CN109680359A - The preparation method of the fluffy snow Neil silk of low boiling water - Google Patents
The preparation method of the fluffy snow Neil silk of low boiling water Download PDFInfo
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- CN109680359A CN109680359A CN201811615720.3A CN201811615720A CN109680359A CN 109680359 A CN109680359 A CN 109680359A CN 201811615720 A CN201811615720 A CN 201811615720A CN 109680359 A CN109680359 A CN 109680359A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
The present invention relates to a kind of preparation methods of the fluffy snow Neil silk of low boiling water, process by FDY technique to modified poly ester, add heat treatment without tension process between nervous heat-setting process and rolling step to get the fluffy snow Neil silk of low boiling water；The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and the binary acid segment with tert-butyl side group, heat treatment without tension refers to the space by polyester tow in relaxed state appropriate Jing Guo certain temperature, relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%, and certain temperature refers to 200~240 DEG C.The present invention is modified polyester by the binary acid with tert-butyl side group, improve the dyeability of fiber, again by the mutual cooperation of heat treatment temperature and higher over feed rate(OFR), improve the integrality of fiber crystallization, reduce the thermal contraction in its application process, preparation method simple process and low cost, application prospect are good.
Description
Technical field
The invention belongs to polyester fiber technical fields, are related to a kind of preparation method of the fluffy snow Neil silk of low boiling water.
Background technique
The production-scale continuous expansion of polyester fiber and development, so that polyester fiber and products thereof obtains in many fields
Be widely applied, especially clothes, luggage and industry with etc. fields.With the continuous development of economy and mentioning for people's lives
Height, requirement of the people to luggage and garment material is higher and higher, and just to the performance of polyester fiber, more stringent requirements are proposed for this.Add
It, the factors such as the price of raw material, the supply and demand in market, the update of equipment and development of technology make the competition of domestic each chemical fiber factory
It is increasingly fierce, enterprise have to update sophisticated equipment, imported technology and the talent, reduce product price, optimization technological design and
It researches and develops the approach such as distinguishing products and improves product competitiveness.
Terylene boiling water shrinkage, refer to the dacron thread of fixed length through boiling water treating after a certain period of time, contracted length and former
The ratio of length is the important indicator for reflecting polyester filament thermal finalization degree and dimensional stability, with post-processing, arrangement and fabric
Dyeability close relation, directly affect the bulkiness of the appearance of fabric, especially finished textile product.Fiber boiling water shrinkage
Height and raw material variety, process equipment and processing technology etc. because being known as very big relationship, the kind of feed change converts processing
Technique can influence the size of fiber boiling water shrinkage, but it is come from two angles of the degree of orientation and crystallinity of fiber
Change fiber boiling water shrinkage.
Chenille Yarns is made of heart yarn and decorative yarn, and heart yarn is interweaved by two one threads, in the laterally inserted cutting in gap
Decorative yarn.Its properity of influence such as fiber number, the twist and thickness of Chenille Yarns and appearance, and its unique long " suede
The fabric that hair " yarn is made into is determined with " velvet " abundant is suitable for wool fabrics, with the shorter snow Neil effect of villus.Snow
A kind of form of the Neil yarn as floriation yarn, have unique effect: villus is long, good hand touch, and richness is good, bulkiness, stretching, extension
Property, elasticity is good, and product has stronger vitality on the market.
Fluffy snow Neil is polyester fiber with silk, but since terylene belongs to hydrophobic fibre, is not contained on molecule hydrophilic
Property group, lack in molecular structure as cellulose or protein fibre can and the active group that combine of dyestuff,
The dyeability of polyester fiber is bad.In addition, polyester fiber finished product is the supramolecular structure of partially crystallizable, crystalline portion molecule
Chain is parallel to each other, and is mostly in anti conformation, and amorphous region is then in cisoid conformation more, and molecules align is quite close, this is into one
Step increases the upper dye difficulty of polyester fiber.Conventional polyester (PET) fiber generally selects disperse dyes at high temperature (130 DEG C) at present
It is dyed under high pressure, only carrying out dyeing at high temperature under high pressure just can guarantee the dye-uptake of fiber, and high temperature and pressure is to equipment
It is more demanding, energy consumption is larger, longer the time required to dyeing simultaneously because upper dye difficulty is big, cause the cost of the technique compared with
Height limits the application of multicolour polyster fibre to a certain extent.
In addition, industry is to polyester industrial yarn with the raising of basic industries development, high-technology and the level of consumption
More stringent requirements are proposed for quality and performance.In addition, with the gradually saturation in market, the exploitation more excellent product of performance is also
The inevitable requirement of development.Shrinking percentage is an important performance indexes of industrial yarn, and general solid matter is reversible expands with heat and contract with cold
Phenomenon is different, after chemical fibre is heated, tends to occur irreversible thermal contraction, and in hot water washing and ironing, contraction shows more
It is obvious.Industrial yarn (such as cord fabric thread, conveyer belt and conveyer belt) more carries out using shrinking percentage at a high temperature of long-time
Performance just increasingly constitutes an important evaluation index.Lower shrinkage type polyester industrial yarn has the characteristics that heated after-contraction is small,
Fabric or the rubber product being made from it have good dimensional stability and heat-resistant stability, can absorb impact load.Mainly
For coated fabric, conveyer belt weft etc..Its yield accounts for about the 20% of polyester industrial yarn yield.Although the prior art passes through control
Over feed rate(OFR) simultaneously carries out nervous thermal finalization also lower shrinkage type polyester industrial yarn can be made, but due to fiber in nervous heat-setting process
Length is fixed immutable, can inhibit the folding of macromolecular chain, limit the growth of crystal grain, causes to crystallize existing defects, this meeting
It is higher to influence industrial yarn percent thermal shrinkage.
Therefore, a kind of preparation method of the fluffy snow Neil silk for the low boiling water that dyeability is good and percent thermal shrinkage is low is developed
Great realistic meaning.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of existing skill, the low boiling water that a kind of dyeability is good and percent thermal shrinkage is low is provided
Fluffy snow Neil silk preparation method.
To achieve the above object, the present invention adopts the following technical scheme:
The preparation method of the fluffy snow Neil silk of low boiling water, processes modified poly ester by FDY technique, in nervous heat
Heat treatment without tension process is added between shaping process and rolling step to get the fluffy snow Neil silk of low boiling water；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol and with the binary acid-mixed of tert-butyl side group
Esterification and polycondensation reaction are successively carried out after closing uniformly；
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 using 5- tert-butyl -1,3- phthalic acid, the own dioctyl phthalate of 2- tert-butyl -1,6-, 3- tert-butyl -1,6- oneself
Dioctyl phthalate or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6- are modified polyester, easily cause the variation of main chain activity, thus
The interaction force between chain element is changed, the distance between molecule chain element can also occur to change accordingly, increase modified poly ester
Empty free volume.Disperse dyes are that molecule is smaller and in structure without the dyestuff of water soluble group, mostly with
Particle shape formula exists, partial size in several hundred nanometers between one micron, when modified poly ester of the present invention starts dyeing, in polyester macromolecule chain
Side group prior to strand setting in motion, when dye bath temperature need to be increased to 120 DEG C, side group movement severe degree be greater than molecule
Chain, simultaneously because the empty free volume that side group tert-butyl is formed is bigger than the slit free volume that strand is formed, therefore
Graininess dyestuff is promoted to the diffusion rate of fibrous inside significantly, so that significantly reducing dye molecule penetrates into modified poly ester
Internal difficulty improves the dyeability of modified poly ester, reduces dyeing temperature, shortens the time of dyeing, reduces energy consumption, and raising changes
The dye-uptake of property polyester；
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 is by the mutual cooperation of heat treatment temperature and over feed rate(OFR) to drop
The shrinking percentage of oligoester industrial yarn, 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, crystallinity increases at this time, and along with the raising of crystallinity, fiber can generate a certain amount of contraction, this
On the one hand invention eliminates influence of the high elastic deformation to winding, on the other hand eliminates crystallinity raising by improving over feed rate(OFR)
The influence of the contraction of fiber in the process.
As a preferred technical scheme:
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the list of the fluffy snow Neil silk of low boiling water
Silk size is 0.5~1.0dtex, and breaking strength >=3.3cN/dtex, elongation at break is 25.0 ± 5.0%, line density deviation
Rate≤1.2%, breaking strength CV value≤3.0%, extension at break CV value≤6.0%, boiling water shrinkage are 4.0 ± 0.5%,
Dye-uptake under the conditions of 130 DEG C of temperature is that 88.3~93.7%, K/S value is 22.37~24.72.Low boiling water of the present invention it is fluffy
The processing of pine snow Neil silk and mechanical property are suitable with the fibre property of the prior art, and boiling water shrinkage is substantially better than existing skill
(dye-uptake of the fiber of prior art under the conditions of 130 DEG C of temperature is 21.38) 86.7%, K/S value is to the fiber of art.
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the space of the certain temperature refers to a pair
Space between arranged in parallel and non-coplanar hot plate, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between；Along the traffic direction of modified poly ester tow, the length of two hot plates is 3.0~4.0m, and the both ends of two hot plates flush；Modified poly ester
When tow passes through among two hot plates, the distance between two hot plates are 5~10mm；The present invention passes through control hot plate temperature
(the i.e. described certain temperature) guarantees that macromolecular rearrangement can obtain energy, controls the length of hot plate to guarantee enough crystallization times,
Control tow guarantees that the efficiency of heat treatment, the mutual coordinated of three improve the integrality of fiber crystallization at a distance from hot plate,
And then reduce the thermal contraction during fiber applications, wherein hot plate temperature is too low, it is difficult to guarantee that macromolecular rearrangement can obtain foot
Enough energy；Hot plate temperature is excessively high to destroy former established structure；Hot plate length is too short, and crystallization time is too short, influences fiber
The integrality of crystallization influences fiber percent thermal shrinkage；The too long efficiency decline manufacturing apparatus waste of hot plate length；Tow is at a distance from hot plate
Too small be easy to cause contacts with the direct of tow；Tow excessive thermal efficiency at a distance from hot plate reduces.
The preparation method of the fluffy snow Neil silk of low boiling water as described above, last group of setting roller and take-up roll it
Between spacing be 300~400mm；Spacing between two hot plates and last group of setting roller is 200~300mm.
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the own dioctyl phthalate of the 2- tert-butyl -1,6-,
The synthetic method of the own dioctyl phthalate of 3- tert-butyl -1,6- and the own dioctyl phthalate of 2,5- di-t-butyl -1,6- 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 the fluffy snow Neil silk of low boiling water as described above, the preparation step of the modified poly ester is such as
Under:
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and binary acid with tert-butyl side group are made into slurry, be added catalyst, delustering agent and
After mixing, pressurization carries out esterification to stabilizer in nitrogen atmosphere, and moulding pressure is normal pressure~0.3MPa, esterification
Temperature be 240~250 DEG C, it is whole for esterification when the water quantity of distillate in esterification reaches 90% or more of theoretical value
Point；
(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 260~270 DEG C, the reaction time is 50~90min.
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the terephthalic acid (TPA), ethylene glycol and band
The molar ratio of the binary acid of tert-butyl side group is 1:1.2~2.0:0.03~0.05, the catalyst, delustering agent and stabilizer
Additional amount is respectively the 0.03~0.05wt%, 0.20~0.25wt% and 0.01~0.05wt% of terephthalic acid (TPA) additional amount.
It is good that the additive amount of binary acid with tert-butyl side group of the invention preferably range both can guarantee that modified fiber had
Mechanical property and crystallinity, while the dyeability of fiber can also be significantly improved, be conducive to the production and application of fiber, the tertiary fourth of band
The additive amount of the binary acid of base side group can appropriate adjustment according to actual needs, but should not too, adding too much divides greatly polyester
The regularity of minor structure destroy it is too big, it is excessive to the crystallinity and Effect on Mechanical Properties of fiber, be unfavorable for fiber production and
Using too low then dyeing effect is promoted unobvious；
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the catalyst are antimony oxide, second
Glycol antimony or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or phosphorous acid
Trimethyl.
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the number-average molecular weight of modified poly ester are
28000~32000, molecular weight distributing index is 1.8~2.2.
The preparation method of the fluffy snow Neil silk of low boiling water as described above, the process of the FDY technique are as follows: metering,
Spinneret squeezes out, cools down, oils, stretching, thermal finalization and winding；
The parameter of the FDY technique are as follows: 275~285 DEG C of spinning temperature, 20~22 DEG C of cooling temperature, network pressure 0.20
~0.30MPa, a 2200~2800m/min of roller speed, 55~65 DEG C of a roll temperature, two roller speed 3800~4200m/min, two
105~125 DEG C of roll temperature, 3680~4070m/min of winding speed.
Invention mechanism:
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 present invention has been obviously improved cationic terylene by introducing the binary acid with tert-butyl side group in polyester molecule chain
The dyeability of full-drawn yarn, the binary acid with tert-butyl side group are 5- tert-butyl -1,3- phthalic acid, 2- tert-butyl -1,6-
Own dioctyl phthalate, the own dioctyl phthalate of 3- tert-butyl -1,6- or 2, the own dioctyl phthalate of 5- di-t-butyl -1,6-, wherein 2- tert-butyl -1,6- oneself
Dioctyl phthalate, 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,
Its rigidity is less than 5- tert-butyl -1,3- phthalic acid, is conducive to the flexibility for promoting polyester segment, the binary with tert-butyl side group
The presence of tert-butyl can cause the variation of main chain activity in acid, thus the interaction force between changing chain element, strand
Distance between unit can also occur to change accordingly, lead to the increase of the empty free volume of modified poly ester.Replace with short-chain branch
Base (such as methyl, ethyl group) is compared, and tert-butyl occupies biggish spatial position, will be obtained in the mode of strand arrangement
Obtain bigger 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
What substituent group increased is slit free volume, and the rigidity of another aspect tert-butyl is greater than chain substituent of drawing money on credit, reduces strand
Between entanglement, thus tert-butyl compared with draw money on credit chain substituent in the mode that strand arranges have more free volumes.This
Outside, when the 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 be formed
One bigger asymmetry segment not only increases the steric hindrance migrated between segment and increases in segment around meta position connecting key
The steric hindrance of rotation, the introducing of meta-isomer are conducive to the increase of free volume.The introducing of binary acid with tert-butyl side group makes
The empty free volume for obtaining modified poly ester increases, and the increase of empty free volume will be such that water or other molecules such as dyestuff etc. is easier
Modified poly ester macromolecule internal is penetrated into, active influence is generated to dyeing of modified poly ester etc., the temperature of dyeing can be reduced, subtracted
Lack energy consumption, while improving the dye-uptake of fiber in dyeing.
In addition, especially fiber is in post-processing stretching process, due to mechanical stress in the preparation process of polyester fiber
Effect, fiber orientation degree is significantly increased and has certain crystallinity, so that elongate fiber and total deformation work be made to reduce, but
In drawing process, although fibrogenic deformation is largely expendable plastic deformation under room temperature, often because crystallization is made
With being fixed, however some can restore because of the relaxation of tensile stress at room temperature, or can be at subsequent heated place
Reply is shunk in reason, this shrinking percentage for shrinking the i.e. fiber of reply will be largely affected by the application process of fiber
The performance (such as security performance, endurance quality) of fiber, it is assumed that the fiber be used as tire cord, tire in use,
Cord fabric thread stretched repeatedly, compressed, bending, is caused tire heated, is led to curtain linear shrinkage creep, but when curtain linear shrinkage is excessive
Possible knife cord fabric delamination, and then tire is caused to disintegrate, this carrys out greatly hidden danger to using of seat belts for tire.At present poly-
It is past after carrying out multiple tracks stretching for the shrinking percentage for reducing polyester industrial fiber as much as possible during the spin-drawing of ester industrial yarn
Toward needing to carry out nervous thermal finalization (carrying out shaping under some tension to fiber using setting roller), arrived after nervous thermal finalization
It is wound with the overfeeding that over feed rate(OFR) is 1~2%, by carrying out nervous thermal finalization to fiber, in the item of certain temperature and some tension
Under part, improve the mobility of molecule segment so that intermolecular combination obtain it is even closer, improve fiber average grain size and
Crystallinity reduces to drop low-fiber shrinking percentage, but since fiber has certain high elastic deformation during stretching in tension
In the case where can generate elastic recovery, therefore, the speed of winding head has to be lower than the speed i.e. needs of last group of setting roller
Certain over feed rate(OFR) is shunk with guaranteeing that the silk after stretching obtains a degree of low-tension, obtains satisfied final product quality and volume
Dress prevents package from causing turned-down edge because of overtension, and over feed rate(OFR) need to control (1~2%) in a certain range, crosses conference to finished product
Quality and package generate adverse effect.Although shrinking percentage can be reduced to a certain extent by nervous thermal finalization+overfeeding,
In nervous heat-setting process, due to the length of fiber be fixed it is immutable, it is suppressed that the folding of macromolecular chain, thus crystal grain is raw
Long rate is restricted, and causes to crystallize existing defects (crystallinity increases less), and only can not be reduced by controlling overfeeding
Crystal defect, when this will lead to fiber obtained and is heat-treated in application process, the macromolecular chain and segment of fiber have
Higher activity, is easy to produce deorientation, causes fiber that a certain amount of contraction occurs (shrinking percentage 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 industrial fiber,
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 industrial fiber when being heat-treated in application process and send out
Raw contraction is replied.The present invention reduces the receipts of polyester industrial fiber 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 utility model has the advantages that
(1) preparation method of the fluffy snow Neil silk of low boiling water of the invention is surpassed by heat treatment temperature with higher
The mutual cooperation for the rate of feeding improves the integrality of fiber crystallization, reduces the thermal contraction in its application process；
(2) preparation method of the fluffy snow Neil silk of low boiling water of the invention, passes through the binary acid with tert-butyl side group
Polyester is modified, the temperature of dyeing is reduced, shortens the time of dyeing, improves the dye-uptake of fiber, reduces energy consumption,
Spinning property is increased simultaneously；
(3) preparation method of the fluffy snow Neil silk of low boiling water of the invention, simple process and low cost are great to answer
Use prospect.
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
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step are as follows:
(1) modified poly ester is prepared；
(1.1) esterification；
Terephthalic acid (TPA), ethylene glycol and 5- tert-butyl -1,3- phthalic acid are matched with the molar ratio of 1:1.2:0.03 and are slurried
Antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing in material, and pressurization be esterified anti-in nitrogen atmosphere
It answers, moulding pressure 0.3MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 90.1%, the additional amount of antimony oxide, titanium dioxide and triphenyl phosphate is respectively terephthaldehyde
0.03wt%, 0.20wt% and 0.01wt% of sour 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 50min
Interior that absolute pressure 400Pa is steadily evacuated to by normal pressure, reaction temperature is 260 DEG C, and reaction time 50min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 80Pa, and reaction temperature is 270 DEG C, instead
It is 90min, the modified poly ester that obtained number-average molecular weight is 32000 and molecular weight distributing index is 1.8 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 275 DEG C of spinning temperature,
20 DEG C of cooling temperature, network pressure 0.20MPa, a roller speed 2200m/min, 65 DEG C of a roll temperature, two roller speed 3800m/
Min, two 105 DEG C of roll temperatures, winding speed 3680m/min；
The polyester tow that it is 3.1% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 180 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 3.0m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 5mm, and the spacing between last group of setting roller and take-up roll is
300mm, the spacing between two hot plates and last group of setting roller are 200mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 0.9dtex, breaking strength 3.5cN/
Dtex, elongation at break 29.0%, line density deviation ratio are 1.1%, and breaking strength CV value is 2.5%, extension at break CV value
It is 4.9%, boiling water shrinkage 3.6%, dye-uptake under the conditions of 130 DEG C of temperature is that 88.9%, K/S value is 22.58.
Comparative example 1
A kind of preparation method of polyester fiber, preparation step is substantially the same manner as Example 1, the difference is that, without
Heat treatment without tension process, and winding speed is 2680m/min, the over feed rate(OFR) of winding is 1.47%, and the list of polyester fiber is made
Silk size is 0.9dtex, and breaking strength 3.3cN/dtex, elongation at break 32%, line density deviation ratio is 1.0%, is broken
Resistance to spalling CV value is 2.5%, and extension at break CV value is 4.8%, boiling water shrinkage 5.7%, under the conditions of 130 DEG C of temperature
Dye-uptake is that 89.1%, K/S value is 21.07.By embodiment 1 and the comparison of comparative example 1 as can be seen that the present invention is by adding relaxation
Heat treatment procedure significantly reduces the boiling water shrinkage of polyester fiber.
Comparative example 2
A kind of preparation method of polyester fiber, preparation step and embodiment 1 are almost the same, the difference is that, step (1)
In polyester be not modified be not added with 5- tert-butyl -1,3- phthalic acid.
The filament number of final polyester fiber obtained is 0.9dtex, breaking strength 3.6cN/dtex, elongation at break
It is 30.0%, line density deviation ratio is 1.1%, and breaking strength CV value is 2.5%, and extension at break CV value is 4.9%, boiling shrinkage
Rate is 3.7%, under the same conditions, dye-uptake under the conditions of 130 DEG C of temperature is with embodiment 1 other test conditions
84.3%, K/S value are 20.43.It compares and finds with embodiment 1, the present invention substantially increases terylene by being modified to polyester
The dyeability and mechanical property of fiber are unaffected.
Comparative example 3
A kind of preparation method of polyester fiber, preparation step and embodiment 1 are almost the same, the difference is that, step (1)
It is middle to substitute 5- tert-butyl -1,3- phthalic acid using 1,2 dodecanediols.
The filament number of final polyester fiber obtained is 0.9dtex, breaking strength 3.3cN/dtex, elongation at break
It is 31.0%, line density deviation ratio is 1.1%, and breaking strength CV value is 2.5%, and extension at break CV value is 4.8%, boiling shrinkage
Rate is 3.8%, under the same conditions, dye-uptake under the conditions of 130 DEG C of temperature is with embodiment 1 other test conditions
85.2%, K/S value are 20.76.
It compares and finds with embodiment 1, the binary acid with tert-butyl side group is relative to 1,2 dodecanes containing chain substituent of drawing money on credit
Base glycol is more advantageous to the dyeability for promoting fiber, this is primarily due to the uncle in the on the one hand binary acid with tert-butyl side group
The free volume that butyl increases is more empty free volume, and the free volume for chain substituent increase of drawing money on credit is more narrow
Free volume is stitched, the rigidity of the tert-butyl in binary acid on the other hand with tert-butyl side group is greater than chain substituent of drawing money on credit, reduces
Entanglement between strand, thus the binary acid with tert-butyl side group is compared with containing drawing money on credit the 1 of chain substituent, 2 dodecanediols
There are more free volumes in the mode of strand arrangement, and then be more advantageous to the dyeability for promoting fiber.
Embodiment 2
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step 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 and the own dioctyl phthalate of 2- tert-butyl -1,6- are matched with the molar ratio of 1:2.0:0.05 and are slurried
Antimony glycol, titanium dioxide and trimethyl phosphate is added after mixing in material, carries out being esterified instead under normal pressure in nitrogen atmosphere
It answers, the temperature of esterification is 250 DEG C, whole for esterification when the water quantity of distillate in esterification reaches the 99% of theoretical value
Point, the additional amount of antimony glycol, titanium dioxide and trimethyl phosphate be respectively terephthalic acid (TPA) additional amount 0.05wt%,
0.25wt% and 0.05wt%；
(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
Interior that absolute pressure 400Pa is steadily evacuated to by normal pressure, reaction temperature is 250 DEG C, and reaction time 30min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 99Pa, and reaction temperature is 260 DEG C, instead
It is 50min, the modified poly ester that obtained number-average molecular weight is 28000 and molecular weight distributing index is 2.2 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 285 DEG C of spinning temperature,
22 DEG C of cooling temperature, network pressure 0.30MPa, a roller speed 2800m/min, 65 DEG C of a roll temperature, two roller speed 4200m/
Min, two 125 DEG C of roll temperatures, winding speed 4070m/min；
The polyester tow that it is 3.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 183 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 3.2m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 6mm, and the spacing between last group of setting roller and take-up roll is
311mm, the spacing between two hot plates and last group of setting roller are 220mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 0.6dtex, breaking strength 3.2cN/
Dtex, elongation at break 21.0%, line density deviation ratio are 1.08%, and breaking strength CV value is 2.9%, extension at break CV value
It is 5.7%, boiling water shrinkage 3.6%, dye-uptake under the conditions of 130 DEG C of temperature is that 93.0%, K/S value is 24.22.
Embodiment 3
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step 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) esterification；
Terephthalic acid (TPA), ethylene glycol and the own dioctyl phthalate of 2- tert-butyl -1,6- are matched with the molar ratio of 1:1.5:0.04 and are slurried
Antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing in material, and pressurization carries out esterification in nitrogen atmosphere,
Moulding pressure is 0.2MPa, and the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches the 94% of theoretical value
When be esterification terminal, the additional amount of antimony acetate, titanium dioxide and Trimethyl phosphite is respectively terephthalic acid (TPA) additional amount
0.04wt%, 0.22wt% and 0.03wt%；
(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
Interior that absolute pressure 450Pa is steadily evacuated to by normal pressure, reaction temperature is 255 DEG C, and reaction time 40min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 90Pa, and reaction temperature is 265 DEG C, instead
It is 70min, the modified poly ester that obtained number-average molecular weight is 30000 and molecular weight distributing index is 2.0 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 280 DEG C of spinning temperature,
20~22 DEG C of cooling temperature, network pressure 0.25MPa, a roller speed 2500m/min, 60 DEG C of a roll temperature, two roller speeds
4000m/min, two 115 DEG C of roll temperatures, winding speed 3880m/min；
The polyester tow that it is 3.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 190 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 3.3m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 7mm, and the spacing between last group of setting roller and take-up roll is
335mm, the spacing between two hot plates and last group of setting roller are 235mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 0.7dtex, breaking strength 3.5cN/
Dtex, elongation at break 25.0%, line density deviation ratio are 1.1%, and breaking strength CV value is 2.6%, extension at break CV value
It is 5.4%, boiling water shrinkage 4.0%, dye-uptake under the conditions of 130 DEG C of temperature is that 91.2%, K/S value is 23.37.
Embodiment 4
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step 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) esterification；
Terephthalic acid (TPA), ethylene glycol and the own dioctyl phthalate of 3- tert-butyl -1,6- are matched with the molar ratio of 1:1.5:0.03 and are slurried
Antimony oxide, titanium dioxide and trimethyl phosphate is added after mixing in material, and pressurization be esterified anti-in nitrogen atmosphere
It answers, moulding pressure 0.15MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 92%, the additional amount of antimony oxide, titanium dioxide and trimethyl phosphate is respectively terephthalic acid (TPA)
0.03wt%, 0.25wt% and 0.01wt% of 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
Interior that absolute pressure 450Pa is steadily evacuated to by normal pressure, reaction temperature is 260 DEG C, and reaction time 50min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 80Pa, and reaction temperature is 270 DEG C, instead
It is 90min, the modified poly ester that obtained number-average molecular weight is 31000 and molecular weight distributing index is 1.9 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 275 DEG C of spinning temperature,
21 DEG C of cooling temperature, network pressure 0.25MPa, a roller speed 2400m/min, 55 DEG C of a roll temperature, two roller speed 3885m/
Min, two 125 DEG C of roll temperatures, winding speed 3700m/min；
The polyester tow that it is 5.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 192 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 3.4m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 8mm, and the spacing between last group of setting roller and take-up roll is
346mm, the spacing between two hot plates and last group of setting roller are 250mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 1.0dtex, breaking strength 3.6cN/
Dtex, elongation at break 30.0%, line density deviation ratio are 1.0%, and breaking strength CV value is 2.4%, extension at break CV value
It is 4.8%, boiling water shrinkage 3.5%, dye-uptake under the conditions of 130 DEG C of temperature is that 88.3%, K/S value is 22.37.
Embodiment 5
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step 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) esterification；
Terephthalic acid (TPA), ethylene glycol and the own dioctyl phthalate of 3- tert-butyl -1,6- are matched with the molar ratio of 1:1.8:0.05 and are slurried
Antimony oxide, titanium dioxide and Trimethyl phosphite is added after mixing in material, and pressurization be esterified anti-in nitrogen atmosphere
It answers, moulding pressure 0.25MPa, the temperature of esterification is 258 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 99%, the additional amount of antimony oxide, titanium dioxide and Trimethyl phosphite is respectively terephthaldehyde
0.035wt%, 0.20wt% and 0.04wt% of sour 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 35min
Interior that absolute pressure 410Pa is steadily evacuated to by normal pressure, reaction temperature is 253 DEG C, and reaction time 35min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 85Pa, and reaction temperature is 260 DEG C, instead
It is 90min, the modified poly ester that obtained number-average molecular weight is 29000 and molecular weight distributing index is 1.8 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 285 DEG C of spinning temperature,
20 DEG C of cooling temperature, network pressure 0.20MPa, a roller speed 2200m/min, 65 DEG C of a roll temperature, two roller speed 4100m/
Min, two 105 DEG C of roll temperatures, winding speed 3970m/min；
The polyester tow that it is 3.2% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 195 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 3.6m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 8.5mm, and the spacing between last group of setting roller and take-up roll is
368mm, the spacing between two hot plates and last group of setting roller are 260mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 0.5dtex, breaking strength 3.3cN/
Dtex, elongation at break 20.0%, line density deviation ratio are 1.2%, and breaking strength CV value is 3.0%, extension at break CV value
It is 6.0%, boiling water shrinkage 3.5%, dye-uptake under the conditions of 130 DEG C of temperature is that 93.7%, K/S value is 24.72.
Embodiment 6
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step 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) esterification；
Terephthalic acid (TPA), ethylene glycol and the own dioctyl phthalate of 2,5- di-t-butyl -1,6- are matched with the molar ratio of 1:1.6:0.04
At slurry, antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing, carries out ester under normal pressure in nitrogen atmosphere
Change reaction, the temperature of esterification is 255 DEG C, anti-for esterification when the water quantity of distillate in esterification reaches the 92% of theoretical value
Terminal is answered, the additional amount of antimony glycol, titanium dioxide and Trimethyl phosphite is respectively terephthalic acid (TPA) additional amount
0.03wt%, 0.20wt% and 0.01wt%；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min
Interior that absolute pressure 499Pa is steadily evacuated to by normal pressure, reaction temperature is 260 DEG C, and reaction time 50min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 80Pa, and reaction temperature is 260 DEG C, instead
It is 50min, the modified poly ester that obtained number-average molecular weight is 29500 and molecular weight distributing index is 1.9 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 285 DEG C of spinning temperature,
20 DEG C of cooling temperature, network pressure 0.20MPa, a roller speed 2400m/min, 55 DEG C of a roll temperature, two roller speed 3890m/
Min, two roll temperatures 105~DEG C, winding speed 3710m/min；
The polyester tow that it is 4.6% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 198 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 3.8m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 9mm, and the spacing between last group of setting roller and take-up roll is
384mm, the spacing between two hot plates and last group of setting roller are 280mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 0.6dtex, breaking strength 3.4cN/
Dtex, elongation at break 25.0%, line density deviation ratio are 1.12%, and breaking strength CV value is 2.7%, extension at break CV value
It is 5.3%, boiling water shrinkage 4.0%, dye-uptake under the conditions of 130 DEG C of temperature is that 89.9%, K/S value is 23.57.
Embodiment 7
A kind of preparation method of the fluffy snow Neil silk of low boiling water, its step 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) esterification；
Terephthalic acid (TPA), ethylene glycol and the own dioctyl phthalate of 2,5- di-t-butyl -1,6- are matched with the molar ratio of 1:1.2:0.04
At slurry, antimony acetate, titanium dioxide and triphenyl phosphate is added after mixing, 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
It is esterification terminal when 92%, the additional amount of antimony acetate, titanium dioxide and triphenyl phosphate is respectively that terephthalic acid (TPA) is added
0.045wt%, 0.21wt% and 0.02wt% of 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 50min
Interior that absolute pressure 400Pa is steadily evacuated to by normal pressure, reaction temperature is 250 DEG C, and reaction time 50min then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 99Pa, and reaction temperature is 270 DEG C, instead
It is 90min, the modified poly ester that obtained number-average molecular weight is 31500 and molecular weight distributing index is 1.9 between seasonable；
(2) the fluffy snow Neil silk of low boiling water is prepared；
Modified poly ester is processed by FDY technique and squeezes out, cool down through metering, spinneret, oiling, stretching, is nervous hot fixed
Type, heat treatment without tension and the fluffy snow Neil silk for winding obtained low boiling water；The parameter of FDY technique are as follows: 285 DEG C of spinning temperature,
20 DEG C of cooling temperature, network pressure 0.20MPa, a roller speed 2800m/min, 65 DEG C of a roll temperature, two roller speed 4050m/
Min, two 105 DEG C of roll temperatures, winding speed 4200m/min；
The polyester tow that it is 3.6% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar
Temperature is the space between 200 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it
Between, along the traffic direction of polyester tow, the length of two hot plates is 4.0m, and the both ends of two hot plates flush, and polyester tow is from two hot plates
When centre passes through, the distance between two hot plates are 10mm, and the spacing between last group of setting roller and take-up roll is
400mm, the spacing between two hot plates and last group of setting roller are 300mm.
The filament number of the fluffy snow Neil silk of final low boiling water obtained is 0.8dtex, breaking strength 3.3cN/
Dtex, elongation at break 25.0%, line density deviation ratio are 1.1%, and breaking strength CV value is 2.6%, extension at break CV value
It is 4.9%, boiling water shrinkage 4.1%, dye-uptake under the conditions of 130 DEG C of temperature is that 90.4%, K/S value is 23.39.
Claims (10)
1. the preparation method of the fluffy snow Neil silk of low boiling water, it is characterized in that: modified poly ester is processed by FDY technique,
Heat treatment without tension process is added between nervous heat-setting process and rolling step to get the fluffy snow Neil silk of low boiling water；
The modified poly ester the preparation method comprises the following steps: terephthalic acid (TPA), ethylene glycol and binary acid with tert-butyl side group are mixed equal
Esterification and polycondensation reaction are successively carried out after even；
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 the fluffy snow Neil silk of low boiling water according to claim 1, which is characterized in that low boiling water
The filament number of fluffy snow Neil silk is 0.5~1.0dtex, breaking strength >=3.3cN/dtex, elongation at break 25.0
± 5.0%, line density deviation ratio≤1.2%, breaking strength CV value≤3.0%, extension at break CV value≤6.0%, boiling shrinkage
Rate is 4.0 ± 0.5%, and dye-uptake under the conditions of 130 DEG C of temperature is that 88.3~93.7%, K/S value is 22.37~24.72.
3. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 1, which is characterized in that described certain
The space of temperature refers to the space between a pair of arranged in parallel and non-coplanar hot plate, and hot plate is located at last group in FDY equipment
Between setting 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, two hot plates
Both ends flush；When modified poly ester tow passes through among two hot plates, the distance between two hot plates are 5~10mm.
4. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 3, which is characterized in that 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.
5. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 1, which is characterized in that uncle 2-
The synthetic method of the own dioctyl phthalate of butyl -1,6-, the own dioctyl phthalate of 3- tert-butyl -1,6- and the own dioctyl phthalate of 2,5- di-t-butyl -1,6-
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.
6. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 5, which is characterized in that the modification
The preparation step of polyester is as follows:
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and binary acid with tert-butyl side group are made into slurry, catalyst, delustering agent and stabilization is added
After mixing, pressurization carries out esterification in nitrogen atmosphere for agent, and moulding pressure is normal pressure~0.3MPa, the temperature of esterification
Degree is 240~250 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；
(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 260~270 DEG C, and the reaction time is 50~90min.
7. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 6, which is characterized in that described to benzene
The molar ratio of dioctyl phthalate, ethylene glycol and the binary acid with tert-butyl side group is 1:1.2~2.0:0.03~0.05, the catalysis
The additional amount of agent, 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%.
8. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 7, which is characterized in that the catalysis
Agent be antimony oxide, antimony glycol or antimony acetate, the delustering agent be titanium dioxide, the stabilizer be triphenyl phosphate,
Trimethyl phosphate or Trimethyl phosphite.
9. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 8, which is characterized in that modified poly ester
Number-average molecular weight be 28000~32000, molecular weight distributing index be 1.8~2.2.
10. the preparation method of the fluffy snow Neil silk of low boiling water according to claim 1, which is characterized in that the FDY
The process of 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: 275~285 DEG C of spinning temperature, 20~22 DEG C of cooling temperature, network pressure 0.20~
0.30MPa, a 2200~2800m/min of roller speed, 55~65 DEG C of a roll temperature, two 3800~4200m/min of roller speed, two rollers
105~125 DEG C of temperature, 3680~4070m/min of winding speed.
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