by side group, necessarily cause to lead The variation of chain activity, to change the interaction force of chain and interchain, chain can also occur to change accordingly at a distance from interchain Become, as a result lead to the variation of cohesive energy and free volume, polarity, size and length of the substituent group on polymer side chain etc. to point The fractional free volume of sub- chain rigidity and intermolecular interaction or even polymer architecture all has a certain impact, therefore, The effect that substituent group difference generates is different, and the permeability and separation performance for often leading to polymer is also different.
For the straight chain molecules such as M-phthalic acid and own dioctyl phthalate, when on M-phthalic acid phenyl ring H atom or oneself two H atom on formic acid methylene is by methyl (- CH3) when replacing, C atom and main chain C atom in side group not in the same plane, Then, four sp3 hybridized orbits on the C of center are Chong Die with the unoccupied orbital on four C atoms around respectively, form four complete phases With σ key, arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, when methyl three hydrogen into When one step is replaced by methyl, it is at this moment equivalent to tert-butyl substitution, forms a bigger tetrahedral structure, this positive tetrahedron The strand of arrangement is arranged with respect to indention, and empty free volume significantly increases very much, can significantly improve small molecule Permeability and diffusivity；And when the H atom on M-phthalic acid phenyl ring or the H atom on own dioctyl phthalate methylene are by long-chain branch When substituent group replaces, what is mainly increased is slit free volume, and it is smaller to increase amplitude, permeability to small molecule and diffusible Promotion effect is limited, simultaneously because the rigidity for chain substituent of drawing money on credit is smaller, entanglement is easy to happen between strand, is unfavorable for freedom The increase of volume.The drop that the present invention has been obviously improved polyester by introducing the binary acid with tert-butyl side group in polyester molecule chain Performance is solved, the binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, uncle 3- The own dioctyl phthalate of butyl -1,6- or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6-, the wherein own dioctyl phthalate of 2- tert-butyl -1,6-, the tertiary fourth of 3- The own dioctyl phthalate of base -1,6- and 2, the own dioctyl phthalate of 5- di-t-butyl -1,6- are adipic acid, are a kind of fatty acid, rigidity is less than 5- Tert-butyl -1,3- phthalic acid is conducive to the flexibility for promoting polyester segment, tert-butyl in the binary acid with tert-butyl side group In the presence of the variation of main chain activity can be caused, so that the interaction force between chain element is changed, the distance between molecule chain element Also it can occur to change accordingly, lead to the increase of the empty free volume of modified poly ester.With short-chain branch substituent group (such as methyl, second The groups such as base) it compares, tert-butyl occupies biggish spatial position, and bigger freedom will be obtained in the mode of strand arrangement Volume；Compared with chain substituent of drawing money on credit, what one side tert-butyl increased is empty free volume, and chain substituent increase of drawing money on credit It is slit free volume, the rigidity of another aspect tert-butyl is greater than chain substituent of drawing money on credit, reduces the entanglement between strand, because And tert-butyl has more free volumes compared with chain substituent of drawing money on credit in the mode that strand arranges.In addition, when band tert-butyl When the binary acid of side group is 5- tert-butyl -1,3- phthalic acid, the phenyl ring of meta position dioctyl phthalate connection will form one bigger non- Symmetry segment not only increases the steric hindrance migrated between segment and increases the steric hindrance rotated in segment around meta position connecting key, The introducing of meta-isomer is conducive to the increase of free volume.The introducing of binary acid with tert-butyl side group is so that modified poly ester Empty free volume increases, and the increase of empty free volume will make water or other molecules be easier to penetrate into modified poly ester macromolecular Inside generates active influence to degradation of modified poly ester etc..
For the dihydric alcohols straight chain molecule such as ethylene glycol, butanediol, the C atom on main chain is arranged in indention one on the other Column, when two H atoms on main chain on some methylene are by methyl (- CH3) when replacing, C atom and master in the two side groups Chain C atom not in the same plane, then, four sp3 hybridized orbits on the C of center respectively with the sky on four C atoms around Orbital Overlap forms four identical σ keys, arranges in positive tetrahedron, and four carbon atom is located at the four of positive tetrahedron At this moment a vertex is equivalent to tert-butyl substitution when three hydrogen of methyl are further replaced by methyl, formed one bigger Tetrahedral structure, the strand that this strand in the arrangement of positive tetrahedron shape is arranged relative to indention, empty free body Product significantly increases very much, can significantly improve the permeability and diffusivity of small molecule；And work as on main chain on some methylene Two H atoms are drawn money on credit chain substituent when replacing, and what is mainly increased is slit free volume, and it is smaller to increase amplitude, to small molecule Permeability and diffusible promotion effect it is limited, simultaneously because chain substituent of drawing money on credit rigidity it is smaller, between strand be easy It tangles, is unfavorable for the increase of free volume.The presence meeting of tert-butyl in 2,5,6,6- tetramethyl -2,5- heptandiol of the present invention Cause the variation of main chain activity, to change the interaction force between chain element, the distance between molecule chain element can also be sent out Raw corresponding change, causes the empty free volume of modified poly ester to increase.With short-chain branch substituent group (such as methyl, ethyl group) It compares, tert-butyl occupies biggish spatial position, and bigger free volume will be obtained in the mode of strand arrangement；With length Branched alkyl substituent is compared, and what one side tert-butyl increased is empty free volume, and draw money on credit chain substituent increase be slit from By volume, the rigidity of another aspect tert-butyl is greater than chain substituent of drawing money on credit, and reduces the entanglement between strand, thus tert-butyl Chain substituent of relatively drawing money on credit has more free volumes in the mode that strand arranges.Empty free volume increases, so that water Etc. being easier to penetrate into modified poly ester macromolecule internal, active influence is generated to degradation of modified poly ester etc..
Fluorine-containing binary acid is as follows to the specific mechanism of action for the degradation property that polyester modification improves polyester fiber:
The hydrolytic degradation process of polyester under alkaline condition is nucleophilic addition-elimination process, when hydrolysis starts, OH-Nucleophilic addition occurs for the C atom of attack ester carbonyl group RCOOR`, is formed intermediate (i.e. tetrahedral anion), four sides The anion of body can eliminate OR` and obtain carboxylic acid RCOOH, make ester linkage breaking, while OR` and H+In conjunction with obtaining alcohol HOR`.However, Since the tetrahedral anion structure formed in hydrolytic process is more crowded, steric hindrance is big, and it is anti-to be unfavorable for nucleophilic addition The progress answered, therefore the degradation rate of polyester is slower.
The present invention significantly improves the degradation of polyester by introducing the fluorine-containing binary acid of special construction in polyester molecule chain Rate, fluorine-containing binary acid is characterized in that fluorine atom on α carbon, when introducing the fluorine-containing binary acid in hydrolytic process, Since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that the cloud density in polyester on C-O key reduces, it is tetrahedral The stability of anion declines, and is conducive to the progress of nucleophilic addition, simultaneously because on α carbon fluorine-containing binary acid steric hindrance Less than terephthalic acid (TPA), the progress of nucleophilic addition is further promoted, thus significantly improves degradation rate.Such as in polyester Fluorine atom is introduced in strand in the fluorine-containing binary acid of β carbon, then the degradation rate of polyester will not be significantly improved, this is because in β There are when electron-withdrawing group on carbon, generated influence is limited only on adjacent carbons, and the influence to C-O key generation in ester bond is very It is small, thus for OH-The reaction that nucleophilic addition occurs for attack ester carbonyl group influences smaller.Conventional melt is directly spun adds coloured gather online Although ester fiber is widely used, but the compact structure of fiber, crystallinity are high, and natural degradation time is very long, as the main of clothes Purposes is difficult in terms of recycling, and the present invention is added fluorine-containing binary acid and significantly promotes by preparing in polyester in raw material The progress of nucleophilic addition, and then improve the degradation rate of polyester.
The utility model has the advantages that
(1) a kind of fused mass directly spinning of the invention adds the preparation method of coloured polyester fiber online, passes through addition fluorine-containing two First acid is modified polyester, promotes the progress of nucleophilic addition in hydrolytic process, while by with tert-butyl side group Binary acid and 2,5,6,6- tetramethyl -2,5- heptandiols are modified polyester, increase the empty free volume of modified poly ester, The degradation rate for improving polyester can effectively solve the problems, such as that waste and old clothes recycle for clothes weaving；
(2) a kind of fused mass directly spinning of the invention adds the preparation method of coloured polyester fiber online, simple process, at low cost It is honest and clean, great application prospect；
(3) a kind of fused mass directly spinning of the invention adds coloured polyester fiber online, and mechanical property is good, at 25 DEG C and relatively wet After degree is placed 60 months under conditions of being 65%, inherent viscosity decline 15~20%.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1:1:1.2:2.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl-2-butanone It is mixed with isopropyl ether, 2h is reacted under condition of ice bath, carry out crystallisation by cooling, centrifuge separation, washing, purification after reaction and done It is dry to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2:10:0.01, in 40 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.2) esterification；
By terephthalic acid (TPA), ethylene glycol, 5- tert-butyl -1,3- phthalic acid, the fluoro- 1,3- malonic acid of 2,2- bis- and 2,5,6, 6- tetramethyl -2,5- heptandiol is made into slurry, and antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, Pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 91% of theoretical value, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol is 1: 1.2,5- tert-butyl -1,3- phthalic acids, fluoro- 1, the 3- malonic acid of 2,2- bis- and 2,5,6,6- tetramethyl -2,5- heptandiols add Enter the 3mol% that the sum of amount is terephthalic acid (TPA) additional amount, 5- tert-butyl -1,3- phthalic acid, fluoro- 1, the 3- malonic acid of 2,2- bis- With 2, the molar ratio of 5,6,6- tetramethyl -2,5- heptandiols is 1:2:4, antimony oxide, titanium dioxide and triphenyl phosphate Additional amount is respectively 0.03wt%, 0.20wt% and 0.04wt% of terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 255 DEG C, reaction time 30min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 270 DEG C, reaction time 40min, the number-average molecular weight of modified poly ester obtained is 26500, molecular weight distributing index 1.8；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 285 DEG C of spinning temperature, cooling temperature 19 DEG C, network pressure 0.25MPa, a roller speed 2500m/min, 80 DEG C of a roll temperature, two roller speed 3600m/min, two roll temperatures 115 DEG C, winding speed 3920m/min.
It is 1.0dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 3.8cN/dtex, breaking strength CV value are 4.3%, and elongation at break 39%, extension at break CV value is 8.3%, boiling shrinkage Rate is 7.0%, strip dry CV value 1.49%, oil content 1.00wt%, and internet pricing is 18/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 15%.
Comparative example 1
A kind of fused mass directly spinning adds the preparation method of coloured polyester fiber online, and step is substantially same as Example 1, no It is with place, step (1) is simultaneously not added with 5- tert-butyl -1,3- phthalic acid, fluoro- 1, the 3- malonic acid of 2,2- bis- and 2,5,6,6- Tetramethyl -2,5- heptandiol, i.e., be not modified polyester, and fused mass directly spinning obtained adds the list of coloured polyester fiber online Silk size is 1.0dtex, and breaking strength 3.6cN/dtex, breaking strength CV value is 4.4%, and elongation at break 38% breaks Splitting elongation CV value is 8.2%, boiling water shrinkage 6.7%, strip dry CV value 1.40%, oil content 1.10wt%, internet pricing For 18/m, after being placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 3.6%.With the comparison of embodiment 1 it can be found that the present invention passes through 5- tert-butyl -1,3- phthalic acid, 2,5,6,6- tetramethyl -2, 5- heptandiol and 2, fluoro- 1, the 3- malonic acid of 2- bis- are modified polyester, improve the degradability of fiber, while the tertiary fourth of 5- The addition of base -1,3- phthalic acid, the fluoro- 1,3- malonic acid of 2,2- bis- and 2,5,6,6- tetramethyl -2,5- heptandiol is to fiber The influence of other performances is smaller, has no effect on its processing performance and mechanical performance.
Comparative example 2
A kind of fused mass directly spinning adds the preparation method of coloured polyester fiber online, and step is substantially same as Example 1, no It is with place, substitute fluoro- 1, the 3- malonic acid of 2,2- bis- using 3,3- difluoro glutaric acid in step (1), melt obtained is straight Spinning and adding the filament number of coloured polyester fiber online is 1.0dtex, breaking strength 3.7cN/dtex, and breaking strength CV value is 4.3%, elongation at break 40%, extension at break CV value is 8.0%, boiling water shrinkage 6.9%, and strip dry CV value is 1.36%, oil content 1.00wt%, internet pricing are 18/m, are put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 4.7%.With embodiment 1 comparison it can be found that fluorine atom α carbon fluorine-containing binary acid The natural degradation performance for promoting fiber is more advantageous in the fluorine-containing binary acid of β carbon relative to fluorine atom, this is because depositing on β carbon In electron-withdrawing group, generated influence is limited only on adjacent carbons, and in ester bond C-O key generate influence very little, because And for OH-Attack ester carbonyl group occur nucleophilic addition reaction influence it is smaller, and then on the natural degradation process of fiber influence compared with It is small.
Embodiment 2
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) it prepares the own dioctyl phthalate of 2- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 10min is added 2- tert. butyl cyclohexanol and first reacts 1h under the conditions of 80 DEG C of temperature, then is warming up to 94 DEG C of reaction 2h, instead During answering, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, tungsten Sour, the pure and mild hydrogen peroxide of 2- t-butylcyclohexyl molar ratio is 1:35:120；
(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1.1:1:1.2:2.3 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 2h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2:10:0.01, in 45 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the own dioctyl phthalate of 2- tert-butyl -1,6-, the fluoro- 1,4- succinic acid of 2,2- bis- and 2,5,6, 6- tetramethyl -2,5- heptandiol is made into slurry, and antimony oxide, titanium dioxide and Trimethyl phosphite is added after mixing, Pressurization carries out esterification, moulding pressure 0.3MPa in nitrogen atmosphere, and the temperature of esterification is 260 DEG C, when esterification is anti- Water quantity of distillate in answering is esterification terminal when reaching the 92% of theoretical value, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol For 1:1.5, the own dioctyl phthalate of 2- tert-butyl -1,6-, the fluoro- 1, 4- succinic acid of 2,2- bis- and 2,5,6,6- tetramethyl -2,5- heptandiols The sum of additional amount be terephthalic acid (TPA) additional amount 3mol%, the own dioctyl phthalate of 2- tert-butyl -1,6-, the fluoro- Isosorbide-5-Nitrae-fourth of 2,2- bis- Diacid and 2, the molar ratio of 5,6,6- tetramethyl -2,5- heptandiols are 1:4:3, antimony oxide, titanium dioxide and phosphorous acid three The additional amount of methyl esters is respectively 0.04wt%, 0.25wt% and 0.01wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min The interior absolute pressure that is steadily evacuated to by normal pressure is 400Pa, and reaction temperature is 250 DEG C, reaction time 40min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 80Pa, reaction temperature 272 DEG C, reaction time 65min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 1.9；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 285 DEG C of spinning temperature, cooling temperature 23 DEG C, network pressure 0.20MPa, a roller speed 1900m/min, 90 DEG C of a roll temperature, two roller speed 4000m/min, two roll temperatures 125 DEG C, winding speed 3700m/min.
It is 1.0dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 4.1cN/dtex, breaking strength CV value are 5.0%, and elongation at break 35%, extension at break CV value is 8.7%, boiling shrinkage Rate is 6.5%, strip dry CV value 1.45%, oil content 0.80wt%, and internet pricing is 20/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 18%.
Embodiment 3
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) it prepares the own dioctyl phthalate of 2- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 12min is added 2- tert. butyl cyclohexanol and first reacts 1.5h under the conditions of 83 DEG C of temperature, then is warming up to 90 DEG C of reaction 2h, In reaction process, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, Wolframic acid, the pure and mild hydrogen peroxide of 2- t-butylcyclohexyl molar ratio be 1:33:120；
(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1.2:1:1.25:2.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- Butanone and isopropyl ether mixing, 3h is reacted under condition of ice bath, carries out crystallisation by cooling, centrifuge separation, washing, purification after reaction Be dried to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.03, in 40 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the own dioctyl phthalate of 2- tert-butyl -1,6-, the fluoro- 1,5- glutaric acid of 2,2- bis- and 2,5,6, 6- tetramethyl -2,5- heptandiol is made into slurry, antimony glycol, titanium dioxide and triphenyl phosphate is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 90% of theoretical value, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol is 1: The own dioctyl phthalate of 1.3,2- tert-butyls -1,6-, fluoro- 1, the 5- glutaric acid of 2,2- bis- and 2,5,6,6- tetramethyl -2,5- heptandiols add Enter the 3.5mol% that the sum of amount is terephthalic acid (TPA) additional amount, the own dioctyl phthalate of 2- tert-butyl -1,6-, fluoro- 1, the 5- penta 2 of 2,2- bis- The molar ratio of acid and 2,5,6,6- tetramethyl -2,5- heptandiols is 1.5:2:3, antimony glycol, titanium dioxide and triphenyl phosphate Additional amount be respectively terephthalic acid (TPA) additional amount 0.04wt%, 0.22wt% and 0.05wt%；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 45min The interior absolute pressure that is steadily evacuated to by normal pressure is 450Pa, and reaction temperature is 256 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 279 DEG C, reaction time 60min, the number-average molecular weight of modified poly ester obtained is 28000, molecular weight distributing index 2.2；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 290 DEG C of spinning temperature, cooling temperature 19 DEG C, network pressure 0.20MPa, a roller speed 1800m/min, 90 DEG C of a roll temperature, two roller speed 3800m/min, two roll temperatures 120 DEG C, winding speed 3920m/min.
It is 2.0dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 3.8cN/dtex, breaking strength CV value are 5.0%, and elongation at break 31%, extension at break CV value is 9.0%, boiling shrinkage Rate is 7.5%, strip dry CV value 1.46%, oil content 1.20wt%, and internet pricing is 16/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 17%.
Embodiment 4
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) it prepares the own dioctyl phthalate of 3- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 13min is added 4- tert. butyl cyclohexanol and first reacts 2h under the conditions of 85 DEG C of temperature, then is warming up to 90 DEG C of reaction 3h, instead During answering, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, tungsten Sour, the pure and mild hydrogen peroxide of 4- t-butylcyclohexyl molar ratio is 1:30:130；
(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1.2:1:1.3:2.5 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 3h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2.5:10:0.02, in 45 DEG C of temperature strip 60min is reacted under part, hydrogen is continually fed into reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the own dioctyl phthalate of 3- tert-butyl -1,6-, the fluoro- 1,4- succinic acid of 2,2,3,3- tetra- and 2, 5,6,6- tetramethyl -2,5- heptandiols are made into slurry, and antimony glycol, titanium dioxide and Trimethyl phosphite is added and is uniformly mixed Afterwards, pressurization carries out esterification, moulding pressure 0.1MPa in nitrogen atmosphere, and the temperature of esterification is 250 DEG C, works as esterification Water quantity of distillate in reaction is esterification terminal when reaching the 90% of theoretical value, wherein mole of terephthalic acid (TPA) and ethylene glycol Than for 1:1.8, the own dioctyl phthalate of 3- tert-butyl -1,6-, 2,2,3,3- tetra- fluoro- 1, 4- succinic acids and 2,5,6,6- tetramethyls -2,5- The sum of additional amount of heptandiol is the 4mol% of terephthalic acid (TPA) additional amount, the own dioctyl phthalate of 3- tert-butyl -1,6-, 2,2,3,3- tetra- Fluoro- 1, 4- succinic acid and 2, the molar ratios of 5,6,6- tetramethyl -2,5- heptandiols are 1.5:3:5, antimony glycol, titanium dioxide and The additional amount of Trimethyl phosphite is respectively 0.05wt%, 0.20wt% and 0.03wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min The interior absolute pressure that is steadily evacuated to by normal pressure is 420Pa, and reaction temperature is 260 DEG C, reaction time 35min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 85Pa, reaction temperature 280 DEG C, reaction time 40min, the number-average molecular weight of modified poly ester obtained is 27700, molecular weight distributing index 1.8；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 292 DEG C of spinning temperature, cooling temperature 22 DEG C, network pressure 0.30MPa, a roller speed 1800m/min, 85 DEG C of a roll temperature, two roller speed 3800m/min, two roll temperatures 110 DEG C, winding speed 3560m/min.
It is 1.8dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 4.1cN/dtex, breaking strength CV value are 4.3%, and elongation at break 31%, extension at break CV value is 9.0%, boiling shrinkage Rate is 7.5%, strip dry CV value 1.47%, oil content 0.90wt%, and internet pricing is 24/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 20%.
Embodiment 5
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) it prepares the own dioctyl phthalate of 3- tert-butyl -1,6-: wolframic acid and hydrogen peroxide being mixed first, are stirred at room temperature Then 14min is added 4- tert. butyl cyclohexanol and first reacts 2h under the conditions of 82 DEG C of temperature, then is warming up to 92 DEG C of reaction 3h, instead During answering, reactant is in reflux state always, finally carries out crystallisation by cooling, washing and purification, wherein when reaction starts, tungsten Sour, the pure and mild hydrogen peroxide of 4- t-butylcyclohexyl molar ratio is 1:40:130；
(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1:1:1.3:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl-2-butanone It is mixed with isopropyl ether, 4h is reacted under condition of ice bath, carry out crystallisation by cooling, centrifuge separation, washing, purification after reaction and done It is dry to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2.5:10:0.02, in 50 DEG C of temperature strip 55min is reacted under part, hydrogen is continually fed into reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the own dioctyl phthalate of 3- tert-butyl -1,6-, the fluoro- 1,3- malonic acid of 2,2- bis- and 2,5,6, 6- tetramethyl -2,5- heptandiol is made into slurry, antimony acetate, titanium dioxide and trimethyl phosphate is added after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure 0.3MPa, the temperature of esterification is 252 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 90% of theoretical value, and wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol is 1: The own dioctyl phthalate of 2.0,3- tert-butyls -1,6-, fluoro- 1, the 3- malonic acid of 2,2- bis- and 2,5,6,6- tetramethyl -2,5- heptandiols add Enter the 4mol% that the sum of amount is terephthalic acid (TPA) additional amount, the own dioctyl phthalate of 3- tert-butyl -1,6-, fluoro- 1, the 3- malonic acid of 2,2- bis- With 2, the molar ratio of 5,6,6- tetramethyl -2,5- heptandiols is 2:3:4, the addition of antimony acetate, titanium dioxide and trimethyl phosphate Amount is respectively 0.03wt%, 0.24wt% and 0.04wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 256 DEG C, reaction time 45min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 88Pa, reaction temperature 278 DEG C, reaction time 75min, the number-average molecular weight of modified poly ester obtained is 29000, molecular weight distributing index 2.0；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 295 DEG C of spinning temperature, cooling temperature 21 DEG C, network pressure 0.23MPa, a roller speed 2500m/min, 85 DEG C of a roll temperature, two roller speed 3600m/min, two roll temperatures 105 DEG C, winding speed 3560m/min.
It is 3.0dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 4.0cN/dtex, breaking strength CV value are 4.8%, and elongation at break 39%, extension at break CV value is 8.0%, boiling shrinkage Rate is 6.8%, strip dry CV value 1.4%, oil content 0.80wt%, and internet pricing is 20/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 19%.
Embodiment 6
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) it prepares the own dioctyl phthalate of 2,5- di-t-butyl -1,6-: first mixing wolframic acid and hydrogen peroxide, at room temperature 15min is stirred, 2,4- di-t-butyl cyclohexanol is then added and first reacts 1.5h under the conditions of 83 DEG C of temperature, then is warming up to 92 DEG C 2.5h is reacted, in reaction process, reactant is in reflux state always, crystallisation by cooling, washing and purification is finally carried out, wherein instead When should start, the molar ratio of wolframic acid, 2,4- di-t-butyl cyclohexanol and hydrogen peroxide is 1:40:120；
(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1.1:1:1.2:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 4h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.03, in 50 DEG C of temperature condition Lower reaction 60min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the own dioctyl phthalate of 2,5- di-t-butyl -1,6-, the fluoro- 1,4- succinic acid of 2,2- bis- and 2, 5,6,6- tetramethyl -2,5- heptandiols are made into slurry, and antimony oxide, titanium dioxide and triphenyl phosphate is added and is uniformly mixed Afterwards, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure, and the temperature of esterification is 260 DEG C, when esterification is anti- Water quantity of distillate in answering is esterification terminal when reaching the 95% of theoretical value, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol For 1:1.6, the own dioctyl phthalate of 2,5- di-t-butyls -1,6-, the fluoro- 1, 4- succinic acid of 2,2- bis- and 2,5,6,6- tetramethyl -2,5- heptan The sum of additional amount of glycol is the 5mol% of terephthalic acid (TPA) additional amount, the own dioctyl phthalate of 2,5- di-t-butyls -1,6-, 2,2- bis- Fluoro- 1, 4- succinic acid and 2, the molar ratios of 5,6,6- tetramethyl -2,5- heptandiols are 2:4:5, antimony oxide, titanium dioxide and The additional amount of triphenyl phosphate is respectively 0.05wt%, 0.25wt% and 0.05wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 490Pa, and reaction temperature is 260 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 90Pa, reaction temperature 282 DEG C, reaction time 55min, the number-average molecular weight of modified poly ester obtained is 30000, molecular weight distributing index 2.0；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 295 DEG C of spinning temperature, cooling temperature 23 DEG C, network pressure 0.30MPa, a roller speed 2100m/min, 75 DEG C of a roll temperature, two roller speed 4000m/min, two roll temperatures 105 DEG C, winding speed 3850m/min.
It is 3.0dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 4.2cN/dtex, breaking strength CV value are 4.6%, and elongation at break 35%, extension at break CV value is 8.3%, boiling shrinkage Rate is 7.5%, strip dry CV value 1.5%, oil content 1.10wt%, and internet pricing is 22/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 15%.
Embodiment 7
Fused mass directly spinning adds the preparation method of coloured polyester fiber online, and steps are as follows:
(1) modified poly ester is prepared；
(1.1) it prepares the own dioctyl phthalate of 2,5- di-t-butyl -1,6-: first mixing wolframic acid and hydrogen peroxide, at room temperature 11min is stirred, 2,4- di-t-butyl cyclohexanol is then added and first reacts 1h under the conditions of 80 DEG C of temperature, then is warming up to 95 DEG C instead Answer 2.2h, in reaction process, reactant is in reflux state always, crystallisation by cooling, washing and purification is finally carried out, wherein reacting When beginning, the molar ratio of wolframic acid, 2,4- di-t-butyl cyclohexanol and hydrogen peroxide is 1:35:150；
(1.2) 2,5,6,6- tetramethyl -2,5- heptandiols, synthetic method are prepared are as follows:
(a) by the molar ratio of 1.2:1:1.2:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 3h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；
(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.02, in 42 DEG C of temperature condition Lower reaction 55min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the own dioctyl phthalate of 2,5- di-t-butyl -1,6-, the fluoro- 1,5- glutaric acid of 2,2- bis- and 2, 5,6,6- tetramethyl -2,5- heptandiols are made into slurry, and antimony glycol, titanium dioxide and Trimethyl phosphite is added and is uniformly mixed Afterwards, pressurization carries out esterification, moulding pressure 0.2MPa in nitrogen atmosphere, and the temperature of esterification is 250 DEG C, works as esterification Water quantity of distillate in reaction is esterification terminal when reaching the 92% of theoretical value, wherein mole of terephthalic acid (TPA) and ethylene glycol Than for 1:1.2, the own dioctyl phthalate of 2,5- di-t-butyls -1,6-, fluoro- 1, the 5- glutaric acid of 2,2- bis- and 2,5,6,6- tetramethyls -2,5- The sum of additional amount of heptandiol is the 4.5mol% of terephthalic acid (TPA) additional amount, the own dioctyl phthalate of 2,5- di-t-butyls -1,6-, 2,2- Two fluoro- 1,5- glutaric acids and 2, the molar ratio of 5,6,6- tetramethyl -2,5- heptandiols are 1.3:2:4, antimony glycol, titanium dioxide Additional amount with Trimethyl phosphite is respectively 0.04wt%, 0.22wt% and 0.01wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min The interior absolute pressure that is steadily evacuated to by normal pressure is 440Pa, and reaction temperature is 260 DEG C, reaction time 40min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 95Pa, reaction temperature 274 DEG C, reaction time 50min, the number-average molecular weight of modified poly ester obtained is 29500, molecular weight distributing index 2.1；
(2) by fused mass directly spinning after line adding technology is in conjunction with FDY technique, by the technique after combination by modified poly ester melt It is made modified poly ester FDY and adds coloured polyester fiber online to get fused mass directly spinning, wherein the online adding technology of fused mass directly spinning Process are as follows: before melt enters spinning manifold, Masterbatch after drying, melting, filtering and metering is injected, with melt one It rises after the full and uniform mixing of high-efficiency dynamic mixer, enters in spinning manifold jointly, the process of FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding, the parameter of FDY technique are as follows: and 288 DEG C of spinning temperature, cooling temperature 19 DEG C, network pressure 0.27MPa, a roller speed 2500m/min, 75 DEG C of a roll temperature, two roller speed 3600m/min, two roll temperatures 120 DEG C, winding speed 3920m/min.
It is 2.6dtex that final fused mass directly spinning obtained adds the filament number of coloured polyester fiber online, and breaking strength is 3.8cN/dtex, breaking strength CV value are 5.0%, and elongation at break 39%, extension at break CV value is 8.6%, boiling shrinkage Rate is 7.0%, strip dry CV value 1.44%, oil content 1.20wt%, and internet pricing is 20/m；
Fused mass directly spinning adds coloured polyester fiber at 25 DEG C online and places 60 months under conditions of relative humidity is 65% Afterwards, inherent viscosity decline 20%.

Claims (10)

1. fused mass directly spinning adds the preparation method of coloured polyester fiber online, it is characterized in that: by the online adding technology of fused mass directly spinning After in conjunction with FDY technique, modified poly ester FDY is made by modified poly ester melt by the technique after combination and is existed to get fused mass directly spinning Line adds coloured polyester fiber；
Masterbatch is added online into modified poly ester melt during fused mass directly spinning；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group, fluorine-containing two First acid and 2,5,6,6- tetramethyl -2,5- heptandiol successively carry out esterification and polycondensation reaction after mixing；
Binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, the tertiary fourth of 3- The own dioctyl phthalate of base -1,6- or the own dioctyl phthalate of 2,5- di-t-butyl -1,6-；
Fluorine-containing binary acid be the fluoro- 1,3- malonic acid of 2,2- bis-, the fluoro- 1,4- succinic acid of 2,2- bis-, the fluoro- 1,5- glutaric acid of 2,2- bis- or The fluoro- 1,4- succinic acid of 2,2,3,3- tetra-；
The structural formula of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:
2. the preparation method that fused mass directly spinning according to claim 1 adds coloured polyester fiber online, which is characterized in that institute It states Masterbatch to be made of the pigment of 20~30wt% and the polyester of 70~80wt%, the matter of the Masterbatch and modified poly ester melt For amount than being 1~3:97~99, the color of the pigment is red, yellow, blue, green, purple or black；
The own dioctyl phthalate of the 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and the own diformazan of 2,5- di-t-butyl -1,6- The synthetic method of acid are as follows:
Wolframic acid and hydrogen peroxide are mixed first, 10~15min is stirred at room temperature, raw alcohol is then added first at 80~85 DEG C Temperature under the conditions of react 1~2h, then be warming up to 90~95 DEG C of 2~3h of reaction, in reaction process, reactant is in reflux always State finally carries out crystallisation by cooling, washing and purification；
When reaction starts, the molar ratio of wolframic acid, raw alcohol and hydrogen peroxide is 1:30~40:120~150；
The own dioctyl phthalate of the 2- tert-butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and the own diformazan of 2,5- di-t-butyl -1,6- The corresponding raw alcohol of acid is respectively 2- tert. butyl cyclohexanol, the pure and mild 2,4- di-t-butyl cyclohexanol of 4- t-butylcyclohexyl；
The synthesis step of the 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:
(1) 1~1.2:1:1.2~1.3:2.0~3.0 molar ratio is pressed by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- bis- Methyl -2- butanone and isopropyl ether mixing, react 2~4h under condition of ice bath, carry out crystallisation by cooling, centrifugation point after reaction From, wash, refine and be dried to obtain octyne glycol；
(2) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2~3:10:0.01~0.03, at 40~50 DEG C 50~60min is reacted under the conditions of temperature, is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2, 5,6,6- tetramethyl -2,5- heptandiol.
3. the preparation method that fused mass directly spinning according to claim 2 adds coloured polyester fiber online, which is characterized in that institute The preparation step for stating modified poly ester is as follows:
(1) esterification；
By terephthalic acid (TPA), ethylene glycol, the binary acid with tert-butyl side group, fluorine-containing binary acid and 2,5,6,6- tetramethyl -2,5- Heptandiol is made into slurry, and catalyst, delustering agent and stabilizer is added after mixing, and pressurization be esterified anti-in nitrogen atmosphere It answers, moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 90% or more when be esterification terminal；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 250~260 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 270~282 DEG C, and the reaction time is 50~90min.
4. the preparation method that fused mass directly spinning according to claim 3 adds coloured polyester fiber online, which is characterized in that institute The molar ratio for stating terephthalic acid (TPA) and ethylene glycol is 1:1.2~2.0, the binary acid with tert-butyl side group, fluorine-containing binary acid With 2, the sum of the additional amount of 5,6,6- tetramethyl -2,5- heptandiols is 3~5mol% of terephthalic acid (TPA) additional amount, the band uncle The molar ratio of the binary acid of butyl side group, fluorine-containing binary acid and 2,5,6,6- tetramethyl -2,5- heptandiol be 1~2:2~4:3~ 5, the additional amount of the catalyst, delustering agent and stabilizer be respectively terephthalic acid (TPA) additional amount 0.03~0.05wt%, 0.20~0.25wt% and 0.01~0.05wt%.
5. the preparation method that fused mass directly spinning according to claim 4 adds coloured polyester fiber online, which is characterized in that institute Stating catalyst is antimony oxide, antimony glycol or antimony acetate, and the delustering agent is titanium dioxide, and the stabilizer is tricresyl phosphate Phenyl ester, trimethyl phosphate or Trimethyl phosphite.
6. the preparation method that fused mass directly spinning according to claim 5 adds coloured polyester fiber online, which is characterized in that change Property polyester number-average molecular weight be 25000~30000, molecular weight distributing index be 1.8~2.2.
7. the preparation method that fused mass directly spinning according to claim 1 adds coloured polyester fiber online, which is characterized in that institute State the process of the online adding technology of fused mass directly spinning are as follows: before melt enters spinning manifold, injection through drying, melting, filtering and Masterbatch after metering enters in spinning manifold jointly together with melt after the full and uniform mixing of high-efficiency dynamic mixer；
The process of the FDY technique are as follows: metering, spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding；
The parameter of the FDY technique are as follows: 285~295 DEG C of spinning temperature, 19~23 DEG C of cooling temperature, network pressure 0.20~ 0.30MPa, a 1800~2500m/min of roller speed, 75~90 DEG C of a roll temperature, two 3600~4000m/min of roller speed, two rollers 105~125 DEG C of temperature, 3560~3920m/min of winding speed.
8. adding the preparation method system of coloured polyester fiber online using fused mass directly spinning as described in any one of claims 1 to 7 The fused mass directly spinning obtained adds coloured polyester fiber online, it is characterized in that: being modified poly ester FDY；The molecule of the modified poly ester Chain includes terephthalic acid (TPA) segment, ethylene glycol segment, the binary acid segment with tert-butyl side group, fluorine-containing binary acid segment and 2,5, 6,6- tetramethyl -2,5- heptandiol segment.
9. fused mass directly spinning according to claim 8 adds coloured polyester fiber online, which is characterized in that fused mass directly spinning is online Add coloured polyester fiber filament number be 1.0~3.0dtex, breaking strength >=3.8cN/dtex, breaking strength CV value≤ 5.0%, elongation at break is 35 ± 4%, extension at break CV value≤9.0%, and boiling water shrinkage is 7.0 ± 0.5%, strip dry CV value ≤ 1.5%, oil content is 1.00 ± 0.20wt%, and internet pricing is 20 ± 4/m.
10. fused mass directly spinning according to claim 8 adds coloured polyester fiber online, which is characterized in that fused mass directly spinning exists After line adds coloured polyester fiber at 25 DEG C and places 60 months under conditions of relative humidity is 65%, inherent viscosity decline 15 ~20%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022511950A (en) * 2018-12-27 2022-02-01 江蘇恒力化繊股▲ふん▼有限公司 Manufacturing method of biodegradable polyester fiber

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1247181A (en) * 1999-08-25 2000-03-15 成都惟精防水材料研究所 One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol
CN103835014A (en) * 2014-03-24 2014-06-04 江苏恒科新材料有限公司 Production process of melt direct-spinning semidull terylene FDY
CN106087100A (en) * 2016-06-12 2016-11-09 福建百宏聚纤科技实业有限公司 A kind of fused mass directly spinning adds the manufacture method of color silk online
CN106757518A (en) * 2017-01-10 2017-05-31 扬州富威尔复合材料有限公司 A kind of long filament low melting point polyester fiber and preparation method thereof
CN108035011A (en) * 2017-12-14 2018-05-15 江苏恒力化纤股份有限公司 Fused mass directly spinning colored polyester fiber and preparation method thereof
CN108048940A (en) * 2017-12-14 2018-05-18 江苏恒力化纤股份有限公司 Soft type polyester fiber and preparation method thereof
CN108071009A (en) * 2017-12-14 2018-05-25 江苏恒力化纤股份有限公司 A kind of method for reducing spun polyester thread filoplume
CN108130624A (en) * 2017-12-14 2018-06-08 江苏恒力化纤股份有限公司 A kind of polyester imitates linen look abnormal contraction composite filament and preparation method thereof
CN108385186A (en) * 2017-12-14 2018-08-10 江苏恒力化纤股份有限公司 A kind of polyester POY fibers and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1247181A (en) * 1999-08-25 2000-03-15 成都惟精防水材料研究所 One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol
CN103835014A (en) * 2014-03-24 2014-06-04 江苏恒科新材料有限公司 Production process of melt direct-spinning semidull terylene FDY
CN106087100A (en) * 2016-06-12 2016-11-09 福建百宏聚纤科技实业有限公司 A kind of fused mass directly spinning adds the manufacture method of color silk online
CN106757518A (en) * 2017-01-10 2017-05-31 扬州富威尔复合材料有限公司 A kind of long filament low melting point polyester fiber and preparation method thereof
CN108035011A (en) * 2017-12-14 2018-05-15 江苏恒力化纤股份有限公司 Fused mass directly spinning colored polyester fiber and preparation method thereof
CN108048940A (en) * 2017-12-14 2018-05-18 江苏恒力化纤股份有限公司 Soft type polyester fiber and preparation method thereof
CN108071009A (en) * 2017-12-14 2018-05-25 江苏恒力化纤股份有限公司 A kind of method for reducing spun polyester thread filoplume
CN108130624A (en) * 2017-12-14 2018-06-08 江苏恒力化纤股份有限公司 A kind of polyester imitates linen look abnormal contraction composite filament and preparation method thereof
CN108385186A (en) * 2017-12-14 2018-08-10 江苏恒力化纤股份有限公司 A kind of polyester POY fibers and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
林尚安等: "《高分子化学》", 30 April 1963, 人民教育出版社 *
陈琳: "《基础有机化学实验》", 28 February 2009, 中国医药科技出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022511950A (en) * 2018-12-27 2022-02-01 江蘇恒力化繊股▲ふん▼有限公司 Manufacturing method of biodegradable polyester fiber
JP7053960B2 (en) 2018-12-27 2022-04-12 江蘇恒力化繊股▲ふん▼有限公司 Manufacturing method of biodegradable polyester fiber

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