CN109722729A - Hexylene glycol modified polyester fiber and preparation method thereof with tert-butyl side group - Google Patents
Hexylene glycol modified polyester fiber and preparation method thereof with tert-butyl side group Download PDFInfo
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- CN109722729A CN109722729A CN201811614004.3A CN201811614004A CN109722729A CN 109722729 A CN109722729 A CN 109722729A CN 201811614004 A CN201811614004 A CN 201811614004A CN 109722729 A CN109722729 A CN 109722729A
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Abstract
The present invention relates to a kind of hexylene glycol modified polyester fiber and preparation method thereof with tert-butyl side group, the preparation method comprises the following steps: being made modified poly ester POY by modified poly ester melt by POY technique is the hexylene glycol modified polyester fiber with tert-butyl side group；Modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), the Sb of ethylene glycol, 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol and doping vario-property2O3Powder successively carries out esterification and polycondensation reaction after mixing.It is 23.65~26.76 that obtained dye-uptake of product under the conditions of 120 DEG C of temperature, which is 86.8~91.2%, K/S value,.Preparation method of the present invention is simple, and dyeability is good, and effectively reduces the additive amount of antimony-based catalyst when synthesizing polyester, and product dye-uptake obtained is high, excellent in mechanical performance, great application prospect.
Description
Technical field
The invention belongs to polyester fiber technical field, be related to a kind of hexylene glycol modified polyester fiber with tert-butyl side group and
Preparation method.
Background technique
Polyester fiber have good heat resistance, chemical resistance, mechanical property and electric property, especially it is transparent it is good,
Insulating properties is good, lower production cost and higher cost performance.PET fiber is due to its regular molecular structure and higher crystallization
It spends and there is excellent physical mechanical property, but this also brings the difficulty of dyeing to PET fiber simultaneously.More function in order to obtain
It can need to be modified conventional PET fiber with the polyester fiber of more preferable service performance.
Currently, there are many research modified about PET both at home and abroad, change generally by some chemical properties for changing polyester
The processing and service performance for becoming polyester product, so that resulting polyester product be made to reach the certain desired value of people.In general, polyester
Method of modifying have that physics (blending) is modified, chemical (copolymerization) is modified, inorganic nanometer modified, reactive extrursion, addition and enhancing change
Property and filling with it is composite modified etc., and physics and chemical modification are most common two classes method of modifying.
The blending of polyester is an important research target of the field of polymers.The physics (blending) of polyester is modified actually
Refer to two kinds and two or more polymer according to a certain percentage in the condition of restriction (such as temperature, pressure, shearing force and screw rod
Revolving speed etc.) under, the blending of the no performance of with ideal performance and single polyester is prepared by the route of melt blending
The method of object, this is simplest method of modifying.This method can not only increase or improve the performance of the polyester as raw material,
And the cost of new polyester development and exploitation can be reduced.Under normal conditions, polyester homopolymer is selected as the matrix of blending and modifying,
Because the basic performances such as the performance of blend and polarity, crystallinity are related, and these performances are the same as between used reactant
Compatibility it is related, therefore, whether the blending of polyester achieves the desired results the compatibility depended primarily between reactant.Institute
With one of the emphasis of blending method study on the modification is exactly the compatibility between polyester.
The modification by copolymerization of polyester is another important research direction in the field of polymers, this is also to produce higher performance to gather
Close the effective ways of object.Modification by copolymerization refer to be added in the synthesis process of polymer other it is one or more be different from stock blend
Monomer, also referred to as third component and the 4th component, pass through copolycondensation and change former polyester chain structure (such as symmetry and
Regularity etc.) come the method for preparing new polymers.And copolymerization method it is modified be divided into random copolymerization modification, block polymerization modification,
The methods of copolymerzation with cross-linking modification and grafting, copolymerization and modification.For the third component or the 4th component introduced during copolyreaction
It can be dibasic aliphatic carboxylic acid, be also possible to binary aromatic carboxylic acid, it is modified that the modification by copolymerization caused by them is referred to as acid.
Common acid has M-phthalic acid (IPA), decanedioic acid and adipic acid etc..And the third component or the 4th component being added can also be
Dihydric alcohol, caused by modification by copolymerization to be known as alcohol modified.And the alcohol for being commonly used for modified poly ester has diethylene glycol (DEG), neopentyl glycol, 1,
4- cyclohexanedimethanol etc..But whether physics (blending) modified or chemical (copolymerization) is modified at present, is all unable to improve PET fibre
The dyeability of dimension, the dye-uptake and dyeing effect of prepared polyester fiber are still very poor.
The dyeability of PET fiber is poor to be primarily due to: lacking the activity that can be bonded with dyestuff in molecular structure
Group can only be dyed using disperse dyes, and disperse dyes belong to nonionic dye, and molecular dimension is larger, water-soluble
It is very low, in addition PET fiber water imbibition is low, it is not easy extruding in water, so the dispersion particle of dyestuff is difficult when being dyed with conventional method
To enter fiber from solution.It is very low the dye-uptake under fluidized state.Carrier dyeing process or high temperature and high pressure method are generally used,
Carrier dyeing is expensive, and brings problem at two aspects of technology and ecology；The internal plasticization of carrier is conducive to dyestuff and exists
The diffusion of fibrous inside, but remaining carrier can make the light resistance of dyestuff be deteriorated, and cause to pollute.High-temperature pressure dyeing need using
Special pressure-resistant equipment, and it is unsuitable for the production of Large Scale and Continuous metaplasia, and it is big to consume energy, and produces dangerous.
In addition, PET polyester material, which produces used synthetic method, is broadly divided into ester-interchange method (DMT method) and straight contracting (PTA
Method), and the catalyst used in process of polyester synthesizing, antimony-based catalyst is mainly used in the market.Metallic antimony has body
Man and nature can be brought harm, contain the environmental issue of the metals such as antimony currently for PET material bottle grade pet chip by evil
Cause the extensive concern of people, but due to compared with other catalyst, the antimony-based catalysts such as antimony oxide it is active it is placed in the middle,
The advantages that cheap and lower to side reaction promotion, therefore, currently, antimony-based catalyst is still widely applied on the market,
Market use ratio reaches 90%, and antimony-based catalyst is also difficult to be substituted comprehensively by other catalyst.At this stage, common on the market
Antimony-based catalyst such as Sb2O3Additive amount in process of polyester synthesizing is larger, and the additive amount of antimony-based catalyst is larger to generate environment
Influence it is also larger, be unfavorable for the environmental protection production of polyester, while antimony-based catalyst can be converted into antimony simple substance in polycondensation reaction, make
Polyester color burnt hair brightness reduces, and antimony-based catalyst additive amount is bigger, bigger on influences such as the color of polyester and quality, but adds
The reaction for all raw materials for participating in polyester synthesis can not be catalyzed by measuring small antimony-based catalyst, be unable to satisfy production of polyester
It needs.
Therefore, a kind of can effectively be modified to polyester to improve fiber dyeing performance and prepare in modified poly ester is developed
The method that Cheng Zhongneng reduces the additive amount of antimony-based catalyst has a very important significance.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of can effectively be modified to improve fibre polyester
The method tieed up dyeability and the additive amount of antimony-based catalyst can be reduced in modified poly ester preparation process.The present invention uses band uncle
The hexylene glycol of butyl side group carries out modification by copolymerization to polyester as Third monomer, can increase the space free volume of polyester, special
It is not empty free volume, the increase of space free volume can increase dye molecule to the infiltration inside fiber molecule, to changing
Property polyester dyeing etc. generate active influence, dyeing temperature can be reduced, shorten the time of dyeing, reduce energy consumption, while also being mentioned
The high dye-uptake of fiber.In addition, the present invention is to Sb2O3It is doped modification, improves the catalytic activity of catalyst, is being guaranteed
While catalytic performance, Sb is significantly reduced2O3Additive amount.
In order to achieve the above object, the present invention adopts the following technical scheme that:
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group, by POY technique by modified poly ester melt system
Modified poly ester POY is obtained to get the hexylene glycol modified polyester fiber with tert-butyl side group；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, 2,2,3,4,5,5- hexamethyl -3,4-
The Sb of hexylene glycol and doping vario-property2O3Powder successively carries out esterification and polycondensation reaction after mixing；
The structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol is as follows:
Sb2O3The process of doping vario-property are as follows: first by metal ion Mx+Solution with contain Sb3+Solution be uniformly mixed,
Then the pH value that precipitating reagent is added dropwise to mixed liquor is 9~10, finally calcines precipitated product；Metal ions Mx+For Mg2+、Ca2+、Ba2+
And Zn2+One or more of.
The present invention is modified polyester using 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, and 2,2,3,4,5,5- six
Methyl -3,4- hexylene glycol can significantly increase the space free volume of polyester, especially 2,2,3,4,5,5- hexamethyls -3,4- oneself
The presence of tert-butyl can cause the variation of main chain activity in glycol, thus the interaction force between changing chain element, molecule
Distance between chain element can also occur to change accordingly, increase the empty free volume of polyester.Simultaneously because empty free volume
There is bigger useful space size compared with slit free volume, more conducively dyestuff penetrates into fibrous inside, the increasing of empty free volume
It can reduce dye molecule greatly and penetrate into difficulty inside modified poly ester, improve the dyeability of modified poly ester, reduce dyeing
Temperature shortens the time of dyeing, reduces energy consumption, improves the dye-uptake of modified poly ester.
The present invention is also by Sb2O3It is doped the modified catalytic activity for improving catalyst, is guaranteeing catalytic performance
Meanwhile significantly reducing Sb2O3Additive amount.
The present invention is by by metal ion Mx+Solution with contain Sb3+Solution first be uniformly mixed reprecipitation finally calcine
So that the doping and blending of metal oxide and antimony oxide with certain catalytic activity is realized, metal oxide MgO,
After one or more of CaO, BaO and ZnO, metal oxide of the invention and antimony oxide doping, metal oxide passes through
Inhibit antimony oxide crystallization and cubic crystal antimony oxide crystal grain grow up and same order elements antimony and enter antimony lattice
Position makes antimony oxide crystal generate defect, and crystal habit generates variation, and crystallite dimension becomes smaller, improves antimony oxide and urge
The specific surface area S of agentg, while metal can also be enriched in part antimony oxide plane of crystal, make antimony oxide unit table
Active r on areasIncrease, specific surface area SgWith the active r in per surface areasBigger, the catalytic activity of catalyst is higher,
Therefore the present invention can be in low Sb2O3Catalyzing and synthesizing for polyester is realized under additive amount, is good for the environment production and guarantees synthesis polyester
Quality.
As a preferred technical scheme:
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, described 2,2,3,4,5,5-
The synthetic method of hexamethyl -3,4- hexylene glycol are as follows: after mixing by palladium acetate and dimethyl di-t-butyl ethylene, quality is added
The hydrogen peroxide solution that concentration is 10~15% reacts 3~4h, through cooling, crystallization and essence under conditions of temperature is 70~75 DEG C
It is made to 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, the dimethyl di-t-butyl ethylene, hydrogen peroxide solution and palladium acetate
Mass ratio be 1:1.5~2.0:0.015.
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, the metal ion Mx+
Solution concentration be 0.5~1.0mol%, solvent is water, the anion in solution be NO3 -；Metal ion M of the inventionx +Solution include but are not limited to this, other solubility properties it is good and can with contain Sb3+Solution dissolve each other to realizing metal ion
Mx+And Sb3+Mixed uniformly solution is equally applicable to the present invention；
It is described to contain Sb3+Solution be 5~10mol% of concentration Sb2O3Solution, solvent is oxalic acid；Of the invention contains Sb3+
Solution include but are not limited to this, other solubility properties are good and can be with metal ion Mx+Solution dissolve each other to realizing gold
Belong to ion Mx+And Sb3+Mixed uniformly solution is equally applicable to the present invention；
The precipitating reagent is the ammonium hydroxide of concentration 2mol/L；Precipitating reagent of the invention includes but are not limited to this, other can
Realize metal ions Mx+And Sb3+It precipitates and for example new metal ion of impurity will not be introduced and will not influence Sb2O3And metal oxygen
The alkaline solution of compound calcining doping vario-property is equally applicable to the present invention；
When precipitating starts, metal ions M in mixed solutionx+With Sb3+Molar ratio be 1~3:100；Sb2O3It is current property
Valence is than highest polyester catalyst, and the present invention is by penetrating into metal oxide (i.e. M2OX) inhibit antimony oxide (Sb2O3) crystalline substance
Change is grown up with cubic crystal antimony oxide crystal grain, while metal ions Mx+The lattice position that antimony and entrance antimony can be replaced, so that three
It aoxidizes two antimony crystal and generates defect, to improve the catalytic activity of antimony oxide.Such as the very few (molar ratio of blended metal oxide amount
It is too low), relatively low on the influence of antimony oxide crystal grain, excessive (molar ratio is excessively high) can make the main body Sb of catalyst3+Fall
It is bigger than normal, it is unfavorable to antimony oxide catalytic activity is improved；
Precipitated product is washed and is dried before the calcining, dry temperature be 105~110 DEG C, the time be 2~
3h；The present invention includes but are not limited to this to the treatment process of precipitated product before calcining after precipitating, as long as can guarantee sufficiently
Remove the OH on precipitated product surface-With moisture therein, the dysgenic processing of impurity and hydrone to calcining can be avoided
Process is suitable for the present invention；
The process of the calcining are as follows: after being warming up to 400 DEG C first keep the temperature 2~3h, after then heating to 900 DEG C keep the temperature 1~
2h is finally cooled down in air；Calcination process of the invention includes but are not limited to this, other can be realized metal oxide
The doping of (MgO, CaO, BaO and ZnO) and antimony oxide are realized to Sb2O3The calcine technology of doping vario-property be suitable for this
Invention；
Sb2O3It is crushed to obtain powder of the average grain diameter less than 0.5 micron after doping vario-property.
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, the system of the modified poly ester
It is standby that steps are as follows:
(1) esterification；
By terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols are made into slurry, and doping is added and changes
The Sb of property2O3After mixing, pressurization carries out esterification in nitrogen atmosphere for powder, delustering agent and stabilizer, 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 theoretical value
It is esterification terminal when 90% or more；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~
Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 260~265 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 265~275 DEG C, the reaction time is 50~90min.
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, the terephthalic acid (TPA),
Ethylene glycol and 2, the molar ratio of 2,3,4,5,5- hexamethyl -3,4- hexylene glycols are 1:1.2~2.0:0.03~0.06, band of the present invention
The additional amount of the dihydric alcohol of trimethylsilyl side group is not limited to this, and those skilled in the art can be adjusted according to the actual situation,
But adjustment amplitude should not be too large, and the excessive regularity destruction to polyester macromolecule structure of additive amount is too big, to the crystallinity of fiber
And Effect on Mechanical Properties is excessive, is unfavorable for the production and application of fiber, additive amount is too low, then effect is unobvious, the doping
Modified Sb2O3The additional amount of powder, delustering agent and stabilizer be respectively terephthalic acid (TPA) additional amount 0.012~
0.015wt%, 0.20~0.25wt% and 0.01~0.05wt%, in the prior art Sb in process of polyester synthesizing2O3Additional amount
The additional amount of usually 0.02~0.04wt% of terephthalic acid (TPA) additional amount, antimony-based catalyst are high, and this is mainly due to do not mix
Miscellaneous Sb2O3Active r in per surface areasLow and specific surface area SgIt is small, therefore Sb2O3Whole catalytic activity is lower, this hair
It is bright by Sb2O3It is doped modification, improves Sb2O3Activity, therefore significantly reduce Sb in process of polyester synthesizing2O3's
Additive amount.
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, the delustering agent are dioxy
Change titanium, the stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, the number of the modified poly ester
Average molecular weight is 25000~30000, and molecular weight distributing index is 1.8~2.2.
The preparation method of hexylene glycol modified polyester fiber with tert-butyl side group as described above, the stream of the POY technique
Journey are as follows: metering, spinneret squeeze out, are cooling, oiling and wind；
The parameter of the POY technique are as follows: 280~290 DEG C of spinning temperature, 18~22 DEG C of cooling temperature, winding speed 3200
~3600m/min.
The present invention also provides a kind of preparations using the hexylene glycol modified polyester fiber with tert-butyl side group as described above
Hexylene glycol modified polyester fiber with tert-butyl side group made from method is modified poly ester POY；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and 2,2,3,4,5,5- pregnancy
Base -3,4- hexylene glycol segment；The Sb of the doping vario-property is dispersed in the modified poly ester2O3Powder.
As a preferred technical scheme:
As described above with the hexylene glycol modified polyester fiber of tert-butyl side group, the hexylene glycol with tert-butyl side group is modified poly-
The filament number of ester fiber be 1.0~2.0dtex, breaking strength >=2.2cN/dtex, elongation at break be 110.0 ±
10.0%, line density deviation ratio≤0.20%, breaking strength CV value≤2.50%, extension at break CV value≤5.0%；The present invention is logical
The introducing for crossing the hexylene glycol (2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol) with tert-butyl side group is modified polyester, institute
The above-mentioned mechanical property of fiber obtained does not decline, with the prior art (be not added with 2,2,3,4,5,5- hexamethyls -3,4- oneself
Glycol) quite；
Dye-uptake of the hexylene glycol modified polyester fiber with tert-butyl side group under the conditions of 120 DEG C of temperature be 86.8~
91.2%, K/S value are 23.65~26.76；In the identical situation of other test conditions, temperature condition of the comparative sample at 130 DEG C
Under dye-uptake be 86.2%, K/S value be 21.64, comparative sample and the hexylene glycol modified poly ester of the invention with tert-butyl side group
The difference of fiber is only that its material is conventional polyester.
Invention mechanism:
The present invention is modified polyester by 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, and it is empty to increase modified poly ester
Hole free volume, the increase of empty free volume can reduce dye molecule and penetrate into difficulty inside modified poly ester, make to make
The POY dyeabilities of modified poly ester obtained are greatly promoted；In addition, the present invention is by being doped antimony trioxide,
The catalytic activity of antimony trioxide is improved to a certain extent, and the catalytic activity raising of antimony trioxide advantageously reduces antimony trioxide
Usage amount in process of polyester synthesizing, in the case where polycondensating process condition remains unchanged and polyester reaches identical index, uses
After metal oxide is doped antimony trioxide, the usage amount of antimony trioxide can reduce 30% or more, efficiently solve at present
The big problem of additive amount existing for antimony trioxide, while can satisfy the needs of production of polyester.
The present invention improves the dyeability of polyester fiber by 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol to polyester modification
The specific mechanism of action of energy 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.
For the dihydric alcohols straight chain molecule such as ethylene glycol, butanediol, the C atom on main chain is arranged in indention one on the other
Column, when the H atom on main chain on some methylene is by methyl (- CH3) when replacing, C atom and main chain C atom in side group do not exist
In 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, shape
It at four identical σ keys, is arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, works as first
When three hydrogen of base is further replaced by methyl, it is at this moment equivalent to tert-butyl substitution, forms a bigger tetrahedral structure,
The strand that this strand in the arrangement of positive tetrahedron shape is arranged relative to indention, empty free volume significantly increase
Very much, the permeability and diffusivity of small molecule can be significantly improved；And when the H atom on main chain on some methylene is 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 is gathered by introducing 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol in polyester molecule chain and being obviously improved
The structural formula of the dyeability of ester, 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is as follows:
The presence of tert-butyl can cause the variation of main chain activity in 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, from
And the interaction force between chain element is changed, the distance between molecule chain element can also occur to change accordingly, lead to modified CDP
The increase of empty free volume.Compared with short-chain branch substituent group (such as methyl, ethyl group), tert-butyl occupies biggish sky
Between position, bigger free volume will be obtained in the mode of strand arrangement；Compared with chain substituent of drawing money on credit, the tertiary fourth of one side
Base increase be empty free volume, and draw money on credit chain substituent increase be slit free volume, another aspect tert-butyl it is rigid
Property be greater than and draw money on credit chain substituent, reduce the entanglement between strand, thus tert-butyl chain substituent of relatively drawing money on credit is arranged in strand
There are more free volumes in the mode of column.Simultaneously because empty free volume have compared with slit free volume it is bigger effective
Bulk, more conducively dyestuff penetrate into fibrous inside, and the introducing of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is so that modified poly-
The empty free volume of ester increases, and significantly reduces water or other molecules such as dyestuff penetrates into difficulty inside polyester macromolecule
Degree generates active influence to dyeing of polyester etc., can reduce dyeing temperature, shorten the time of dyeing, reduces energy consumption, while
Improve the dye-uptake of fiber.
Antimony trioxide is doped as follows to reduce the specific mechanism of action of the usage amount of antimony trioxide:
Polyester catalyst mainly based on antimonial, such as antimony oxide, antimony glycol and antimony acetate, industrially gathers
The additional amount of antimony is greater than 200ppm in Lipase absobed, and since antimony is heavy metal, the progress in epoch is more next for the restriction of antimony catalyst
It is tighter, it, still can not be in the short time due to color and activity control etc. are various although the catalysis of titanium system is applied
Interior substitution antimony system.
The catalytic activity of catalyst and the specific surface area S of catalystg, in utilization rate of inner surface f and per surface area
Active rsDirectly proportional, certain for component catalyst, catalytic activity depend on the specific surface area S of the catalystgAnd inner surface
Utilization rate f, the active r in catalyst per surface areasOne timing, specific surface area is bigger, and catalytic activity is higher.
The present invention is co-precipitated to calcine again again by first solution blending realizes the gold with certain catalyzed polycondensation reactivity
Belong to the doping and blending of oxide and antimony oxide, one or more of metal oxide MgO, CaO, BaO and ZnO, valence
Position and the price of antimony have a certain difference, and there is also certain difference, these differences can change for ionic radius and antimony
The crystal plane structure of antimony oxide, to influence correlated performance.In addition, MgO, CaO, BaO, ZnO are white crystal, as poly-
Ester catalyst will not bring the variation on color.
Influence of the metal oxide to antimony oxide is mainly reflected in: on the one hand, metal oxide can inhibit three oxidations
The crystallization of two antimony and growing up for cubic crystal antimony oxide crystal grain make the specific surface area S of antimony oxide catalystgIt improves, mentions
The high catalytic activity of antimony oxide；On the other hand, metal understands the lattice position of same order elements antimony and entrance antimony, makes three oxidations two
Antimony crystal generates defect, and crystal habit generates variation, and crystallite dimension becomes smaller, specific surface area SgIncrease, while in partial crystals table
Face makes metal enrichment, makes the active r in its per surface areasIt improves, improves the catalytic activity of antimony oxide.As will be only had
There is the metal oxide of certain catalyzed polycondensation reactivity to be blended with antimony oxide simple physical, the catalysis of antimony oxide is living
Property will not significantly improve because simple physical be blended, crystal defect will not be generated, crystal habit does not generate variation, crystal grain
Size remains unchanged, and the total surface area of crystal is constant, will not have an impact to catalytic activity.
The present invention improves the catalytic activity of antimony trioxide, three oxygen by being doped to antimony trioxide in a degree
The catalytic activity for changing antimony, which improves, advantageously reduces the usage amount of antimony trioxide, in process of polyester synthesizing, protects in polycondensating process condition
It holds in the case that constant and polyester reaches identical index, after being doped using metal oxide to antimony trioxide, three oxidations
The usage amount of antimony can reduce 30% or more, efficiently solve the problems, such as that additive amount existing for current antimony trioxide is big, while can
Meet the needs of production of polyester.
The utility model has the advantages that
(1) preparation method of the hexylene glycol modified polyester fiber of the invention with tert-butyl side group, simple process and low cost
It is honest and clean, by introducing modified component in the polyester --- 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols significantly improve polyester
The dyeability of FDY fiber；
(2) preparation method of the hexylene glycol modified polyester fiber of the invention with tert-butyl side group is centainly urged by having
Change active metal oxide to the doping vario-property of antimony oxide, improves antimony oxide specific surface area SgAnd per surface
Active r in products, to improve the catalytic activity of antimony oxide, polymerization efficiency is improved, and then polyester can met
The additive amount of antimony-based catalyst when reducing synthesis polyester while production needs effectively reduces the antimony row that fiber is made thereafter
It puts, is advantageously implemented environmentally friendly production；
(3) the hexylene glycol modified polyester fiber of the invention with tert-butyl side group, dyeability is good, excellent in mechanical performance,
Great application 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 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Mg (the NO that concentration is 0.8mol% by (1.1.1)3)2The Sb that aqueous solution and concentration are 8mol%2O3Solution mixing
Uniformly, Sb2O3The solvent of solution be oxalic acid, Mg in mixed liquor2+With Sb3+Molar ratio be 2:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 9 to obtain precipitated product, then to precipitating
Product is washed and is dried, and dry temperature is 105 DEG C, time 2.5h；
(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C
1.5h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 10%, reacts 3h under conditions of temperature is 72 DEG C, pass through
Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen
Aqueous solution and the mass ratio of palladium acetate are 1:2.0:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols
(I) shown in；
(1.3) esterification；
By molar ratio be 1:1.5:0.03 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and triphenyl phosphate after mixing, in nitrogen atmosphere
Pressurization carries out esterification, and moulding pressure 0.2MPa, the temperature of esterification is 260 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 95% of theoretical value, and wherein the additional amount of triphenyl phosphate is terephthalic acid (TPA) additional amount
0.03wt%, the Sb of doping vario-property2O3Additional amount be terephthalic acid (TPA) additional amount 0.015wt%, the additional amount of titanium dioxide
For the 0.20wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min
Interior that absolute pressure 490Pa is steadily evacuated to by normal pressure, reaction temperature is 265 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 85Pa, and reaction temperature is 275 DEG C, instead
It is 90min between seasonable, it is 30000 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 2.2；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
280 DEG C of degree, 18 DEG C of cooling temperature, winding speed 3200m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
2.0dtex, breaking strength 2.4cN/dtex, elongation at break 120.0%, line density deviation ratio are 0.16%, and fracture is strong
Spending CV value is 2.0%, and extension at break CV value is 4.0%；Its dye-uptake under the conditions of 120 DEG C of temperature is 86.8%, K/S value
It is 23.65.
Comparative example 1
A kind of polyester POY preparation methods, step is substantially same as Example 1, the difference is that, step (1)
And 2 are not added with, 2,3,4,5,5- hexamethyl -3,4- hexylene glycols, polyester POY filament numbers obtained are 2.0dtex, are broken
Resistance to spalling is 2.5cN/dtex, elongation at break 116.0%, line density deviation ratio are 0.16%, and breaking strength CV value is
2.0%, extension at break CV value is 3.9%；In situation identical with other test conditions of embodiment 1, in 130 DEG C of temperature
Under the conditions of dye-uptake be 86.2%, K/S value be 21.64.
With the comparison of embodiment 1 it can be found that the present invention is significant by 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols of addition
The dyeability of fiber, while 2 are improved, the addition of 2,3,4,5,5- hexamethyl -3,4- hexylene glycols is to other performance shadows of fiber
Sound is smaller, has no effect on its processing performance and mechanical performance.
Comparative example 2
A kind of polyester DTY preparation methods, step is substantially same as Example 1, the difference is that, step (1)
In use 1,2 dodecanediols substitute 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, polyester DTY lists obtained
Silk size is 2.0dtex, breaking strength 2.3cN/dtex, elongation at break 116.0%, and line density deviation ratio is
0.16%, breaking strength CV value is 2.0%, and extension at break CV value is 4.0%；Identical with other test conditions of embodiment 1
In the case of, dye-uptake under the conditions of 130 DEG C of temperature is that 86.4%, K/S value is 21.78.
It is compared with embodiment 1 it can be found that tert-butyl in 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is relative to 1,
Chain substituent of drawing money on credit in 2 dodecanediols is more advantageous to the dyeability for promoting fiber, this is primarily due to one side 2,
The free volume that tert-butyl in 2,3,4,5,5- hexamethyl -3,4- hexylene glycols increases is more empty free volume, and 1,2
The free volume of chain substituent increase of drawing money on credit in dodecanediol is more slit free volume, another aspect 2,2,3,
The rigidity of tert-butyl in 4,5,5- hexamethyl -3,4- hexylene glycols is greater than the chain substituent of drawing money on credit in 1,2 dodecanediols, subtracts
The entanglement between strand, thus 2 are lacked, 2,3,4,5,5- hexamethyl -3,4- hexylene glycols are compared with 1, and 2 dodecanediols are in polyester
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 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Ca (the NO that concentration is 0.5mol% by (1.1.1)3)2The Sb that aqueous solution and concentration are 5mol%2O3Solution mixing
Uniformly, Sb2O3The solvent of solution be oxalic acid, Ca in mixed liquor2+With Sb3+Molar ratio be 1:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy
Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2h；
(1.1.3) keeps the temperature 2h after the product after drying is warming up to 400 DEG C first, keeps the temperature 1h after then heating to 900 DEG C,
It is crushed after finally cooling down in air and obtains the Sb for the doping vario-property that average grain diameter is 0.4 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 11%, reacts 4h under conditions of temperature is 70 DEG C, pass through
Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen
Aqueous solution and the mass ratio of palladium acetate are 1:1.8:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols
(I) shown in；
(1.3) esterification；
By molar ratio be 1:1.2:0.06 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and trimethyl phosphate after mixing, in nitrogen atmosphere
Esterification is carried out under normal pressure, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 94%, wherein the additional amount of trimethyl phosphate is the 0.01wt% of terephthalic acid (TPA) additional amount, doping
Modified Sb2O3Additional amount be terephthalic acid (TPA) additional amount 0.012wt%, the additional amount of titanium dioxide is terephthalic acid (TPA)
The 0.25wt% of 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
Interior that absolute pressure 490Pa is steadily evacuated to by normal pressure, reaction temperature is 260 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 90Pa, and reaction temperature is 265 DEG C, instead
It is 50min between seasonable, it is 25000 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 1.8；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
290 DEG C of degree, 22 DEG C of cooling temperature, winding speed 3600m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
1.1dtex, breaking strength 2.22cN/dtex, elongation at break 101.0%, line density deviation ratio are 0.17%, and fracture is strong
Spending CV value is 2.48%, and extension at break CV value is 4.85%；Its dye-uptake under the conditions of 120 DEG C of temperature is 91.2%, K/S
Value is 26.76.
Embodiment 3
A kind of preparation method of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Ba (the NO that concentration is 1.0mol% by (1.1.1)3)2The Sb that aqueous solution and concentration are 10mol%2O3Solution it is mixed
It closes uniformly, Sb2O3The solvent of solution be oxalic acid, Ba in mixed liquor2+With Sb3+Molar ratio be 3:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 9.5 to obtain precipitated product, then to heavy
Shallow lake product is washed and is dried, and dry temperature is 105 DEG C, time 3h；
(1.1.3) keeps the temperature 3h after the product after drying is warming up to 400 DEG C first, keeps the temperature 2h after then heating to 900 DEG C,
It is crushed after finally cooling down in air and obtains the Sb for the doping vario-property that average grain diameter is 0.5 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 12%, reacts 4h under conditions of temperature is 74 DEG C, pass through
Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen
Aqueous solution and the mass ratio of palladium acetate are 1:1.6:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols
(I) shown in；
(1.3) esterification；
By molar ratio be 1:2.0:0.045 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and Trimethyl phosphite after mixing, in nitrogen atmosphere
Middle pressurization carries out esterification, and moulding pressure 0.25MPa, the temperature of esterification is 255 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 97% of theoretical value, and wherein the additional amount of Trimethyl phosphite is terephthalic acid (TPA) addition
The 0.05wt% of amount, the Sb of doping vario-property2O3Additional amount be terephthalic acid (TPA) additional amount 0.0125wt%, titanium dioxide
Additional amount is the 0.22wt% 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
Interior that absolute pressure 495Pa is steadily evacuated to by normal pressure, reaction temperature is 265 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 90Pa, and reaction temperature is 265 DEG C, instead
It is 50min between seasonable, it is 26000 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 1.9；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
285 DEG C of degree, 20 DEG C of cooling temperature, winding speed 3400m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
1.5dtex, breaking strength 2.3cN/dtex, elongation at break 110.0%, line density deviation ratio are 0.18%, and fracture is strong
Spending CV value is 2.2%, and extension at break CV value is 4.5%；Its dye-uptake under the conditions of 120 DEG C of temperature is 88.2%, K/S value
It is 25.06.
Embodiment 4
A kind of preparation method of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Zn (the NO that concentration is 0.6mol% by (1.1.1)3)2The Sb that aqueous solution and concentration are 6mol%2O3Solution mixing
Uniformly, Sb2O3The solvent of solution be oxalic acid, Zn in mixed liquor2+With Sb3+Molar ratio be 1.2:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy
Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；
(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C
1h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 13%, reacts 3.5h under conditions of temperature is 74 DEG C,
It through cooling, crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, double
Oxygen aqueous solution and the mass ratio of palladium acetate are 1:1.5:0.015, and the structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is such as
Shown in formula (I)；
(1.3) esterification；
By molar ratio be 1:1.5:0.06 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and triphenyl phosphate after mixing, in nitrogen atmosphere
Esterification is carried out under normal pressure, the temperature of esterification is 257 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 95%, wherein the additional amount of triphenyl phosphate is the 0.03wt% of terephthalic acid (TPA) additional amount, doping
Modified Sb2O3Additional amount be terephthalic acid (TPA) additional amount 0.013wt%, the additional amount of titanium dioxide is terephthalic acid (TPA)
The 0.25wt% of 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 35min
Interior that absolute pressure 495Pa is steadily evacuated to by normal pressure, reaction temperature is 262 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 90Pa, and reaction temperature is 265 DEG C, instead
It is 40min between seasonable, it is 27000 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 2.0；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
290 DEG C of degree, 20 DEG C of cooling temperature, winding speed 3200m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
1.0dtex, breaking strength 2.2cN/dtex, elongation at break 100.0%, line density deviation ratio are 0.20%, and fracture is strong
Spending CV value is 2.50%, and extension at break CV value is 5.0%；Its dye-uptake under the conditions of 120 DEG C of temperature is 87.0%, K/S
Value is 23.60.
Embodiment 5
A kind of preparation method of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Mg (the NO that concentration is 0.7mol% by (1.1.1)3)2The Sb that aqueous solution and concentration are 8mol%2O3Solution mixing
Uniformly, Sb2O3The solvent of solution be oxalic acid, Mg in mixed liquor2+With Sb3+Molar ratio be 2:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy
Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；
(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C
2h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.5 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 14%, reacts 3.5h under conditions of temperature is 71 DEG C,
It through cooling, crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, double
Oxygen aqueous solution and the mass ratio of palladium acetate are 1:1.7:0.015, and the structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is such as
Shown in formula (I)；
(1.3) esterification；
By molar ratio be 1:1.6:0.04 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and triphenyl phosphate after mixing, in nitrogen atmosphere
Esterification is carried out under normal pressure, the temperature of esterification is 257 DEG C, when the water quantity of distillate in esterification reaches theoretical value
It is esterification terminal when 94%, wherein the additional amount of triphenyl phosphate is the 0.035wt% of terephthalic acid (TPA) additional amount, doping
Modified Sb2O3Additional amount be terephthalic acid (TPA) additional amount 0.0135wt%, the additional amount of titanium dioxide is terephthalic acid (TPA)
The 0.20wt% of additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min
Interior that absolute pressure 490Pa is steadily evacuated to by normal pressure, reaction temperature is 263 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 90min between seasonable, it is 28000 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 2.0；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
290 DEG C of degree, 18 DEG C of cooling temperature, winding speed 3200m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
1.7dtex, breaking strength 2.35cN/dtex, elongation at break 112.0%, line density deviation ratio are 0.17%, and fracture is strong
Spending CV value is 2.1%, and extension at break CV value is 4.3%；Its dye-uptake under the conditions of 120 DEG C of temperature is 87.9%, K/S value
It is 24.55.
Embodiment 6
A kind of preparation method of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Concentration is the Mg (NO of 0.8mol% by (1.1.1)3)2Aqueous solution and Ca (NO3)21:1 is mixed by volume for aqueous solution
Conjunction obtains metal ion Mx+Aqueous solution, metal ion Mx+Aqueous solution and concentration be 8mol% Sb2O3Solution it is mixed
It closes uniformly, Sb2O3The solvent of solution be oxalic acid, M in mixed liquorx+With Sb3+Molar ratio be 2.5:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy
Shallow lake product is washed and is dried, and dry temperature is 105 DEG C, time 3h；
(1.1.3) keeps the temperature 3h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C
1.5h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 15%, reacts 3h under conditions of temperature is 75 DEG C, pass through
Cooling crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl ethylene, dioxygen
Aqueous solution and the mass ratio of palladium acetate are 1:1.9:0.015, the structural formula such as formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols
(I) shown in；
(1.3) esterification；
By molar ratio be 1:1.7:0.05 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and trimethyl phosphate after mixing, in nitrogen atmosphere
Pressurization carries out esterification, and moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 95% of theoretical value, and wherein the additional amount of trimethyl phosphate is terephthalic acid (TPA) additional amount
0.04wt%, the Sb of doping vario-property2O3Additional amount be terephthalic acid (TPA) additional amount 0.014wt%, the additional amount of titanium dioxide
For the 0.25wt% 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
Interior that absolute pressure 490Pa is steadily evacuated to by normal pressure, reaction temperature is 262 DEG C, and reaction time 45min 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 275 DEG C, instead
It is 70min between seasonable, it is 28500 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 2.0；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
280 DEG C of degree, 22 DEG C of cooling temperature, winding speed 3200m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
1.4dtex, breaking strength 2.25cN/dtex, elongation at break 107.0%, line density deviation ratio are 0.19%, and fracture is strong
Spending CV value is 2.40%, and extension at break CV value is 4.8%；Its dye-uptake under the conditions of 120 DEG C of temperature is 89.8%, K/S
Value is 25.76.
Embodiment 7
A kind of preparation method of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers, the specific steps are as follows:
(1) modified poly ester is prepared；
(1.1) Sb of doping vario-property is prepared2O3；
Concentration is the Mg (NO of 0.5mol% by (1.1.1)3)2Aqueous solution, Ba (NO3)2Aqueous solution and Ca (NO3)2It is water-soluble
1:1:1 is mixed to get metal ion M to liquid by volumex+Aqueous solution, metal ion Mx+Aqueous solution be with concentration
The Sb of 10mol%2O3Solution be uniformly mixed, Sb2O3The solvent of solution be oxalic acid, metal ions M in mixed liquorx+With Sb3+'s
Molar ratio is 2:100；
The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 9 to obtain precipitated product, then to precipitating
Product is washed and is dried, and dry temperature is 108 DEG C, time 2.5h；
(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C
2h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron2O3Powder；
(1.2) 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, method are as follows: by palladium acetate and the tertiary fourth of dimethyl two are synthesized
Base ethylene after mixing, is added the hydrogen peroxide solution that mass concentration is 13.5%, reacts under conditions of temperature is 73 DEG C
3.4h through cooling, is crystallized and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, wherein dimethyl di-t-butyl second
The mass ratio of alkene, hydrogen peroxide solution and palladium acetate is 1:1.8:0.015, the knot of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols
Shown in structure formula such as formula (I)；
(1.3) esterification；
By molar ratio be 1:2.0:0.06 terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- oneself two
Alcohol is made into slurry, and the Sb of doping vario-property is added2O3Powder, titanium dioxide and trimethyl phosphate after mixing, in nitrogen atmosphere
Pressurization carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 94% of theoretical value, and wherein the additional amount of trimethyl phosphate is terephthalic acid (TPA) additional amount
0.04wt%, the Sb of doping vario-property2O3Additional amount be terephthalic acid (TPA) additional amount 0.014wt%, the additional amount of titanium dioxide
For the 0.25wt% of terephthalic acid (TPA) additional amount；
(1.4) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min
Interior that absolute pressure 495Pa is steadily evacuated to by normal pressure, reaction temperature is 265 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 90Pa, and reaction temperature is 272 DEG C, instead
It is 65min between seasonable, it is 28200 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 2.2；
(2) it is squeezed out by modified poly ester melt through metering, spinneret by POY technique, is cooling, oiled and wound and being made modified poly-
Ester POY to get 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fibers；The parameter of POY technique are as follows: spinning temperature
280 DEG C of degree, 22 DEG C of cooling temperature, winding speed 3600m/min.
Finally the filament number of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol modified polyester fiber obtained is
1.1dtex, breaking strength 2.21cN/dtex, elongation at break 102.0%, line density deviation ratio are 0.19%, and fracture is strong
Spending CV value is 2.4%, and extension at break CV value is 4.8%；Its dye-uptake under the conditions of 120 DEG C of temperature is 90.4%, K/S value
It is 26.70.
Claims (10)
1. the preparation method of the hexylene glycol modified polyester fiber with tert-butyl side group, it is characterized in that: by POY technique by modified poly ester
Melt is made modified poly ester POY to get the hexylene glycol modified polyester fiber with tert-butyl side group；
The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, 2,2,3,4,5,5- hexamethyl -3,4- oneself two
The Sb of pure and mild doping vario-property2O3Powder successively carries out esterification and polycondensation reaction after mixing；
The structural formula of 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycol is as follows:
Sb2O3The process of doping vario-property are as follows: first by metal ion Mx+Solution with contain Sb3+Solution be uniformly mixed, then
The pH value that precipitating reagent is added dropwise to mixed liquor is 9~10, finally calcines precipitated product；Metal ions Mx+For Mg2+、Ca2+、Ba2+With
Zn2+One or more of.
2. the preparation method of the hexylene glycol modified polyester fiber according to claim 1 with tert-butyl side group, feature exist
In the synthetic method of described 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols are as follows: by palladium acetate and dimethyl di-t-butyl ethylene
After mixing, be added mass concentration be 10~15% hydrogen peroxide solution, temperature be 70~75 DEG C under conditions of reaction 3~
4h through cooling, crystallizes and is refining to obtain 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols, the dimethyl di-t-butyl ethylene,
Hydrogen peroxide solution and the mass ratio of palladium acetate are 1:1.5~2.0:0.015.
3. the preparation method of the hexylene glycol modified polyester fiber according to claim 2 with tert-butyl side group, feature exist
In the metal ion Mx+Solution concentration be 0.5~1.0mol%, solvent is water, the anion in solution be NO3 -；
It is described to contain Sb3+Solution be 5~10mol% of concentration Sb2O3Solution, solvent is oxalic acid；The precipitating reagent is concentration 2mol/
The ammonium hydroxide of L；When precipitating starts, metal ions M in mixed solutionx+With Sb3+Molar ratio be 1~3:100；
Precipitated product is washed and dried before the calcining, dry temperature is 105~110 DEG C, and the time is 2~3h；Institute
State the process of calcining are as follows: keep the temperature 2~3h after being warming up to 400 DEG C first, 1~2h is kept the temperature after then heating to 900 DEG C, finally in sky
It is cooling in gas；Sb2O3It is crushed to obtain powder of the average grain diameter less than 0.5 micron after doping vario-property.
4. the preparation method of the hexylene glycol modified polyester fiber according to claim 3 with tert-butyl side group, feature exist
In the preparation step of the modified poly ester is as follows:
(1) esterification；
By terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols are made into slurry, doping vario-property are added
Sb2O3After mixing, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure for powder, delustering agent and stabilizer
~0.3MPa, the temperature of esterification are 250~260 DEG C, when the water quantity of distillate in esterification reach the 90% of theoretical value with
It was esterification terminal when upper；
(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
It is interior that absolute pressure 500P is steadily evacuated to by normal pressureaHereinafter, reaction temperature is 260~265 DEG C, the reaction time is 30~50min, so
After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, reaction pressure made to be further reduced to absolute pressure 100PaHereinafter,
Reaction temperature is 265~275 DEG C, and the reaction time is 50~90min。
5. the preparation method of the hexylene glycol modified polyester fiber according to claim 4 with tert-butyl side group, feature exist
In the molar ratio of the terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyl -3,4- hexylene glycols is 1:1.2~2.0:
0.03~0.06, the Sb of the doping vario-property2O3The additional amount of powder, delustering agent and stabilizer is respectively that terephthalic acid (TPA) is added
The 0.012~0.015 of amountwt%, 0.20~0.25wt% and 0.01~0.05wt%.
6. the preparation method of the hexylene glycol modified polyester fiber according to claim 5 with tert-butyl side group, feature exist
In the delustering agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
7. the preparation method of the hexylene glycol modified polyester fiber according to claim 6 with tert-butyl side group, feature exist
In the number-average molecular weight of the modified poly ester is 25000~30000, and molecular weight distributing index is 1.8~2.2.
8. the preparation method of the hexylene glycol modified polyester fiber according to claim 1 with tert-butyl side group, feature exist
In the process of the POY technique are as follows: metering, spinneret squeeze out, are cooling, oiling and wind；
The parameter of the POY technique are as follows: 280~290 DEG C of spinning temperature, 18~22 DEG C of cooling temperature, winding speed 3200~
3600m/min。
9. using the preparation side of the hexylene glycol modified polyester fiber as described in any one of claims 1 to 8 with tert-butyl side group
Hexylene glycol modified polyester fiber with tert-butyl side group made from method, it is characterized in that: being modified poly ester POY；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and hexamethyl -3 2,2,3,4,5,5-,
4- hexylene glycol segment；The Sb of the doping vario-property is dispersed in the modified poly ester2O3Powder.
10. the hexylene glycol modified polyester fiber according to claim 9 with tert-butyl side group, which is characterized in that the tertiary fourth of band
The filament number of the hexylene glycol modified polyester fiber of base side group is 1.0~2.0dtex, breaking strength >=2.2cN/dtex, fracture
Elongation is 110.0 ± 10.0%, line density deviation ratio≤0.20%, breaking strength CV value≤2.50%, extension at break CV value
≤ 5.0%；
Dye-uptake of the hexylene glycol modified polyester fiber with tert-butyl side group under the conditions of 120 DEG C of temperature be 86.8~
91.2%, K/S value are 23.65~26.76.
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