CN109722735A - Lower shrinkage type polyester drawn yarns and preparation method thereof - Google Patents
Lower shrinkage type polyester drawn yarns and preparation method thereof Download PDFInfo
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- CN109722735A CN109722735A CN201811615746.8A CN201811615746A CN109722735A CN 109722735 A CN109722735 A CN 109722735A CN 201811615746 A CN201811615746 A CN 201811615746A CN 109722735 A CN109722735 A CN 109722735A
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Abstract
The present invention relates to a kind of lower shrinkage type polyester drawn yarns and preparation method thereof, the preparation method comprises the following steps: processing by FDY technique to modified poly ester, add heat treatment without tension process between nervous heat-setting process and rolling step to get lower shrinkage type polyester drawn yarns；Modified poly ester the preparation method comprises the following steps: terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the binary acid with tert-butyl side group successively to be carried out to esterification and polycondensation reaction after mixing.The boiling water shrinkage of lower shrinkage type polyester drawn yarns obtained is 3.0 ± 0.5%, and dye-uptake under the conditions of 125 DEG C of temperature is that 86.3~89.8%, K/S value is 22.32~24.34.Preparation method of the invention, simple process and low cost, the dyeability and percent thermal shrinkage of lower shrinkage type polyester drawn yarns obtained are low.
Description
Technical field
The invention belongs to modified polyester fiber technical field, it is related to a kind of lower shrinkage type polyester drawn yarns and its preparation side
Method.
Background technique
Terylene is the product name of China's polyester fiber, is an important species in synthetic fibers.It is with essence to benzene
Dioctyl phthalate (PTA) or terephthalic acid (TPA) diformazan vinegar (DMT) and ethylene glycol (EG) are raw material through esterification or transesterification and polycondensation reaction
Prepared by fiber-forming polymer-polyethylene terephthalate (PET) through spinning and post-process made of fiber.With washing
The production-scale expansion of synthetic fibre, production technology are also greatly improved, by the production of the incipient product that routinizes, gradually
Develop to production mode reforms such as high-tech, functionalization, fibres in differentiation, the application field of polyester fiber also takes fiber from initial
Gradually develop to the fields such as decoration, industry.With fiber production technology continuously improve and it is perfect, improve the extra price of fiber
Value is the inexorable trend of chemical fibre development.
With Levels of Social Economic Development and the improvement of people's living standards, people are to the superior, comfortable of clothing fabric
Change has urgent need.Low shrink terylene filament can be made fluffy because it has the advantages that shrinking percentage is low and good stability of the dimension
The relatively good fabric of Song Xing, drapability and feel, market prospects are boundless.Low-shrinkage and dimensional stability are polyester fibres
Tie up development a direction, and influence fiber quality be polyester macromolecule collection state structure, be mainly concerned between polyester molecule
Active force, the form and structure of crystallization, orientation structure etc., and the form and structure that crystallize are emphasis therein.Low receipts
Contracting dacron thread has good dimensional stability and heat-resistant stability, therefore the field that is widely used.
Shrinking percentage is an important performance indexes of civilian dacron thread, the reversible thermal expansion and contraction with general solid matter
Difference tends to occur irreversible thermal contraction after chemical fibre is heated, and in hot water washing and ironing, contraction shows more bright
It is aobvious.The civilian dacron thread of lower shrinkage type has the characteristics that heated after-contraction is small.Although the prior art is by control over feed rate(OFR) and carries out
The civilian silk of lower shrinkage type terylene can be also made in nervous thermal finalization, but since the length of fiber in nervous heat-setting process is fixed not
It is changeable, the folding of macromolecular chain can be inhibited, limit the growth of crystal grain, cause to crystallize existing defects, this will affect dacron thread
It is heat-shrinked recoverability (percent thermal shrinkage is higher).
Further, since terylene belongs to hydrophobic fibre, hydrophilic radical is not contained on molecule, is lacked in molecular structure yet
Can be with the active group in conjunction with dyestuff, the dyeability of polyester fiber is bad.In addition, polyester fiber finished product is partially crystallizable
Supramolecular structure, it is in anti conformation that crystalline portion strand is parallel to each other mostly, and amorphous region is then in cis- structure more
As, and its molecules align is quite close, which further increases the upper dye difficulty of polyester fiber.The dyeing one of conventional PET fiber
As use disperse dyeing, it usually needs dyed under high temperature (be greater than 130 DEG C) high pressure, this method is in addition to increasing in technique
Complexity except, the high requirements on the equipment, high production cost, dyeing effect is poor.
Therefore, the great realistic meaning of lower shrinkage type dacron thread that a kind of dyeability is good and percent thermal shrinkage is low is developed.
Summary of the invention
The purpose of the invention is to overcome problems of the prior art, provide a kind of dyeability it is good and be heat-shrinked
The low lower shrinkage type polyester drawn yarns and preparation method thereof of rate.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
The preparation method of lower shrinkage type polyester drawn yarns, processes modified poly ester by FDY technique, in nervous thermal finalization
Heat treatment without tension process is added between process and rolling step to get lower shrinkage type polyester drawn yarns；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and
Binary acid with tert-butyl side group successively carries out esterification and polycondensation reaction after mixing；
The structural formula of dihydric alcohol with trimethylsilyl side group is as follows:
In formula, R is-CH2-、-CH(CH3)-or-C ((CH3)2)-；
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 heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；
The relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；
The certain temperature refers to 180~200 DEG C.
The present invention in the strand of polyester by introducing the dihydric alcohol segment with trimethylsilyl side group and with tert-butyl side
The binary acid segment of base, so that the dyeability of modified poly ester is significantly improved, specifically:
The present invention uses dihydric alcohol (3- trimethylsilyl -1,2- propylene glycol, 3- trimethylsilyl -3- with trimethylsilyl side group
Methyl-1,2- propylene glycol or 3- trimethylsilyl -3,3- dimethyl -1,2- propylene glycol) and binary acid segment with tert-butyl side group
Polyester is modified, the dihydric alcohol with trimethylsilyl side group and the binary acid segment with tert-butyl side group can significantly increase and change
The space free volume of property polyester, in the dihydric alcohol especially with trimethylsilyl side group trimethylsilyl and with tert-butyl side group two
The presence of first acid segment can cause the variation of main chain activity, so that the interaction force between chain element is changed, strand list
Distance between member can also occur to change accordingly, increase modified poly ester cavity free volume, the increase of empty free volume can
It reduces dye molecule and penetrates into the difficulty inside modified poly ester, improve the dyeability of modified poly ester, reduce dyeing temperature, contracting
The time of short dyeing reduces energy consumption, improves the dye-uptake of modified poly ester.It is that molecule compares this is mainly due to disperse dyes
It is small, without the dyestuff of water soluble group in structure, exist in granular form mostly, partial size is in several hundred nanometers between one micron.
Dyestuff dyeing rate within 100 DEG C is very slow, even if dyeing in the dye bath of boiling, dyeing rate and dyeing percentage are not yet
Height, when lower shrinkage type polyester drawn yarns dyeing of the invention, with the continuous improvement of temperature, side group is first in polyester macromolecule chain
In strand setting in motion, when dye bath temperature is increased to 120~130 DEG C, the dihydric alcohol with trimethylsilyl side group and with tert-butyl
The severe degree of the binary acid sub-chain motion of side group is greater than strand, and graininess dyestuff is diffused to fibrous inside
When, because the empty free volume that side group trimethylsilyl is formed is bigger than the slit free volume that strand is formed, therefore dyestuff expands
Scattered rate is higher, and fiber dyeing performance is more preferable.
In addition, the present invention reduces the shrinking percentage of polyester industrial fiber by the mutual cooperation of heat treatment temperature and over feed rate(OFR),
Fiber is in heat treatment, and macromolecular chain folded chain easy to form in amorphous area is conducive to the further growth of crystal grain, at this time
Crystallinity increases, and along with the raising of crystallinity, fiber can generate a certain amount of contraction, and the present invention, which passes through, improves over feed rate(OFR), and one
Aspect eliminates influence of the high elastic deformation to winding, on the other hand eliminates the shadow of the contraction of fiber during crystallinity improves
It rings.
As a preferred technical scheme:
The preparation method of lower shrinkage type polyester drawn yarns as described above, the space of the certain temperature refer to a pair of parallel
Space between arrangement and non-coplanar hot plate, hot plate are located in FDY equipment between last group of setting roller and take-up roll；Edge
The length of the traffic direction of modified poly ester tow, two hot plates is 3.0~4.0m, and the both ends of two hot plates flush；Modified poly ester tow
When passing through among from two hot plates, the distance between two hot plates are 5~10mm；The present invention passes through control hot plate temperature (i.e. institute
State certain temperature) guarantee that macromolecular rearrangement can obtain energy, the length of hot plate is controlled to guarantee enough crystallization times, controls silk
Beam guarantees the efficiency of heat treatment at a distance from hot plate, and the mutual coordinated of three improves the integrality of fiber crystallization, and then subtracts
Thermal contraction during few fiber applications, wherein hot plate temperature is too low, it is difficult to guarantee that macromolecular rearrangement can obtain enough energy
Amount；Hot plate temperature is excessively high to destroy the former structure that oneself forms；Hot plate length is too short, and crystallization time is too short, influences fiber crystallization
Integrality influences fiber percent thermal shrinkage；The too long efficiency decline manufacturing apparatus waste of hot plate length；Tow too small appearance at a distance from hot plate
It easily causes and is contacted with the direct of tow；Tow excessive thermal efficiency at a distance from hot plate reduces；
Spacing between last group of setting roller and take-up roll is 300~400mm；Two hot plates and last group of thermal finalization
Spacing between roller is 200~300mm.
The preparation method of lower shrinkage type polyester drawn yarns as described above, the conjunction of the dihydric alcohol with trimethylsilyl side group
At steps are as follows:
(1) trimethylsilyl propylene, peracetic acid and methylene chloride are mixed by the molar ratio of 1:5~10:10~15,35~
5~8h is reacted under the conditions of 40 DEG C of temperature, when reaction, accompanies by stirring, removes solvent after reaction, it is purified be refining to obtain
Trimethylsilyl epoxidation of propylene object；
(2) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object are mixed, under agitation heating water bath to 80~85
DEG C, insulation reaction l0~15min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain band front three silicon
The dihydric alcohol of base side group, the concentrated sulfuric acid is the sulfuric acid of mass concentration 70%, when reaction starts, trimethylsilyl epoxidation of propylene object
Molar ratio with water is 1:20~40, and the quality of the concentrated sulfuric acid accounts for the 0.1~0.15% of the sum of mixture quality；
R is-CH (CH in the structural formula of the dihydric alcohol with trimethylsilyl side group3)-and-C ((CH3)2)-when, described three
First silicon substrate propylene corresponds to 3- trimethylsilyl -3- metering system and 3- trimethylsilyl -3,3- dimethyl allene；
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 preparation method of lower shrinkage type polyester drawn yarns as described above, the preparation step of the modified poly ester are as follows:
(1) esterification；
Terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the binary acid with tert-butyl side group are made into
Catalyst, delustering agent and stabilizer is added after mixing in slurry, and pressurization carries out esterification, pressurization pressure in nitrogen atmosphere
Power is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches 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 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.
The preparation method of lower shrinkage type polyester drawn yarns as described above, the molar ratio of the terephthalic acid (TPA) and ethylene glycol
For 1:1.2~2.0, the sum of the dihydric alcohol with trimethylsilyl side group and the additional amount of binary acid with tert-butyl side group are pair
3~5mol% (molar percentage) of phthalic acid additional amount, the dihydric alcohol with trimethylsilyl side group with tert-butyl side
The molar ratio of the binary acid of base is 1~2:2~3；Dihydric alcohol of the present invention with trimethylsilyl side group and two with tert-butyl side group
The additional amount of first acid is not limited to this, those skilled in the art can actual conditions be adjusted, but adjust amplitude and should not be too large, add
The excessive regularity destruction to polyester macromolecule structure of dosage is too big, excessive to the crystallinity and Effect on Mechanical Properties of fiber,
It is unfavorable for the production and application of fiber, additive amount is too low, then effect is unobvious；
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% (mass percent).
The preparation method of lower shrinkage type polyester drawn yarns as described above, the catalyst are antimony oxide, ethylene glycol
Antimony or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or phosphorous acid front three
Ester.
The preparation method of lower shrinkage type polyester drawn yarns as described above, the number-average molecular weight of modified poly ester is 25000~
30000, molecular weight distributing index is 1.8~2.2.
The preparation method of lower shrinkage type polyester drawn yarns as described above, the process of the FDY technique are as follows: metering, spinneret
Plate squeezes out, cools down, oils, stretching, thermal finalization and winding；
The parameter of the FDY technique are as follows: 285~300 DEG C of spinning temperature, 20~25 DEG C of cooling temperature, network pressure 0.20
~0.30MPa, a 2600~2800m/min of roller speed, 83~92 DEG C of a roll temperature, two roller speed 4200~4500m/min, two
125~145 DEG C of roll temperature, 4130~4420m/min of winding speed.
The present invention also provides low receipts made from a kind of preparation method using lower shrinkage type polyester drawn yarns as described above
Miniature polyester drawn yarns are modified poly ester FDY；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, two with trimethylsilyl side group
First alcohol segment and binary acid segment with tert-butyl side group.
As a preferred technical scheme:
Lower shrinkage type polyester drawn yarns as described above, the filament number of lower shrinkage type polyester drawn yarns are 1~2dtex,
Breaking strength >=4.5cN/dtex, elongation at break be 18.0 ± 2.0%, internet pricing be 10 ± 5/m, line density deviation ratio≤
1.0%, breaking strength CV value≤8.0%, extension at break CV value≤8.0%；Lower shrinkage type polyester drawn yarns produced by the present invention
Other mechanical performances (in addition to thermal contraction performance) it is suitable with conventional polyester product made from the prior art, not because improve dye
Performance and reduce other mechanical performances；
Boiling water shrinkage is 3.0 ± 0.5%；The boiling water shrinkage of civilian dacron thread in the prior art is 6~10%, this
Invention improves the stability of fiber size, reduces the thermal contraction in its application process；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 86.3~89.8%, K/S value is
22.32~24.34, fastness to soaping (washing staining and cotton staining) reaches 5 grades, and dry fastness reaches 5 grades, fastness to wet rubbing
Greater than 4 grades；Other test conditions under the same conditions, dye-uptake of comparative sample under the conditions of 130 DEG C of temperature be 86.2%,
K/S value is 21.78, and for fastness to soaping less than 5 grades, washing staining is 4~5 grades, and cotton staining is 4 grades, and dry fastness is 4~5
Grade, fastness to wet rubbing are 3~4 grades, and the difference of comparative sample and lower shrinkage type polyester drawn yarns of the invention is only that its material is
Conventional polyester.
Invention mechanism:
The present invention in the strand of polyester by introducing the dihydric alcohol segment with trimethylsilyl side group and with tert-butyl side
The binary acid of base, so that the dyeability of polyester is significantly improved, by increasing between nervous heat-setting process and rolling step
If heat treatment without tension process, to reduce the percent thermal shrinkage of polyester drawn yarns.
The mechanism for reducing percent thermal shrinkage is as follows:
Fiber is in post-processing stretching process, and due to the effect of mechanical stress, fiber orientation degree is significantly increased and has
Certain crystallinity, to make elongate fiber and total deformation work reduce, during stretching, although the big portion of fibrogenic deformation
It point is expendable plastic deformation under room temperature, often oneself is fixed because of crystallization, however some can be in room temperature
It is lower to restore because of the relaxation of tensile stress, or reply can be shunk in subsequent heat-treated, in the application process of fiber
In this shrink that reply be that the shrinking percentage of fiber will be largely affected by performance (such as security performance, endurance quality of fiber
Deng), it is assumed that the fiber is used as tire cord, and in use, cord fabric thread is stretched repeatedly, compressed, is bent tire, causes
Tire is heated, leads to curtain linear shrinkage creep, but when curtain linear shrinkage is excessive may knife cord fabric delamination, and then lead to tire
Disintegrate, this carrys out greatly hidden danger to using of seat belts for tire.
It is the shrinking percentage for reducing polyester drafting silk as much as possible at present during the spin-drawing of polyester drafting silk,
It generally requires to carry out nervous thermal finalization (carrying out shaping fiber under some tension using setting roller) after carrying out multiple tracks stretching,
To overfeeding of the over feed rate(OFR) for 1~2% is wound with after nervous thermal finalization, by carrying out nervous thermal finalization to fiber, in certain temperature
Under conditions of degree and some tension, the mobility of molecule segment is improved, so that intermolecular combination obtains even closer, raising fiber
Average grain size and crystallinity, to drop low-fiber shrinking percentage, but since fiber has certain height during stretching
Deformation is played, elastic recovery can be generated in the case where tension reduces, therefore, it is fixed that the speed of winding head has to be lower than last group heat
The speed of type roller needs certain over feed rate(OFR), is shunk, is expired with guaranteeing that the silk after stretching obtains a degree of low-tension
The final product quality of meaning and package prevent package from causing turned-down edge because of overtension, over feed rate(OFR) need to control in a certain range (1~
2%) it, crosses conference and adverse effect is generated to final product quality and package.Although can be to a certain extent by nervous thermal finalization+overfeeding
Reduce shrinking percentage, but in nervous heat-setting process, due to the length of fiber be fixed it is immutable, it is suppressed that macromolecular chain
Folding, thus the rate of grain growth is restricted, and causes to crystallize existing defects (crystallinity increases less), and only pass through
Control overfeeding can not reduce crystal defect, when this will lead to fiber obtained and is heat-treated in application process, fiber it is big
Strand and segment have higher activity, are easy to produce deorientation, cause fiber that a certain amount of shrink occurs and (shrink
Rate is larger).
In fact, the thermal finalization mode of fiber is not only nervous thermal finalization, further includes relaxation heat setting.Relaxation heat setting is again
Referred to as free shrink thermal finalization is fiber under complete no-station pole canopy or the lesser situation of tension, by certain temperature to fiber
Be heat-treated, under the conditions of relaxation heat setting, fiber can free shrink, the macromolecular chain folding easy to form in amorphous area
Chain is conducive to the further growth of crystal grain, in addition more abundant heat treatment time, therefore after heat treatment without tension, the knot of fiber
Brilliant degree increases more (compared to nervous thermal finalization), to make that fibrous inside high elastic deformation is restored while internal stress is filled
Divide relaxation, so that fibrogenic contraction reply is smaller when being heat-treated in application process.Current relaxation heat is fixed
Type be mainly used for polyester staple fiber carry out thermal finalization processing, heat treatment temperature is lower (130 DEG C or so), heat treatment time compared with
It is long, it is difficult to be suitable for long filament and produce.
The present invention by the way that the over feed rate(OFR) that polyester tow is wound is promoted to 3~5% in the process of polyester drafting silk,
Hot plate arranged in parallel above and below a pair of is set between one of setting roller last in FDY equipment and take-up roll simultaneously, by polyester
Tow passes through among two hot plates, improves the crystallinity of polyester tow, has restored the high elastic deformation inside polyester tow, so that
Polyester tow internal stress obtains a certain amount of relaxation, and then reduces polyester drafting silk when being heat-treated in application process and send out
Raw contraction is replied.The present invention reduces the receipts of polyester drafting silk by the mutual cooperation of heat treatment temperature and higher over feed rate(OFR)
Shrinkage, fiber is in heat treatment, and macromolecular chain folded chain easy to form in amorphous area is conducive to the further life of crystal grain
Long, crystallinity increases at this time, and along with the raising of crystallinity, fiber can generate a certain amount of contraction, and the present invention is super by improving
The rate of feeding, on the one hand eliminates influence of the high elastic deformation to winding, on the other hand eliminates the receipts of fiber during crystallinity improves
The influence of contracting.In addition, the present invention is by the mutual cooperation of heat treatment temperature, hot plate length and tow and hot plate apart from three, one
Aspect overcomes the defect that prior art heat treatment without tension is not suitable for long filament production, on the other hand, improves fiber crystallization
Integrality improves the stability of fiber size, reduces the thermal contraction in its application process.
The mechanism for improving dyeability 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 body has bigger bulk compared with slit free volume,
Promotion for the permeability of small molecule, empty free volume are more obvious compared with slit free volume effect.
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, side group structure etc..When position a certain on main polymer chain is replaced by side group, necessarily cause main chain
The variation of activity, to change the interaction force of chain and interchain, chain can also occur to change accordingly at a distance from interchain,
As a result lead to the variation of cohesive energy and free volume, polarity, size, length of the substituent group on polymer side chain etc. are to strand
Rigid, intermolecular interaction so that the fractional free volume of polymer architecture all have a certain impact, therefore, substituent group
The effect that difference generates is different, and the permeability and separation performance for often leading to polymer is also different.
The structural formula of dihydric alcohol with trimethylsilyl side group of the invention is as follows:
In formula, R is-CH2(dihydric alcohol with trimethylsilyl side group is 3- trimethylsilyl -1,2- propylene glycol),-CH (CH3)-
(dihydric alcohol with trimethylsilyl side group is 3- trimethylsilyl -3- methyl-1,2- propylene glycol) or-C ((CH3)2)-(band trimethylsilyl
The dihydric alcohol of side group is 3- trimethylsilyl -3,3- dimethyl -1,2- propylene glycol).
For ethylene glycol straight chain molecule, the C atom on main chain is arranged in indention one on the other, when on main chain some
H atom on methylene is by methyl (- CH3) when replacing, C atom and main chain C atom on substituent group not in the same plane, in
It is that four on the C of center sp3 hybridized orbit is Chong Die with the unoccupied orbital on four C atoms around respectively, formation four is identical
σ key, arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, when three hydrogen of methyl are into one
When step is replaced by methyl or trimethylsilyl, it is capable of forming a bigger tetrahedral structure, this is in the arrangement of positive tetrahedron shape
The strand that strand is arranged relative to indention, empty free volume significantly increase very much, can significantly improve small point
The permeability and diffusivity of son are conducive to atom further, since the bond distance of carbon silicon bonds is greater than the bond distance of carbon-carbon bond in trimethylsilyl
It rotates freely, and then is conducive to increase empty free volume；And when the H atom on main chain on some methylene is replaced by long-chain branch
When base replaces, what is mainly increased is slit free volume, and increase amplitude is smaller, permeability and diffusible promotion to small molecule
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 free volume
Increase.
The presence of trimethylsilyl can cause the variation of main chain activity in dihydric alcohol with trimethylsilyl side group, to change
Interaction force between chain element, the distance between molecule chain element can also occur to change accordingly, lead to the sky of modified poly ester
Hole free volume increases.Compared with short-chain branch substituent group (such as methyl, ethyl group), trimethylsilyl occupies biggish space
Position will obtain bigger free volume in the mode of strand arrangement；Compared with chain substituent of drawing money on credit, one side front three silicon
The free volume that base increases is more empty free volume, and the free volume for chain substituent increase of drawing money on credit is more slit
The rigidity of free volume, another aspect trimethylsilyl is greater than chain substituent of drawing money on credit, and reduces the entanglement between strand, thus three
First silicon substrate has more free volumes compared with chain substituent of drawing money on credit in the mode that strand arranges.Two with trimethylsilyl side group
So that the space free volume of modified poly ester increases, especially empty free volume increase is become apparent for the introducing of first alcohol.
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.
Binary acid with tert-butyl side group of the invention be 5- tert-butyl -1,3- phthalic acid, 2- tert-butyl -1,6- oneself two
Formic acid, the own dioctyl phthalate of 3- tert-butyl -1,6- or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6-, the wherein own diformazan of 2- tert-butyl -1,6-
Acid, the own dioctyl phthalate of 3- tert-butyl -1,6- and 2, the own dioctyl phthalate of 5- di-t-butyl -1,6- are adipic acid, are a kind of fatty acid, just
Property be less than 5- tert-butyl -1,3- phthalic acid, be conducive to the flexibility for promoting polyester segment, in the binary acid with tert-butyl side group
The presence of tert-butyl can cause the variation of main chain activity, thus the interaction force between changing chain element, molecule chain element
Between distance can also occur to change accordingly, lead to the increase of the empty free volume of modified poly ester.(such as with short-chain branch substituent group
The groups such as methyl, ethyl) it compares, tert-butyl occupies biggish spatial position, will obtain more in the mode of strand arrangement
Big free volume；Compared with chain substituent of drawing money on credit, what one side tert-butyl increased is empty free volume, and long-chain branch replaces
What base increased is slit free volume, and the rigidity of another aspect tert-butyl is greater than chain substituent of drawing money on credit, reduces between strand
Entanglement, thus tert-butyl compared with draw money on credit chain substituent in the mode that strand arranges have more free volumes.In addition, working as
When binary acid with tert-butyl side group is 5- tert-butyl -1,3- phthalic acid, the phenyl ring of meta position dioctyl phthalate connection will form one
Bigger asymmetry segment not only increases the steric hindrance migrated between segment and increases in segment around the rotation of meta position connecting key
Steric hindrance, the introducing of meta-isomer is conducive to the increase of free volume, the introducing of the binary acid with tert-butyl side group but also
The empty free volume of modified poly ester increases.
The increase of empty free volume will make water or other molecules such as dyestuff etc. be easier to penetrate into modified poly ester macromolecular
Inside generates active influence to dyeing of modified poly ester etc., can reduce the temperature of dyeing, reduces energy consumption, while in dyeing
Improve the dye-uptake of fiber.
The utility model has the advantages that
(1) preparation method of lower shrinkage type polyester drawn yarns of the invention, passes through heat treatment temperature and higher over feed rate(OFR)
Mutual cooperation, improve fiber crystallization integrality, reduce the thermal contraction in its application process；
(2) preparation method of lower shrinkage type polyester drawn yarns of the invention, by introducing band tert-butyl side group in the polyester
Binary acid and dihydric alcohol with trimethylsilyl side group polyester is modified, reduce the temperature of dyeing, shorten dyeing
Time improves the dye-uptake of fiber, reduces energy consumption, while increasing spinning property；
(3) lower shrinkage type polyester drawn yarns of the invention, dyeability is excellent, good mechanical performance, and application prospect is good.
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
The preparation method of lower shrinkage type polyester drawn yarns, steps are as follows:
(1) modified poly ester is prepared；
(1.1) esterification；
Terephthalic acid (TPA), ethylene glycol, 3- trimethylsilyl -1,2- propylene glycol and 5- tert-butyl -1,3- phthalic acid are made into
Antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing in slurry, and pressurization be esterified anti-in nitrogen atmosphere
It answers, moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 91%, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol is 1:2.1,3- trimethylsilyl -1,2- third
The sum of additional amount of two pure and mild 5- tert-butyl -1,3- phthalic acids is the 4mol% of terephthalic acid (TPA) additional amount, 3- trimethylsilyl -
The molar ratio of 1,2-PD and 5- tert-butyl -1,3- phthalic acid is 1:3, antimony oxide, titanium dioxide and phosphoric acid triphen
The additional amount of ester is respectively 0.03wt%, 0.20wt% and 0.04wt% of terephthalic acid (TPA) additional amount；
(1.2) 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 25000, molecular weight distributing index 1.8；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 4.9% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 200 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 3.0m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
5mm, the spacing between last group of setting roller and take-up roll is 300mm, between two hot plates and last group of setting roller
Spacing is 200mm；
The parameter of FDY technique are as follows: 285 DEG C of spinning temperature, 20 DEG C of cooling temperature, network pressure 0.23MPa, a roller speed
2800m/min, 88 DEG C of a roll temperature, two roller speed 4200m/min, two 125 DEG C of roll temperatures, winding speed 4220m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 2dtex, and fracture is strong
Degree is 4.8cN/dtex, and elongation at break 18.0%, internet pricing is 12/m, and line density deviation ratio is 0.95%, and fracture is strong
Spending CV value is 7.8%, and extension at break CV value is 8.0%, boiling water shrinkage 3.5%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 88.6%, K/S value is 24.34, resistance to
WASHING COLOR FASTNESS reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 6 grades.
Comparative example 1
A kind of preparation method of lower shrinkage type polyester drawn yarns, step is substantially same as Example 1, and difference exists
In step (1) is simultaneously not added with 3- trimethylsilyl -1,2-PD and 5- tert-butyl -1,3- phthalic acid, i.e., does not carry out to polyester
Modified, the filament number of lower shrinkage type polyester drawn yarns obtained is 2.0dtex, breaking strength 4.5cN/dtex, fracture
Elongation is 19.0%, and internet pricing is 12/m, and line density deviation ratio is 1.00%, and breaking strength CV value is 7.7%, and fracture is stretched
Long CV value is 8.0%, boiling water shrinkage 3.5%；With embodiment 1 other test conditions under the same conditions, at 130 DEG C
Temperature under the conditions of dye-uptake be 84.7%, K/S value be 21.58, for fastness to soaping less than 5 grades, washing staining is 4~5 grades,
Cotton staining is 4 grades, and dry fastness is 4~5 grades, and fastness to wet rubbing is 3~4 grades.
With the comparison of embodiment 1 it can be found that the present invention passes through addition 3- trimethylsilyl -1,2-PD and 5- tert-butyl -
1,3- phthalic acid has been obviously improved the dyeability of fiber, while 3- trimethylsilyl -1,2-PD and 5- tert-butyl -1,3-
The addition of phthalic acid is smaller on the influence of other performances of fiber, has no effect on its processing performance and mechanical performance.
Comparative example 2
A kind of preparation method of lower shrinkage type polyester drawn yarns, step is substantially same as Example 1, and difference exists
In step (1) is using 1,2 dodecanediols substitution 3- trimethylsilyl -1,2-PD and 5- tert-butyl -1,3- benzene diformazan
Acid, the filament numbers of lower shrinkage type polyester drawn yarns obtained are 2.0dtex, breaking strength 4.6cN/dtex, and fracture is stretched
Long rate is 18.0%, and internet pricing is 12/m, and line density deviation ratio is 1.00%, and breaking strength CV value is 7.6%, extension at break
CV value is 8.0%, boiling water shrinkage 3.5%；With embodiment 1 other test conditions under the same conditions, at 130 DEG C
Dye-uptake under the conditions of temperature is that 85.6%, K/S value is 21.67, and fastness to soaping is less than 5 grades, and washing staining is 4~5 grades, cotton
Staining is 4 grades, and dry fastness is 4~5 grades, and fastness to wet rubbing is 3~4 grades.
It compares with embodiment 1 it can be found that binary acid (5- tert-butyl -1,3- phthalic acid) and band with tert-butyl side group
The dihydric alcohol (3- trimethylsilyl -1,2- propylene glycol) of trimethyl silicane side group is relative to 1,2 dodecyls containing chain substituent of drawing money on credit
Glycol is more advantageous to the dyeability for promoting fiber, this is primarily due to the on the one hand binary acid with tert-butyl side group and with front three
The free volume that tert-butyl in the dihydric alcohol of base silicon side group increases is more empty free volume, and chain substituent increasing of drawing money on credit
Big free volume is more slit free volume, the rigidity of the tert-butyl in binary acid on the other hand with tert-butyl side group
Greater than chain substituent of drawing money on credit, reduce the entanglement between strand, thus the binary acid with tert-butyl side group takes compared with containing long-chain branch
The 1 of Dai Ji, 2 dodecanediols have more free volumes in the mode that strand arranges, and then are more advantageous to promotion
The dyeability of fiber.
Comparative example 3
A kind of preparation method of lower shrinkage type polyester drawn yarns, substantially with embodiment 1, the difference is that in step (2)
Without heat treatment without tension process, and winding speed is 2680m/min, and the over feed rate(OFR) of winding is 1.47%, final obtained low
The filament number of shrinkage type polyester drawn yarns be 2.0dtex, breaking strength 4.3cN/dtex, elongation at break 22.0%,
Internet pricing is 12/m, and line density deviation ratio is 1.10%, and breaking strength CV value is 7.9%, and extension at break CV value is 8.0%,
Boiling water shrinkage is 5.5%；With embodiment 1 other test conditions under the same conditions, under the conditions of 130 DEG C of temperature
Dye-uptake is that 88.3%, K/S value is 23.87, and for fastness to soaping less than 5 grades, washing staining is 4~5 grades, and cotton staining is 4 grades, is done
Crock fastness is 4~5 grades, and fastness to wet rubbing is 3~4 grades.By embodiment 1 with the comparison of comparative example 3 as can be seen that the present invention passes through
It adds heat treatment without tension process and significantly reduces the shrinking percentage of lower shrinkage type polyester drawn yarns.
Embodiment 2
The preparation method of lower shrinkage type polyester drawn yarns, 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) esterification；
Terephthalic acid (TPA), ethylene glycol, 3- trimethylsilyl -1,2- propylene glycol and the own dioctyl phthalate of 2- tert-butyl -1,6- are made into
Slurry is added antimony oxide, titanium dioxide and Trimethyl phosphite after mixing, pressurizes and be esterified in nitrogen atmosphere
Reaction, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical value
92% when be esterification terminal, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol be 1:2.0,3- trimethylsilyl -1,2-
The sum of propylene glycol and the additional amount of the own dioctyl phthalate of 2- tert-butyl -1,6- are the 3mol% of terephthalic acid (TPA) additional amount, 3- front three silicon
The molar ratio of base -1,2-PD and the own dioctyl phthalate of 2- tert-butyl -1,6- is 2:2, antimony oxide, titanium dioxide and phosphorous acid
The additional amount of trimethyl is respectively 0.04wt%, 0.25wt% and 0.01wt% 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 40min
The interior absolute pressure that is steadily evacuated to by normal pressure is 400Pa, and reaction temperature is 272 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 28000, molecular weight distributing index 1.8；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 4.2% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 207 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 3.2m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
6mm, the spacing between last group of setting roller and take-up roll is 311mm, between two hot plates and last group of setting roller
Spacing is 220mm；
The parameter of FDY technique are as follows: 285 DEG C of spinning temperature, 25 DEG C of cooling temperature, network pressure 0.20MPa, a roller speed
2700m/min, 90 DEG C of a roll temperature, two roller speed 4500m/min, two 145 DEG C of roll temperatures, winding speed 4130m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 1.5dtex, fracture
Intensity is 4.5cN/dtex, and elongation at break 18.0%, internet pricing is 5/m, and line density deviation ratio is 0.96%, and fracture is strong
Spending CV value is 7.2%, and extension at break CV value is 7.6%, boiling water shrinkage 3.5%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 86.3%, K/S value is 23.65, resistance to
WASHING COLOR FASTNESS reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 6 grades.
Embodiment 3
The preparation method of lower shrinkage type polyester drawn yarns, 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) dihydric alcohol with trimethylsilyl side group is prepared；
(a) 3- trimethylsilyl -3- metering system, peracetic acid and methylene chloride are mixed by the molar ratio of 1:5:10,35
DEG C temperature under the conditions of react 5h, when reaction, accompanies by stirring, removes solvent after reaction, purified and be refining to obtain front three silicon
Base epoxidation of propylene object；
(b) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 80 DEG C under agitation,
Insulation reaction 10min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain the band as shown in formula (I)
The dihydric alcohol of trimethylsilyl side group, the R in formula (I) are-CH (CH3)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, reaction
When beginning, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:20, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality
0.1%；
(1.3) esterification；
Terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the own dioctyl phthalate of 2- tert-butyl -1,6- are made into
Antimony glycol, titanium dioxide and triphenyl phosphate is added after mixing in slurry, and pressurization be esterified anti-in nitrogen atmosphere
It answers, moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value
When 90% be esterification terminal, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol be 1:1.2, two with trimethylsilyl side group
The sum of the additional amount of the pure and mild own dioctyl phthalate of 2- tert-butyl -1,6- of member is the 3mol% of terephthalic acid (TPA) additional amount, band trimethylsilyl
The dihydric alcohol of side group and the molar ratio of the own dioctyl phthalate of 2- tert-butyl -1,6- are 1:2.4, antimony glycol, titanium dioxide and tricresyl phosphate
The additional amount of phenyl ester is respectively 0.04wt%, 0.22wt% 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 45min
The interior absolute pressure that is steadily evacuated to by normal pressure is 450Pa, and reaction temperature is 276 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 275
DEG C, reaction time 60min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 2.0；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 3.3% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 215 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 3.3m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
7mm, the spacing between last group of setting roller and take-up roll is 335mm, between two hot plates and last group of setting roller
Spacing is 235mm；
The parameter of FDY technique are as follows: 290 DEG C of spinning temperature, 20 DEG C of cooling temperature, network pressure 0.20MPa, a roller speed
2600m/min, 92 DEG C of a roll temperature, two roller speed 4300m/min, two 125 DEG C of roll temperatures, winding speed 4130m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 1dtex, and fracture is strong
Degree is 4.5cN/dtex, and elongation at break 20.0%, internet pricing is 10/m, and line density deviation ratio is 0.97%, and fracture is strong
Spending CV value is 7.6%, and extension at break CV value is 8.0%, boiling water shrinkage 2.5%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 86.3%, K/S value is 22.32, resistance to
WASHING COLOR FASTNESS reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 5 grades.
Embodiment 4
The preparation method of lower shrinkage type polyester drawn yarns, 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) dihydric alcohol with trimethylsilyl side group is prepared；
(a) 3- trimethylsilyl -3- metering system, peracetic acid and methylene chloride are mixed by the molar ratio of 1:10:15,40
DEG C temperature under the conditions of react 8h, when reaction, accompanies by stirring, removes solvent after reaction, purified and be refining to obtain front three silicon
Base epoxidation of propylene object；
(b) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 85 DEG C under agitation,
Insulation reaction 15min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain the band as shown in formula (I)
The dihydric alcohol of trimethylsilyl side group, the R in formula (I) are-CH (CH3)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, reaction
When beginning, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:40, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality
0.15%；
(1.3) esterification；
Terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the own dioctyl phthalate of 3- tert-butyl -1,6- are made into
Antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing in slurry, and pressurization be esterified anti-in nitrogen atmosphere
It answers, moulding pressure 0.1MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value
When 90% be esterification terminal, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol be 1:1.5, two with trimethylsilyl side group
The sum of the additional amount of the pure and mild own dioctyl phthalate of 3- tert-butyl -1,6- of member is the 5mol% of terephthalic acid (TPA) additional amount, band trimethylsilyl
The dihydric alcohol of side group and the molar ratio of the own dioctyl phthalate of 3- tert-butyl -1,6- are 1.6:2.8, antimony glycol, titanium dioxide and phosphorous
The additional amount of sour trimethyl 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 280 DEG C, reaction time 80min, 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 270
DEG C, reaction time 40min, the number-average molecular weight of modified poly ester obtained is 29000, molecular weight distributing index 2.2；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 4.8% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 222 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 3.4m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
8mm, the spacing between last group of setting roller and take-up roll is 346mm, between two hot plates and last group of setting roller
Spacing is 250mm；
The parameter of FDY technique are as follows: 290 DEG C of spinning temperature, 22 DEG C of cooling temperature, network pressure 0.30MPa, a roller speed
2600m/min, 83 DEG C of a roll temperature, two roller speed 4300m/min, two 130 DEG C of roll temperatures, winding speed 4420m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 1dtex, and fracture is strong
Degree is 4.44cN/dtex, and elongation at break 16.0%, internet pricing is 15/m, and line density deviation ratio is 1.0%, and fracture is strong
Spending CV value is 7.6%, and extension at break CV value is 7.9%, boiling water shrinkage 3.0%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 89.8%, K/S value is 22.32, resistance to
WASHING COLOR FASTNESS reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 5 grades.
Embodiment 5
The preparation method of lower shrinkage type polyester drawn yarns, 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) dihydric alcohol with trimethylsilyl side group is prepared；
(a) 3- trimethylsilyl -3- metering system, peracetic acid and methylene chloride are mixed by the molar ratio of 1:10:10,36
DEG C temperature under the conditions of react 6h, when reaction, accompanies by stirring, removes solvent after reaction, purified and be refining to obtain front three silicon
Base epoxidation of propylene object；
(b) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 84 DEG C under agitation,
Insulation reaction 12min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain the band as shown in formula (I)
The dihydric alcohol of trimethylsilyl side group, the R in formula (I) are-CH (CH3)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, reaction
When beginning, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:30, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality
0.14%；
(1.3) esterification；
Terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the own dioctyl phthalate of 3- tert-butyl -1,6- are made into
Antimony acetate, titanium dioxide and trimethyl phosphate is added after mixing in slurry, and pressurization carries out esterification in nitrogen atmosphere,
Moulding pressure is 0.3MPa, and the temperature of esterification is 252 DEG C, when the water quantity of distillate in esterification reaches the 90% of theoretical value
When be esterification terminal, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol be 1:1.8, the dihydric alcohol with trimethylsilyl side group
It is the 4mol% of terephthalic acid (TPA) additional amount, band trimethylsilyl side group with the sum of the additional amount of the own dioctyl phthalate of 3- tert-butyl -1,6-
Dihydric alcohol and the molar ratio of the own dioctyl phthalate of 3- tert-butyl -1,6- be 1.2:2, antimony acetate, titanium dioxide and trimethyl phosphate
Additional 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 282 DEG C, reaction time 80min, 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 272
DEG C, reaction time 75min, the number-average molecular weight of modified poly ester obtained is 30000, molecular weight distributing index 1.9；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 4.0% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 232 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 3.6m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
8.5mm, the spacing between last group of setting roller and take-up roll is 368mm, between two hot plates and last group of setting roller
Spacing be 260mm；
The parameter of FDY technique are as follows: 300 DEG C of spinning temperature, 21 DEG C of cooling temperature, network pressure 0.28MPa, a roller speed
2800m/min, 83 DEG C of a roll temperature, two roller speed 4200m/min, two 135 DEG C of roll temperatures, winding speed 4350m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 2dtex, and fracture is strong
Degree is 4.6cN/dtex, and elongation at break 18.0%, internet pricing is 10/m, and line density deviation ratio is 0.95%, and fracture is strong
Spending CV value is 8.0%, and extension at break CV value is 8.0%, boiling water shrinkage 3.2%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 87.38%, K/S value is 24.34,
Fastness to soaping reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 5 grades.
Embodiment 6
The preparation method of lower shrinkage type polyester drawn yarns, 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) dihydric alcohol with trimethylsilyl side group is prepared；
(a) 3- trimethylsilyl -3,3- dimethyl allene, peracetic acid and methylene chloride are mixed by the molar ratio of 1:8:12,
React 5h under the conditions of 40 DEG C of temperature, when reaction accompanies by stirring, removes solvent after reaction, purified and be refining to obtain three
First silicon substrate epoxidation of propylene object；
(b) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 85 DEG C under agitation,
Insulation reaction 10min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain the band as shown in formula (I)
The dihydric alcohol of trimethylsilyl side group, the R in formula (I) are-C ((CH3)2)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, reaction
When beginning, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:25, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality
0.12%；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the own dioctyl phthalate of 2,5- di-t-butyl -1,6-
It is made into slurry, antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, pressurization carries out ester in nitrogen atmosphere
Change reaction, moulding pressure is normal pressure, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical value
95% when be esterification terminal, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol be 1:2.0, with trimethylsilyl side group
Dihydric alcohol and 2, the sum of additional amount of the own dioctyl phthalate of 5- di-t-butyl -1,6- are the 5mol% of terephthalic acid (TPA) additional amount, band three
The dihydric alcohol and 2 of first silicon substrate side group, the molar ratio of the own dioctyl phthalate of 5- di-t-butyl -1,6- are 2:3, antimony oxide, titanium dioxide
The additional amount of titanium and 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 270 DEG C, reaction time 90min, 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 270
DEG C, reaction time 55min, the number-average molecular weight of modified poly ester obtained is 27000, molecular weight distributing index 1.9；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 3.0% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 235 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 3.8m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
9mm, the spacing between last group of setting roller and take-up roll is 384mm, between two hot plates and last group of setting roller
Spacing is 280mm；
The parameter of FDY technique are as follows: 300 DEG C of spinning temperature, 25 DEG C of cooling temperature, network pressure 0.30MPa, a roller speed
2750m/min, 83 DEG C of a roll temperature, two roller speed 4200m/min, two 145 DEG C of roll temperatures, winding speed 4420m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 1.3dtex, fracture
Intensity is 4.5cN/dtex, and elongation at break 16.0%, internet pricing is 13/m, and line density deviation ratio is 1.0%, and fracture is strong
Spending CV value is 7.5%, and extension at break CV value is 7.8%, boiling water shrinkage 2.5%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 89.8%, K/S value is 22.99, resistance to
WASHING COLOR FASTNESS reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 6 grades.
Embodiment 7
The preparation method of lower shrinkage type polyester drawn yarns, 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) dihydric alcohol with trimethylsilyl side group is prepared；
(a) 3- trimethylsilyl -3,3- dimethyl allene, peracetic acid and methylene chloride are mixed by the molar ratio of 1:10:10,
React 6h under the conditions of 35 DEG C of temperature, when reaction accompanies by stirring, removes solvent after reaction, purified and be refining to obtain three
First silicon substrate epoxidation of propylene object；
(b) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 80 DEG C under agitation,
Insulation reaction 15min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain the band as shown in formula (I)
The dihydric alcohol of trimethylsilyl side group, the R in formula (I) are-C ((CH3)2)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, reaction
When beginning, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:35, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality
0.14%；
(1.3) esterification；
By terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the own dioctyl phthalate of 2,5- di-t-butyl -1,6-
It is made into slurry, antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing, pressurization carries out ester in nitrogen atmosphere
Change reaction, moulding pressure 0.2MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical
Value 92% when be esterification terminal, wherein the molar ratio of terephthalic acid (TPA) and ethylene glycol be 1:1.9, band trimethylsilyl side group
Dihydric alcohol and 2, the sum of additional amount of the own dioctyl phthalate of 5- di-t-butyl -1,6- be terephthalic acid (TPA) additional amount 4mol%, band
The dihydric alcohol of trimethylsilyl side group and 2, the molar ratio of the own dioctyl phthalate of 5- di-t-butyl -1,6- are 1:2.6, antimony glycol, dioxy
Change titanium and Trimethyl phosphite additional amount be respectively terephthalic acid (TPA) additional amount 0.04wt%, 0.22wt% and
0.01wt%；
(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 280 DEG C, reaction time 60min, 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 30000, molecular weight distributing index 2.0；
(2) lower shrinkage type polyester drawn yarns are prepared；
Modified poly ester is processed to get lower shrinkage type polyester drawn yarns, the process of FDY technique by FDY technique are as follows: meter
Amount, spinneret squeeze out, cool down, oil, stretching, thermal finalization, heat treatment without tension and winding, and heat treatment without tension refers to surpassing winding
The polyester tow that the rate of feeding is 5.0% passes through the space between the hot plate that a pair of arranged in parallel and non-co-planar while temperature is 240 DEG C,
Hot plate is located in FDY equipment between last group of setting roller and take-up roll, along the traffic direction of polyester tow, the length of two hot plates
Degree is 4.0m, and the both ends of two hot plates flush, and when polyester tow passes through among two hot plates, the distance between two hot plates are
10mm, the spacing between last group of setting roller and take-up roll is 400mm, between two hot plates and last group of setting roller
Spacing is 300mm；
The parameter of FDY technique are as follows: 295 DEG C of spinning temperature, 20 DEG C of cooling temperature, network pressure 0.25MPa, a roller speed
2800m/min, 92 DEG C of a roll temperature, two roller speed 4500m/min, two 125 DEG C of roll temperatures, winding speed 4390m/min.
Final lower shrinkage type polyester drawn yarns obtained are modified poly ester FDY, filament number 2dtex, and fracture is strong
Degree is 4.65cN/dtex, and elongation at break 19.0%, internet pricing is 8/m, and line density deviation ratio is 1.0%, breaking strength
CV value is 7.92%, and extension at break CV value is 7.88%, boiling water shrinkage 2.5%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 89.8%, K/S value is 24.34, resistance to
WASHING COLOR FASTNESS reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is 6 grades.
Claims (10)
1. the preparation method of lower shrinkage type polyester drawn yarns, it is characterized in that: being processed by FDY technique to modified poly ester, tight
It opens and adds heat treatment without tension process between heat-setting process and rolling step to get lower shrinkage type polyester drawn yarns；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and with uncle
The binary acid of butyl side group successively carries out esterification and polycondensation reaction after mixing；
The structural formula of dihydric alcohol with trimethylsilyl side group is as follows:
In formula, R is-CH2-、-CH(CH3)-or-C ((CH3)2)-；
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-；
The heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；
The relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；
The certain temperature refers to 180~200 DEG C.
2. the preparation method of lower shrinkage type polyester drawn yarns according to claim 1, which is characterized in that the certain temperature
Space refer to the space between a pair of arranged in parallel and non-coplanar hot plate, hot plate is located in FDY equipment last group heat calmly
Between type roller and take-up roll；Along the traffic direction of modified poly ester tow, the length of two hot plates is 3.0~4.0m, the two of two hot plates
End flushes；When modified poly ester tow passes through among two hot plates, the distance between two hot plates are 5~10mm；Last group
Spacing between setting roller and take-up roll is 300~400mm；Spacing between two hot plates and last group of setting roller is
200~300mm.
3. the preparation method of lower shrinkage type polyester drawn yarns according to claim 1, which is characterized in that the band front three silicon
The synthesis step of the dihydric alcohol of base side group is as follows:
(1) trimethylsilyl propylene, peracetic acid and methylene chloride are mixed by the molar ratio of 1:5~10:10~15, at 35~40 DEG C
Temperature under the conditions of react 5~8h, when reaction, accompanies by stirring, removes solvent after reaction, it is purified be refining to obtain front three
Silicon substrate epoxidation of propylene object；
(2) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 80~85 DEG C under agitation,
Insulation reaction l0~15min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain band trimethylsilyl side
The dihydric alcohol of base, the concentrated sulfuric acid is the sulfuric acid of mass concentration 70%, when reaction starts, trimethylsilyl epoxidation of propylene object and water
Molar ratio be 1:20~40, the quality of the concentrated sulfuric acid accounts for the 0.1~0.15% of the sum of mixture quality；
R is-CH (CH in the structural formula of the dihydric alcohol with trimethylsilyl side group3)-and-C ((CH3)2)-when, the front three silicon
Base propylene corresponds to 3- trimethylsilyl -3- metering system and 3- trimethylsilyl -3,3- dimethyl allene；
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.
4. the preparation method of lower shrinkage type polyester drawn yarns according to claim 3, which is characterized in that the modified poly ester
Preparation step it is as follows:
(1) esterification；
Terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and the binary acid with tert-butyl side group are made into slurry,
Catalyst, delustering agent and stabilizer is added after mixing, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal
Pressure~0.3MPa, the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches the 90% of theoretical value
It is esterification terminal when above；
(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.
5. the preparation method of lower shrinkage type polyester drawn yarns according to claim 4, which is characterized in that the terephthaldehyde
The molar ratio of acid and ethylene glycol is 1:1.2~2.0, the dihydric alcohol with trimethylsilyl side group and the binary with tert-butyl side group
The sum of additional amount of acid is 3~5mol% of terephthalic acid (TPA) additional amount, the dihydric alcohol with trimethylsilyl side group with uncle
The molar ratio of the binary acid of butyl side group is 1~2:2~3, and the additional amount of the catalyst, delustering agent and stabilizer is respectively pair
0.03~0.05wt%, 0.20~0.25wt% and the 0.01~0.05wt% of phthalic acid additional amount.
6. the preparation method of lower shrinkage type polyester drawn yarns according to claim 5, which is characterized in that the catalyst is
Antimony oxide, antimony glycol or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, phosphoric acid
Trimethyl or Trimethyl phosphite.
7. the preparation method of lower shrinkage type polyester drawn yarns according to claim 6, which is characterized in that the number of modified poly ester
Average molecular weight is 25000~30000, and molecular weight distributing index is 1.8~2.2.
8. the preparation method of lower shrinkage type polyester drawn yarns according to claim 1, which is characterized in that the FDY technique
Process are as follows: metering, spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding；The parameter of the FDY technique are as follows: spinning
285~300 DEG C of temperature, 20~25 DEG C of cooling temperature, network pressure 0.20~0.30MPa, a 2600~2800m/ of roller speed
Min, 83~92 DEG C of a roll temperature, two 4200~4500m/min of roller speed, two 125~145 DEG C of roll temperatures, winding speed 4130
~4420m/min.
9. lower shrinkage made from the preparation method using lower shrinkage type polyester drawn yarns as described in any one of claims 1 to 8
Type polyester drawn yarns, it is characterized in that: being modified poly ester FDY；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, the dihydric alcohol with trimethylsilyl side group
Segment and binary acid segment with tert-butyl side group.
10. lower shrinkage type polyester drawn yarns according to claim 9, which is characterized in that lower shrinkage type polyester drawn yarns
Filament number is 1~2dtex, and breaking strength >=4.5cN/dtex, elongation at break is 18.0 ± 2.0%, and internet pricing is 10 ± 5
A/m, line density deviation ratio≤1.0%, breaking strength CV value≤8.0%, extension at break CV value≤8.0%, boiling water shrinkage are
3.0 ± 0.5%；
Dye-uptake of lower shrinkage type polyester drawn yarns under the conditions of 125 DEG C of temperature is that 86.3~89.8%, K/S value is 22.32
~24.34, fastness to soaping reaches 5 grades, and dry fastness reaches 5 grades, and fastness to wet rubbing is greater than 4 grades.
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