CN106283252A - A kind of porous PBT fiber HOY silk and preparation method thereof - Google Patents

A kind of porous PBT fiber HOY silk and preparation method thereof Download PDF

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Publication number
CN106283252A
CN106283252A CN201610784919.3A CN201610784919A CN106283252A CN 106283252 A CN106283252 A CN 106283252A CN 201610784919 A CN201610784919 A CN 201610784919A CN 106283252 A CN106283252 A CN 106283252A
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phthalic acid
preparation
esterification
porous
spinneret
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CN106283252B (en
Inventor
范红卫
王丽丽
邵义伟
温浩
孙晓华
金管范
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • 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
    • 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
    • C08G63/78—Preparation processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention relates to a kind of porous PBT fiber HOY silk and preparation method thereof, the employing porous spinneret spinning of modified PBT polyester is prepared porous PBT fiber HOY silk；On porous spinneret, the arrangement mode of spinneret orifice is that the hole of oval shaped arrangements, i.e. spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.Porous PBT fiber HOY silk is prepared through measuring, extrude, cool down, oil and winding by modified PBT polyester, the preparation method of modified PBT polyester is: p-phthalic acid and 1,4 butanediol reactions prepare p-phthalic acid 1,4 butanediol esters, add the p-phthalic acid binary alcohol esters that p-phthalic acid prepares with the diol reaction containing side chain, continue reaction and obtain modified PBT polyester.The fibre property that the present invention prepares is excellent, line density deviation ratio≤0.2%, fracture strength CV value≤2.5%, extension at break CV value≤5.0%.

Description

A kind of porous PBT fiber HOY silk and preparation method thereof
Technical field
The invention belongs to PBT fiber art, relate to a kind of porous PBT fiber HOY silk and preparation method thereof.
Background technology
The existing aromatic rings identical with polyester in the molecular structure of PBT fiber, has again identical with chinlon longer time Methyl segment, therefore, it has the durability of terylene concurrently, dimensional stability, crease resistance and hygrometric state strength and the property such as strength is the most constant Matter, and the softness of chinlon and rub resistance, and its stainability and coloring exceed terylene and chinlon, can be without carrier with dispersion Property fuel directly carries out boiling dyeing at normal pressure.The great advantage of PBT fiber is to have good resilience, and its Curl is good, extends Property is close to spandex, and both of which is higher than terylene.In recent years along with the development of fibre in differentiation, PBT as fiber use value by Step is obtained certainly, and its product being processed into has high resiliency, high wrinkling property, good hand touch, third dimension is strong, style is peculiar top grade Quality, in every field to being widely applied.Be particularly well-suited to make swimsuit, tights, training clothes, gym outfit, The high resiliency such as gym wear, tennis togs, dancing tights, elastic force jean, ski trousers, stocking, the binder medically applied spin Fabric, is a kind of rising fiber.
The method preparing PBT fiber is a lot, the one that wherein melt spinning method is more in being the application of current commercial production.Molten Melting and have many parameters in spinning process, these parameters determine the course of fiberizing and spin structure and the performance of fiber, produce On be through the fiber that controls these parameters to prepare desired properties.Mainly spin according to what technical process can control in producing Silk summary of parameters.An is melting condition, spinning conditions, condition of cure, wrapping wire condition etc., and wherein strand cooling and solidifying condition is to fiber Structure and performance have conclusive impact, for controlling rate of cooling and the uniformity thereof of polyester fondant thread, generally adopt in production Take cooling blowing.Cooling blowing can accelerate the rate of cooling of melt stream, is conducive to improving spinning speed；Strengthen around strand empty The convection current of gas, makes the cooling of ectonexine strand uniformly, for using porous spinneret to create condition；Cooling blowing can make as-spun fibre Quality advance, tensile property improves, the beneficially production capacity of raising equipment.
Experimental branch line all uses cross air blasting as the type of cooling for a long time, and energy resource consumption accounts for long filament production cost very Major part, along with chemical fibre performance and quality requirements are improved by people day by day, the exploitation of chemical-fibres filaments new product is to high added value Fibre in differentiation direction is developed, it is desirable to higher cooling blowing condition, then proposes ring blowing device.Ring blowing device is not only Possess every uniform advantage of synnema wind-engaging, and energy consumption is compared relatively low, effectively solve cross air blasting owing to blowing area is big The wind energy loss problem caused.
In spinning process, although ring blowing has obvious advantage, but still the cooling of porous yarn cannot be solved well Uneven problem, owing to spun silk is after circular jetting filament plate is extruded, by ring quenching, due to the circular jetting filament plate number of turns relatively It is many so that ring blowing hardly enters innermost layer, causes the silk at outermost silk innermost layer the most after cooling may be the most uncolled, Thus the problems such as fiber number is irregular, and intensity is irregular, uneven dyeing occurs in the silk of gained, follow-up silk is processed further is caused to occur Difficulty.
HOY i.e. high oriented fibers, has stable internal structure and preferable uniformity, and the degree of orientation is high, and crystal region orientation is filled Point but amorphous area orientation is the lowest, dye and be easier to inhale color and evenly than FDY.Strength ratio routine FDY is on the low side, and elongation is big, boiling water Shrinking low, therefore fiber softening is good, can directly weave use as final products.But HOY product typically need 6000m/min with On super high-speed spinning technique produce, need special spinning oil, and high to equipment and technological requirement.
Summary of the invention
It is an object of the invention to overcome the problems such as existing PBT stock-dye is irregular, mechanical property is poor, it is achieved large-scale Production spinning, it is provided that a kind of porous PBT fiber HOY silk and preparation method thereof.The raw material of the PBT fiber of the present invention is modified PBT polyester, introduces the dihydroxylic alcohols segment containing side chain, is modified modification prepared by PBT polyester in the strand of modified PBT polyester PBT fiber, under the conditions of uniform temperature, the increasing degree of the spatial joint clearance of modified PBT fibrous inside molecule interchain is far longer than same The degree within molecule entrance such as unbranched common PBT fiber, beneficially stain under equitemperature, improves dyeing speed Rate；The melt viscosity of modified PBT fiber reduces, and reduces processing temperature, reduces degradation rate, is conducive to processing；Additionally containing side chain Dihydroxylic alcohols segment the structural regularity of modified PBT fiber is not had big destruction, maintain the premium properties of PBT fiber.This Invention spinning process uses the spinneret of spinneret orifice oval shaped arrangements, beneficially uniform, abundant in spinning process of fiber Cooling, performance and structure difference between fiber are less, improve dyeing uniformity and the mechanical property of fiber.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of porous PBT fiber HOY silk, the material of described porous PBT fiber HOY silk is modified PBT polyester, described modification PBT polyester forms by p-phthalic acid segment, BDO segment with containing the dihydroxylic alcohols segment of side chain, described containing side chain two Unit's alcohol segment refers on the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and side chain is straight containing 5-10 carbon atom The dihydroxylic alcohols segment of chain carbochain；
The filament number of described porous PBT fiber HOY silk is 0.3～1.0dtex, fracture strength >=2.6cN/dtex, disconnected Splitting percentage elongation is 50.0 ± 5.0%；Described porous PBT fiber HOY silk at temperature is 80～130 DEG C, fibrous inside strand Between spatial joint clearance increase 10～30v/v%；Line density deviation ratio≤0.2% of described porous PBT fiber HOY silk, fracture is strong Degree CV value≤2.5%, extension at break CV value≤5.0%, described molecule interchain spatial joint clearance increase refer to modified poly ester and Normal polyester is in the contrast of the spatial joint clearance of mutually synthermal molecule interchain.
Present invention also offers the preparation method of a kind of porous PBT fiber HOY silk, modified PBT polyester is used porous spray Filament plate spinning prepares porous PBT fiber HOY silk；On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, institute Stating oval shaped arrangements and refer to that the hole of spinneret orifice is centrally located on concentration ellipse, described concentration ellipse is that series is oval, all ellipses Major axis conllinear, and short axle conllinear；
The preparation method of described porous PBT fiber HOY silk is: modified PBT polyester obtains Modified polyester chips through pelletizing；Again Through measuring, extrude, cool down, oil and high-speed winding, prepare porous polyester fiber HOY silk；
The preparation method of described porous PBT fiber HOY silk is: p-phthalic acid, dihydroxylic alcohols containing side chain and 1,4-fourth two Alcohol polycondensation prepares modified PBT polyester, then obtains modified PBT polyester slice through pelletizing；Again through measuring, extrude, cool down, oil and rolling up Around, prepare porous PBT fiber HOY silk；
The preparation process of described modified PBT polyester is:
(1) preparation of p-phthalic acid binary alcohol esters；
After p-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, it is esterified Reaction obtains p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain refer to one that side chain is positioned in dihydroxylic alcohols segment non- On end group carbon and dihydroxylic alcohols that side chain is the linear carbon chain containing 5-10 carbon atom；
For the dihydroxylic alcohols containing side chain, its side chain is alkyl, is electron withdraw group, in the existence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociation so that the dihydroxylic alcohols containing side chain and terephthaldehyde Sour reactivity, less than BDO, according to the mixing of same BDO and terephthaldehyde's acid reaction, can cause containing propping up The diol reaction of chain is imperfect, thus the ratio that the dihydroxylic alcohols that impact is containing side chain is in polyester macromolecule, and then affect polyester Performance.The present invention uses and the dihydroxylic alcohols containing side chain first carries out under the catalytic action of sulphuric acid esterification with p-phthalic acid instead Should, its product adds after BDO and p phthalic acid esterification terminate, it is ensured that the dihydroxylic alcohols proportioning containing side chain steady Qualitative；
(2) preparation of p-phthalic acid 1,4-butanediol ester；
After p-phthalic acid and BDO are made into slurry, carry out esterification under negative pressure, obtain terephthaldehyde Acid 1,4-butanediol ester；
(3) preparation of modified PBT polyester；
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out successively the coarse vacuum stage polycondensation reaction and The polycondensation reaction of high vacuum stage of Fig, prepares modified PBT polyester.
As preferred technical scheme:
The preparation method of a kind of porous PBT fiber HOY silk as above, described modified PBT polyester specifically prepare step Suddenly it is:
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, works as ester Change reaction in water quantity of distillate reach theoretical value more than 90% time be esterification terminal, obtain p-phthalic acid dihydroxylic alcohols Ester；
(2) preparation of p-phthalic acid 1,4-butanediol ester；
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is less than absolute pressure 1KPa, and temperature is at 160～220 DEG C, when the water quantity of distillate in esterification reaches theoretical value More than 90% time be esterification terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester；
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mixing mixing 15-20 minute, under the effect of catalyst and stabilizer, the polycondensation starting the coarse vacuum stage under conditions of negative pressure is anti- Should, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, and the response time is 30～50 minutes；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 270～275 DEG C, response time 50～90 minutes, prepares modified PBT polyester；
The main spinning technology parameter of described porous PBT fiber HOY silk is:
The temperature of extrusion: 260～290 DEG C；
The pathogenic wind-warm of cooling: 20～30 DEG C；
The oil applying rate oiled: 0.42～1.5wt%；
The speed of winding: 6000～7000m/min.
The preparation method of a kind of porous PBT fiber HOY silk as above, in step (1), p-phthalic acid with containing side chain The mol ratio of dihydroxylic alcohols be 1:1.3-1.5；Concentrated sulphuric acid addition is the 0.3-0.5% of p-phthalic acid weight；Described dense sulfur The concentration of acid is 50-60wt%；
In step (2), p-phthalic acid is 1:1.2～2.0 with the mol ratio of BDO；
In step (3), described p-phthalic acid binary alcohol esters and the molar percentage of p-phthalic acid BDO ester Value is 2～5%；Described catalyst is butyl titanate, metatitanic acid four isopropyl ester, tetraethyl titanate, stannous acetate or two acetic acid two Butyl tin, catalyst charge is the 0.01%～0.05% of p-phthalic acid gross weight；Described stabilizer be triphenyl phosphate, Trimethyl phosphate or NSC 6513, stabilizer addition is the 0.01%～0.05% of described p-phthalic acid gross weight；
The number-average molecular weight of described modified PBT polyester is 15000～30000.
The preparation method of a kind of porous PBT fiber HOY silk as above, the described dihydroxylic alcohols containing side chain be 2-amyl group- 1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 propylene glycol, 2-nonyl-1,3 the third two Alcohol, 2-decyl-1,3 propylene glycol, 2-amyl group-1,4 butanediol, 2-hexyl-1,4 butanediol, 2-heptyl-1,4 butanediol, 2-are pungent Base-1,4 butanediol, 2-nonyl-1,4 butanediol, 2-decyl-1,4 butanediol, 2-amyl group-1,5 pentanediol, 2-hexyl-1,5 penta Glycol, 2-heptyl-1,5 pentanediol, 2-octyl group-1,5 pentanediol, 2-nonyl-1,5 pentanediol, 2-decyl-1,5 pentanediol, 2-penta Base-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 hexanediol, 2-nonyl-1,6 are own Glycol or 2-decyl-1,6 hexanediol base-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 hexanediol, 2-nonyl- More than one in 1,6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of a kind of porous PBT fiber HOY silk as above, described spinneret orifice be arranged as major axis and/or Short axial symmetry.
The preparation method of a kind of porous PBT fiber HOY silk as above, oval major axis with the ratio of minor axis length is 1.3～1.8；The spacing of adjacent spinneret orifice adds 1.5mm more than or equal to the guide hole diameter of spinneret orifice.Effective area when spinneret Mutually simultaneously as the girth of ellipse is more than circular girth, the number of plies of spinneret orifice oval shaped arrangements is less than the layer of circular arrangement Number, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and therefore, spinneret orifice oval shaped arrangements is conducive to ring to dry Cooling, improve ring blowing cooling effectiveness, the fibre property of preparation is the most more excellent.Major axis more connects with the ratio of minor axis length Being bordering on 1, ellipse is more similar to circle, and the difference of cooling effectiveness and cooling effect is little；Major axis is 1.3 with the ratio of minor axis length Time, cooling effect significantly improves, and individual pen hole count increases by 16% accordingly；When the ratio of major axis and minor axis length is 1.8, cooling effect Improving relatively big, individual pen hole count increases by 33% accordingly, and in the case of identical hole count, the oval shaped arrangements of the present invention is than conventional concentric circle row The number of turns of row reduces, it is easy to cooling wind is saturating, makes the fiber cooling condition of Internal and external cycle evenly；Major axis and the ratio of minor axis length During more than 1.8, ellipse is partial to form flat shape, is difficult to punching, and cooling no longer raises.Therefore, series is ellipse The major axis of circle is 1.3～1.8 with the ratio of minor axis length, it is possible to reach higher cooling effectiveness and preferable cooling effect.
The preparation method of a kind of porous PBT fiber HOY silk as above, described spinneret is circular jetting filament plate or ellipse Shape spinneret；The difference of the long axis length that the diameter of described circular jetting filament plate is maximum with series ellipse is more than 10mm, described ellipse The difference of the long axis length that shape spinneret is maximum with series ellipse is more than 10mm.
The preparation method of a kind of porous PBT fiber HOY silk as above, the guide hole a diameter of 1.5 of described spinneret orifice～ 2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192.
The preparation method of a kind of porous PBT fiber HOY silk as above, the cross section of the spinneret orifice of described spinneret Generally circular in shape, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type.
The principle of the present invention is:
For unbranched PBT fiber, its molecular chain structure is the linear macromolecule containing benzene ring structure, on strand Functional group's marshalling, regularity is good, flexible poor；When temperature raises, its free volume increments is little, and these characteristics hinder Dyestuff enters PBT fibrous inside, thus dyeability is poor.
The raw material of the PBT fiber of the present invention is modified PBT polyester, modified PBT polyester macromolecule contains containing side chain Dihydroxylic alcohols segment, when temperature is higher than vitrification point, side chain is prior to backbone motion, and the increasing degree making free volume is the biggest In the characteristic of unbranched polyester macromolecule chain, the increase of free volume improves molecule and enters the degree within polyester, The free volume being modified PBT fiber prepared by PBT polyester is far longer than unbranched PBT fiber at equal temperature, increases dye The diffusion of material, improves the dyeability of PBT fiber.Meanwhile, the PBT fiber that prepared by modified PBT polyester advantageously reduces molten Body viscosity, is conducive to improving its processing characteristics.The introducing of the dihydroxylic alcohols segment containing side chain is the biggest to PBT fibre structure regularity Destruction, maintain the premium properties of PBT fiber.
When the effective area phase of spinneret is simultaneously as the girth of ellipse is more than circular girth, and spinneret orifice is oval The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements, more than the hole count of circular arrangement, uses spray The spinneret of silk hole oval shaped arrangements enables to fiber quickly, uniformly cool down, and between fiber, the difference of structure and performance is less, Be conducive to improving even dyeing rate and the performance of fiber of fiber.
Beneficial effect:
1) on the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, and the effective area of spinneret is identical Time, the number of plies of spinneret orifice oval shaped arrangements is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning less than the number of plies of circular arrangement, ring blowing Cooling effect more preferable, the fibre property of preparation is the most more excellent.
2) on the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, and the effective area of spinneret is identical Time, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and oval shaped arrangements is capable of cooling down greatly, Significantly improve cooling effectiveness.
3) material of the porous PBT fiber HOY silk that the present invention prepares is modified PBT polyester, in modified PBT polyester macromolecule The dihydroxylic alcohols segment containing side chain contained, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free volume Increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule and enters poly- Degree within ester, is added the free volume diffusion with increase dyestuff of PBT fiber, improves PBT fiber by side chain Dyeability.
4) the porous PBT fiber HOY silk that the present invention prepares, the increase of PBT fiber free volume advantageously reduces melt and glues Degree, is conducive to improving its processing characteristics.
5) present invention prepares porous PBT fiber HOY silk, the dihydroxylic alcohols segment containing side chain introduce to PBT fiber Structural regularity does not has big destruction, maintains the premium properties of PBT fiber.
6) present invention prepares porous PBT fiber HOY silk dyeability and good mechanical performance, porous PBT fiber HOY silk Line density deviation ratio≤0.2%, fracture strength CV value≤2.5%, extension at break CV value≤5.0%.
Accompanying drawing explanation
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of short axle Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of short axle Degree ratio is 1.6.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited Fixed scope.
Embodiment 1
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.3 and 2-amyl group-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.3% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 160 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 90% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 15 minutes, Addition is the catalyst butyl titanate of the 0.01% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.01%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 260 DEG C, and the response time is 30 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 270 DEG C, in 50 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 15000, by p-phthalic acid segment, BDO segment With 2-amyl group-1,3 propylene glycol segment compositions, 2-amyl group-1,3 propylene glycol segments and the Mole percent ratio of BDO segment It is 2%.
Embodiment 2
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.38 and 2-hexyl-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.32% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.13MPa, and temperature is 181 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 91% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 165 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 90% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.1% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 16 minutes, Catalyst butyl titanate and addition at 0.011% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.02%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 262 DEG C, and the response time is 31 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 99Pa, and reaction temperature controls at 275 DEG C, In 51 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 16000, by p-phthalic acid segment, BDO segment With 2-hexyl-1,3 propylene glycol segment compositions, 2-hexyl-1,3 propylene glycol segments and the Mole percent ratio of BDO segment It is 2.1%.
Embodiment 3
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.33 and 2-heptyl-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.33% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.12MPa, and temperature is 183 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 170 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 90% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.2% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 16 minutes, Catalyst butyl titanate and addition at 0.03% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.02%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature controls at 263 DEG C, and the response time is 32 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 80Pa, and reaction temperature controls at 271 DEG C, In 57 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 15900, by p-phthalic acid segment, BDO segment With 2-heptyl-1,3 propylene glycol segment compositions, 2-heptyl-1,3 propylene glycol segments and the Mole percent ratio of BDO segment It is 2.2%.
Embodiment 4
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.34 and 2-octyl group-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.34% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.13MPa, and temperature is 184 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 180 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 90% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.3% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 17 minutes, Catalyst butyl titanate and addition at 0.033% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.023%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 497Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 264 DEG C, and the response time is 33 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 272 DEG C, in 58 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 15800, by p-phthalic acid segment, BDO segment With 2-octyl group-1,3 propylene glycol segment compositions, 2-octyl group-1,3 propylene glycol segments and the Mole percent ratio of BDO segment It is 2.3%.
Embodiment 5
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.35 and 2-nonyl-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.36% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.14MPa, and temperature is 185 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.2% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 190 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 90% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.4% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 17 minutes, Catalyst butyl titanate and addition at 0.034% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.024%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 34 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 273 DEG C, in 59 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 15900, by p-phthalic acid segment, BDO segment With 2-nonyl-1,3 propylene glycol segment compositions, 2-nonyl-1,3 propylene glycol segments and the Mole percent ratio of BDO segment It is 2.4%.
Embodiment 6
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.36 and 2-decyl-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.37% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.15MPa, and temperature is 186 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.3% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 200 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 91% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.5% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst butyl titanate and addition at 0.035% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 266 DEG C, and the response time is 35 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 275 DEG C, in 60 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 16000, by p-phthalic acid segment, BDO segment With 2-decyl-1,3 propylene glycol segment compositions, 2-decyl-1,3 propylene glycol segments and the Mole percent ratio of BDO segment It is 2.5%.
Embodiment 7
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid that mol ratio is 1:1.37 is made into slurry with 2-amyl group-Isosorbide-5-Nitrae butanediol and adds in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.38% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.16MPa, and temperature is 187 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.4% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 210 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 91% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.6% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 minutes, Catalyst metatitanic acid four isopropyl ester and addition at 0.036% that addition is p-phthalic acid weight are p-phthalic acid weight 0.025% stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, should Staged pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 270 DEG C, in 61 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 16000, by p-phthalic acid segment, BDO segment With 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-amyl group-Isosorbide-5-Nitrae butanediol segment and the Mole percent ratio of BDO segment It is 2.6%.
Embodiment 8
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid that mol ratio is 1:1.38 is made into slurry with 2-hexyl-Isosorbide-5-Nitrae butanediol and adds in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.39% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 220 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 91% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.7% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 minutes, Catalyst metatitanic acid four isopropyl ester and addition at 0.036% that addition is p-phthalic acid weight are p-phthalic acid weight 0.025% stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, should Staged pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls 273 DEG C, in 61 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 17000, by p-phthalic acid segment, BDO segment With 2-hexyl-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-Isosorbide-5-Nitrae butanediol segment and the Mole percent ratio of BDO segment It is 2.7%.
Embodiment 9
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid that mol ratio is 1:1.39 is made into slurry with 2-heptyl-Isosorbide-5-Nitrae butanediol and adds in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 160 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 91% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.8% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 16 minutes, Catalyst metatitanic acid four isopropyl ester and addition at 0.04% that addition is p-phthalic acid weight are p-phthalic acid weight 0.026% stabilizer trimethyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, should Staged pressure is steadily evacuated to absolute pressure 497Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 38 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 50Pa, and reaction temperature controls 275 DEG C, in 62 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 18000, by p-phthalic acid segment, BDO segment With 2-heptyl-Isosorbide-5-Nitrae butanediol segment composition, 2-heptyl-Isosorbide-5-Nitrae butanediol segment and the Mole percent ratio of BDO segment It is 2.8%.
Embodiment 10
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid that mol ratio is 1:1.4 is made into slurry with 2-octyl group-Isosorbide-5-Nitrae butanediol and adds in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.7KPa, and temperature is at 160 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 91% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 3% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 17 minutes, Addition is catalyst metatitanic acid four isopropyl ester of the 0.03% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.027%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature controls at 269 DEG C, and the response time is 39 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 50Pa, and reaction temperature controls 270 DEG C, in 64 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 19000, by p-phthalic acid segment, BDO segment With 2-octyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-octyl group-Isosorbide-5-Nitrae butanediol segment and the Mole percent ratio of BDO segment It is 3%.
Embodiment 11
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid that mol ratio is 1:1.4 is made into slurry with 2-nonyl-Isosorbide-5-Nitrae butanediol and adds in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.18MPa, and temperature is 189 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.6% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.7KPa, and temperature is at 170 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 91% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Addition is catalyst metatitanic acid four isopropyl ester of the 0.04% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.03%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 497Pa by normal pressure, and temperature controls at 260 DEG C, and the response time is 40 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls 271 DEG C, in 63 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 20000, by p-phthalic acid segment, BDO segment With 2-nonyl-Isosorbide-5-Nitrae butanediol segment composition, 2-nonyl-Isosorbide-5-Nitrae butanediol segment and the Mole percent ratio of BDO segment It is 4%.
Embodiment 12
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid that mol ratio is 1:1.4 is made into slurry with 2-nonyl-Isosorbide-5-Nitrae butanediol and adds in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.2MPa, and temperature is 200 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 94% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.7KPa, and temperature is at 190 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.5% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst tetraethyl titanate and addition at 0.038% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.03%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 497Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 42 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls 272 DEG C, in 70 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 26000, by p-phthalic acid segment, BDO segment With 2-decyl-Isosorbide-5-Nitrae butanediol segment composition, 2-decyl-Isosorbide-5-Nitrae butanediol segment and the Mole percent ratio of BDO segment It is 4%.
Embodiment 13
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.5 and 2-decyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.5% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.7KPa, and temperature is at 180 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 5% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 20 minutes, Addition is the catalyst tetraethyl titanate of the 0.05% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.05%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should It is 450Pa that staged pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 270 DEG C, and the response time is 50 minutes；Then continue Continuous evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 30Pa, and reaction temperature controls 270 DEG C, in 90 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 30000, by p-phthalic acid segment, BDO segment With 2-decyl-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments and the Mole percent ratio of BDO segment It is 5%.
Embodiment 14
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.7KPa, and temperature is at 190 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Addition is the catalyst tetraethyl titanate of the 0.04% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.04%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 263 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 270 DEG C, In 85 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 28000, by p-phthalic acid segment, BDO segment With 2-nonyl-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments and the Mole percent ratio of BDO segment It is 4%.
Embodiment 15
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 200 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.5% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 minutes, Catalyst tetraethyl titanate and addition at 0.044% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.046%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 269 DEG C, and the response time is 48 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 270 DEG C, In 87 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment With 2-octyl group-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments and the Mole percent ratio of BDO segment It is 4.5%.
Embodiment 16
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.49 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 210 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 minutes, Catalyst tetraethyl titanate and addition at 0.048% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 48 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 272 DEG C, In 83 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 27000, by p-phthalic acid segment, BDO segment With 2-heptyl-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments and the Mole percent ratio of BDO segment It is 4.7%.
Embodiment 17
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.467 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Being 60wt% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.6KPa, and temperature is at 220 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst tetraethyl titanate and addition at 0.04% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 48 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls 272 DEG C, in 85 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment With 2-hexyl-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments and the Mole percent ratio of BDO segment It is 4.3%.
Embodiment 18
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.48 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 160 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst acetic acid stannous and addition at 0.047% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 272 DEG C, In 85 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 28000, by p-phthalic acid segment, BDO segment With 2-amyl group-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments and the Mole percent ratio of BDO segment It is 4.7%.
Embodiment 19
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-decyl-1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 170 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 minutes, Catalyst acetic acid stannous and addition at 0.046% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.048%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should It is 446Pa that staged pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 267 DEG C, and the response time is 49 minutes；Then continue Continuous evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls 272 DEG C, in 87 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment With 2-decyl-1,5 pentanediol segment compositions, 2-decyl-1,5 pentanediol segments and the Mole percent ratio of BDO segment It is 4.7%.
Embodiment 20
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-nonyl-1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 180 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.1% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst acetic acid stannous and addition at 0.041% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 273 DEG C, In 85 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 28000, by p-phthalic acid segment, BDO segment With 2-nonyl-1,5 pentanediol segment compositions, 2-nonyl-1,5 pentanediol segments and the Mole percent ratio of BDO segment It is 4.1%.
Embodiment 21
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 and 2-octyl group-1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 190 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 17 minutes, Catalyst acetic acid stannous and addition at 0.043% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.049%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 273 DEG C, In 85 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 28000, by p-phthalic acid segment, BDO segment With 2-octyl group-1,5 pentanediol segment compositions, 2-octyl group-1,5 pentanediol segments and the Mole percent ratio of BDO segment It is 4.3%.
Embodiment 22
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 and 2-heptyl-1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 200 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst acetic acid stannous and addition at 0.047% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.04%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 470Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 45 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 273 DEG C, In 83 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment With 2-heptyl-1,5 pentanediol segment compositions, 2-heptyl-1,5 pentanediol segments and the Mole percent ratio of BDO segment It is 4.6%.
Embodiment 23
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.457 and 2-hexyl-1,5 pentanediols are made into slurry and add in reactor, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.8KPa, and temperature is at 210 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 92% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.41% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 points Clock, catalyst dibutyltin diacetate and addition at 0.042% that addition is p-phthalic acid weight are terephthaldehyde Under the effect of the stabilizer NSC 6513 of the 0.048% of acid weight, under conditions of negative pressure, start the contracting in coarse vacuum stage Poly-reaction, this staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 points Clock；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature Degree controls at 273 DEG C, 85 minutes response time, prepares modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 28000, by p-phthalic acid segment, BDO segment With 2-hexyl-1,5 pentanediol segment compositions, 2-hexyl-1,5 pentanediol segments and the Mole percent ratio of BDO segment It is 4.41%.
Embodiment 24
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-amyl group-1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.5KPa, and temperature is at 220 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 93% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.67% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 19 points Clock, catalyst dibutyltin diacetate and addition at 0.041% that addition is p-phthalic acid weight are terephthaldehyde Under the effect of the stabilizer triphenyl phosphate of the 0.042% of acid weight, under conditions of negative pressure, start the polycondensation in coarse vacuum stage Reaction, this staged pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes； Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature control System, at 274 DEG C, in 89 minutes response time, prepares modified PBT polyester.
The number-average molecular weight of the modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment With 2-amyl group-1,5 pentanediol segment compositions, 2-amyl group-1,5 pentanediol segments and the Mole percent ratio of BDO segment It is 4.67%.
Embodiment 25
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,5 pentanediol and 2-amyl group-1,4 butanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1, and the mol ratio of 5 pentanediols and 2-amyl group-Isosorbide-5-Nitrae butanediol is 3:1, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.5KPa, and temperature is at 220 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 93% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst dibutyltin diacetate and addition at 0.042% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of the 0.047% of amount, the polycondensation starting the coarse vacuum stage under conditions of negative pressure is anti- Should, this staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；So Rear continuation evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls At 274 DEG C, in 88 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment, 2-hexyl-1,5 pentanediol segments and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,5 pentanediol segments and 2-amyl group- The summation of 1,4 butanediol segments is 4.4% with the Mole percent ratio of 1,4-butanediol segment.
Embodiment 26
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By 2-octyl group-1,6 hexanediol of p-phthalic acid sum that mol ratio is 1:1.45 and 2-amyl group-1,5 pentanediol Mixture is made into slurry and adds in reactor, wherein 2-octyl group-1,6 hexanediol and 2-amyl group-1, and the mol ratio of 5 pentanediols is 3: 2, it is 60% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.5KPa, and temperature is at 160 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 93% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst dibutyltin diacetate and addition at 0.0423% that addition is p-phthalic acid weight are p-phthalic acid Under the effect of the stabilizer NSC 6513 of the 0.045% of weight, under conditions of negative pressure, start the polycondensation in coarse vacuum stage Reaction, this staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes； Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature control System, at 274 DEG C, in 85 minutes response time, prepares modified PBT polyester.
The number-average molecular weight of modified PBT polyester prepared is 28000, by p-phthalic acid segment, BDO segment, 2-octyl group-1,6 hexanediol segments and 2-amyl group-1,5 pentanediol segments compositions, 2-octyl group-1,6 hexanediol segments and 2-amyl group- 1,5 pentanediol segments are 4.6% with the Mole percent ratio of 1,4-butanediol segment.
Embodiment 27
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,5 pentanediol and 2-amyl group-1,4 butanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1, and the mol ratio of 5 pentanediols and 2-amyl group-Isosorbide-5-Nitrae butanediol is 3:1, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 96% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.5KPa, and temperature is at 180 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 93% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 minutes, Catalyst dibutyltin diacetate and addition at 0.042% that addition is p-phthalic acid weight are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of the 0.047% of amount, the polycondensation starting the coarse vacuum stage under conditions of negative pressure is anti- Should, this staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；So Rear continuation evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls At 275 DEG C, in 88 minutes response time, prepare modified PBT polyester.
The number-average molecular weight of modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment, 2-hexyl-1,5 pentanediol segments and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,5 pentanediol segments and 2-amyl group- The summation of 1,4 butanediol segments is 4.4% with the Mole percent ratio of 1,4-butanediol segment.
Embodiment 28
The preparation method of a kind of modified PBT polyester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.45 and 2-octyl group-1,3 propylene glycol, 2-amyl group-1,4 butanediol and 2-oneself Base-1, the mixture of 6 hexanediol is made into slurry and adds in reactor, wherein 2-octyl group-1,3 propylene glycol, 2-amyl group-Isosorbide-5-Nitrae fourth two Alcohol and 2-hexyl-1, the mol ratio of 6 hexanediol is 3:2:1, is 60% in concentration, and addition is p-phthalic acid weight Under the catalytic action of the concentrated sulphuric acid of 0.47%, carrying out esterification, esterification is compressive reaction in nitrogen atmosphere, moulding pressure For 0.29MPa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value, Obtain p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester:
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, Stress control is at 0.5KPa, and temperature is at 190 DEG C, anti-for being esterified when the water quantity of distillate in esterification reaches the 93% of theoretical value Answer terminal, obtain p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.71% with the Mole percent ratio of p-phthalic acid BDO ester, stirring mixing 18 points Clock, catalyst dibutyltin diacetate and addition at 0.04% that addition is p-phthalic acid weight are p-phthalic acid Under the effect of the stabilizer NSC 6513 of the 0.041% of weight, under conditions of negative pressure, start the polycondensation in coarse vacuum stage Reaction, this staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 49 minutes； Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature control System, at 275 DEG C, in 84 minutes response time, prepares modified PBT polyester.
The number-average molecular weight of modified PBT polyester prepared is 29000, by p-phthalic acid segment, BDO segment, Branched glycol segment forms, and the most branched glycol segment is 2-octyl group-1,3 propylene glycol segments, 2-amyl group-Isosorbide-5-Nitrae fourth Glycol segment and 2-hexyl-1,6 hexanediol segment compositions, branched glycol segment and the Mole percent of BDO segment Ratio is 4.71%.
Embodiment 29
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
As it is shown in figure 1, the ratio of the major axis of ellipse and minor axis length is 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circular.
The modified PBT polyester that embodiment 1 prepares, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion is 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the oil applying rate oiled is 0.42wt%, and the speed of winding is 6200m/min。
The fracture strength of the porous PBT fiber HOY silk prepared is 3.0cN/dtex, and elongation at break is 48.0%；Porous PBT fiber HOY silk is at temperature is 80 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%；The line of polyester fiber Density variation rate is 0.09%, and fracture strength CV value is 2.0%, and extension at break CV value is 4.0%, and yarn unevenness CV value is 2.0%, fracture strength is 0.3dtex.
Embodiment 30
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
As it is shown on figure 3, the ratio of the major axis of ellipse and minor axis length is 1.6, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circular.
The modified PBT polyester that embodiment 1 prepares, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion is 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the oil applying rate oiled is 0.42wt%, and the speed of winding is 6600m/min。
The fracture strength of the porous PBT fiber HOY silk prepared is 2.6cN/dtex, and elongation at break is 53%, porous PBT Fiber HOY silk is at temperature is 80 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 18v/v%；The line of polyester fiber is close Degree deviation ratio is 0.08%, and fracture strength CV value is 1.0%, and extension at break CV value is 3.0%, and yarn unevenness CV value is 1.0%, filament number is 0.3dtex.
Comparative example 1
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to that the hole of spinneret orifice is centrally located on concentric circular, with one heart Circle is circular for series.As in figure 2 it is shown, the spacing of adjacent spinneret orifice adds 1.5mm equal to the guide hole diameter of spinneret orifice, spinneret is Circular jetting filament plate, the difference of the diameter that the diameter of circular jetting filament plate is maximum with series circle is 11mm, the guide hole diameter of spinneret orifice For 2.0mm, the spray webbing hole count of spinneret is 370, and the shape of cross section of the spinneret orifice of spinneret is circular.
The modified PBT polyester that embodiment 1 prepares, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion is 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the oil applying rate oiled is 0.42wt%, and the speed of winding is 7000m/min。
The fracture strength of the porous PBT fiber HOY silk prepared is 3.0cN/dtex, and elongation at break is 52%；Porous PBT Fiber HOY silk is at temperature is 80 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 10v/v%；The line of polyester fiber is close Degree deviation ratio is 0.3%, and fracture strength CV value is 3.0%, and extension at break CV value is 6.0%, and yarn unevenness CV value is 5.0%, filament number is 0.5dtex.
When contrasting it can be seen that the effective area of spinneret is identical with embodiment 29, (circular arrangement when spray webbing hole count is close Spray webbing hole count is 370, and oval shaped arrangements spray webbing hole count is 374), the spinneret orifice number of plies of oval shaped arrangements is 6, less than circular arrangement The spinneret orifice number of plies 8, cooling effect is more preferable；When contrasting it can be seen that the effective area of spinneret is identical with embodiment 30, oval The spinneret orifice number of plies of shape arrangement is 5, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spray webbing of oval shaped arrangements The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, and cooling effectiveness is higher.The comparing result of fibre property shows, Fiber linear density deviation ratio, fracture strength CV value, extension at break CV value and the evenness fault that embodiment 29 and embodiment 30 prepare Rate CV value is less than comparative example 1, under the conditions of same process is described, uses the fibroid that the spinneret of spinneret orifice oval shaped arrangements prepares Can be better than using the spinneret of spinneret circular arrangement.
Embodiment 31～33
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 288 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 282 DEG C, and the pathogenic wind-warm of cooling is 21 DEG C, and the oil applying rate oiled is 0.6wt%, and the speed of winding is 6700m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 80 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 34～36
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.7mm, spinneret is elliptical spinneret plate, and elliptical spinneret plate and series ellipse are The difference of big long axis length is 12mm, a diameter of 1.8mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 384, spinneret The shape of cross section of spinneret orifice be rhombus.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 274 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, and the oil applying rate oiled is 0.8wt%, and the speed of winding is 6800m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 90 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 37～39
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as major axis and short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, adjacent spray webbing The spacing in hole is equal to the guide hole diameter of spinneret orifice plus 1.8mm, and spinneret is circular jetting filament plate, the diameter of circular jetting filament plate be The difference of the oval maximum long axis length of row is 13mm, and a diameter of 2.5mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 216, the shape of cross section of the spinneret orifice of spinneret is yi word pattern.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 285 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, and the oil applying rate oiled is 1.5wt%, and the speed of winding is 6900m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 100 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 40～42
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as major axis and short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.7, adjacent spray webbing The spacing in hole adds 1.9mm equal to the guide hole diameter of spinneret orifice, and spinneret is elliptical spinneret plate, elliptical spinneret plate and series The difference of oval maximum long axis length is 14mm, a diameter of 1.5mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 216, The shape of cross section of the spinneret orifice of spinneret is triangular form.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 286 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the oil applying rate oiled is 1.0wt%, and the speed of winding is 7000m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 110 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 43～45
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.5mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 15mm, and a diameter of 1.8mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 240, spray webbing The shape of cross section of the spinneret orifice of plate is trilobal cross.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 260 DEG C, and the pathogenic wind-warm of cooling is 24 DEG C, and the oil applying rate oiled is 1.2wt%, and the speed of winding is 6550m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 120 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 46～49
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 16mm, and a diameter of 2.2mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 250, spray webbing The shape of cross section of the spinneret orifice of plate is hollow type.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 270 DEG C, and the pathogenic wind-warm of cooling is 27 DEG C, and the oil applying rate oiled is 1.3wt%, and the speed of winding is 6200m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 130 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 50～53
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.8mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 15mm, and a diameter of 2.5mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 288, spray webbing The shape of cross section of the spinneret orifice of plate is platypelloid type.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 280 DEG C, and the pathogenic wind-warm of cooling is 28 DEG C, and the oil applying rate oiled is 0.9wt%, and the speed of winding is 6180m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 100 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 54～57
The preparation method of a kind of porous PBT fiber HOY silk, porous PBT fiber HOY silk uses porous spinneret to prepare, spray On filament plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.5mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 16mm, and a diameter of 1.8mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 300, spray webbing The shape of cross section of the spinneret orifice of plate is hollow type.
Modified PBT polyester, through measuring, extrude, cool down, oil and winding, prepares porous PBT fiber HOY silk, the temperature of extrusion Degree is 290 DEG C, and the pathogenic wind-warm of cooling is 30 DEG C, and the oil applying rate oiled is 0.8wt%, and the speed of winding is 6200m/min.Prepare The spatial joint clearance Magnification of porous PBT fiber HOY silk fibrous inside molecule interchain at 120 DEG C and the mechanical property number of fiber According to such as following table.
Embodiment 58
The dyeing of porous PBT fiber HOY silk:
Dyeing the porous PBT fiber HOY silk of embodiment 29 preparation in High Temperature High Pressure machine, actual conditions is: dye Before color, porous PBT fiber HOY silk nonionic surfactant processes 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dyeing Disperse dyes consumption in liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath raio For 1:50, at 60 DEG C, enter dye, then heat to each constant temperature dyeing 1h of 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C.
Use identical dyeing condition that general fibre is dyeed.The upper dye of the porous PBT fiber HOY silk after dyed Percentage rate obtains by the following method:
Dye uptake uses residual liquid colorimetry to determine, draws appropriate dyeing stock solution and dyeing residual liquid, adds N, N-2 first Base Methanamide (DMF) and distilled water, DMF and the ratio of water in dye liquor to be measured are 70/30 (v/v), and dye liquor absorbance uses purple Outward-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively dyeing stock solution and the absorbance of dyeing residual liquid.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, porous PBT fiber HOY silk and general The dye uptake result such as following table of perforating fiber:
Contrasted by the Color of porous PBT fiber HOY silk with general fibre, it can be seen that porous PBT fiber HOY silk Color be substantially better than general fibre, the modified PBT polyester macromolecule that also from side illustration prepared by the present invention contains The dihydroxylic alcohols segment containing side chain, make the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, The increase of free volume improves molecule and enters degree within polyester, is modified polyester fiber prepared by PBT polyester Free volume is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improves polyester fiber Dyeability.
Embodiment 59
The dyeing of porous PBT fiber HOY silk:
Dyeing the porous PBT fiber HOY silk of embodiment 31 preparation in High Temperature High Pressure machine, actual conditions is: dye Before color, porous PBT fiber HOY silk nonionic surfactant processes 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dyeing Disperse dyes consumption in liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath raio For 1:50, at 60 DEG C, enter dye, then heat to each constant temperature dyeing 1h of 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C.
Use identical dyeing condition that general fibre is dyeed.The upper dye of the porous PBT fiber HOY silk after dyed Percentage rate obtains by the following method:
Dye uptake uses residual liquid colorimetry to determine, draws appropriate dyeing stock solution and dyeing residual liquid, adds N, N-2 first Base Methanamide (DMF) and distilled water, DMF and the ratio of water in dye liquor to be measured are 70/30 (v/v), and dye liquor absorbance uses purple Outward-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively dyeing stock solution and the absorbance of dyeing residual liquid.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, porous PBT fiber HOY silk and general The dye uptake result such as following table of perforating fiber:
Contrasted by the Color of porous PBT fiber HOY silk with general fibre, it can be seen that porous PBT fiber HOY silk Color be substantially better than general fibre, the modified PBT polyester macromolecule that also from side illustration prepared by the present invention contains The dihydroxylic alcohols segment containing side chain, make the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, The increase of free volume improves molecule and enters degree within polyester, is modified polyester fiber prepared by PBT polyester Free volume is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improves polyester fiber Dyeability.

Claims (10)

1. a porous PBT fiber HOY silk, is characterized in that: the material of described porous PBT fiber HOY silk is modified PBT polyester, Described modified PBT polyester forms by p-phthalic acid segment, BDO segment with containing the dihydroxylic alcohols segment of side chain, described contains The dihydroxylic alcohols segment of side chain refers on the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and side chain is for containing 5-10 carbon The dihydroxylic alcohols segment of the linear carbon chain of atom；
The filament number of described porous PBT fiber HOY silk is 0.3～1.0dtex, and fracture strength >=2.6cN/dtex, fracture is stretched Long rate is 50.0 ± 5.0%；Described porous PBT fiber HOY silk at temperature is 80～130 DEG C, fibrous inside molecule interchain Spatial joint clearance increases 10～30v/v%；Line density deviation ratio≤0.2% of described porous PBT fiber HOY silk, fracture strength CV Value≤2.5%, extension at break CV value≤5.0%, the spatial joint clearance increase of described molecule interchain refers to that modified poly ester is with conventional Polyester is in the contrast of the spatial joint clearance of mutually synthermal molecule interchain.
The preparation method of a kind of porous PBT fiber HOY silk the most as claimed in claim 1, is characterized in that: by modified PBT polyester Porous spinneret spinning is used to prepare porous PBT fiber HOY silk；On described porous spinneret, the arrangement mode of spinneret orifice is oval Shape arranges, and described oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, and described concentration ellipse is that series is oval, The major axis conllinear of all ellipses, and short axle conllinear；
The preparation method of described porous PBT fiber HOY silk is: p-phthalic acid, dihydroxylic alcohols containing side chain and the contracting of 1,4-butanediol Poly-prepared modified PBT polyester, then obtain modified PBT polyester slice through pelletizing；Again through measuring, extrude, cool down, oil and rolling up at a high speed Around, prepare porous PBT fiber HOY silk；
The preparation process of described modified PBT polyester is:
(1) preparation of p-phthalic acid binary alcohol esters；
After p-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carry out esterification Obtain p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain refers to the non-end group that side chain is positioned in dihydroxylic alcohols segment On carbon and dihydroxylic alcohols that side chain is the linear carbon chain containing 5-10 carbon atom；
(2) preparation of p-phthalic acid 1,4-butanediol ester；
After p-phthalic acid and BDO are made into slurry, carry out esterification under negative pressure, obtain p-phthalic acid 1, 4-butanediol ester；
(3) preparation of modified PBT polyester；
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in coarse vacuum stage successively The polycondensation reaction in empty stage, prepares modified PBT polyester.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that described modification The concrete preparation process of PBT polyester is:
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification, ester Changing reaction compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, works as esterification In water quantity of distillate reach theoretical value more than 90% time be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of p-phthalic acid 1,4-butanediol ester；
After p-phthalic acid and BDO are made into slurry, carry out esterification, esterification in nitrogen atmosphere, pressure Controlling less than absolute pressure 1KPa, temperature is at 160～220 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when more than 90%, obtains p-phthalic acid BDO ester；
(3) preparation of modified PBT polyester；
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under the effect of catalyst and stabilizer, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, the response time be 30～ 50 minutes；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 270～275 DEG C, response time 50～90 minutes, prepares modified PBT polyester；
The main spinning technology parameter of described porous PBT fiber HOY silk is:
The temperature of extrusion: 260～290 DEG C；
The pathogenic wind-warm of cooling: 20～30 DEG C；
The oil applying rate oiled: 0.42～1.5wt%；
The speed of winding: 6000～7000m/min.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that in step (1), P-phthalic acid is 1:1.3-1.5 with the mol ratio of the dihydroxylic alcohols containing side chain；Concentrated sulphuric acid addition is p-phthalic acid weight 0.3-0.5%；The concentration of described concentrated sulphuric acid is 50-60wt%；
In step (2), p-phthalic acid is 1:1.2～2.0 with the mol ratio of BDO；
In step (3), described p-phthalic acid binary alcohol esters is 2 with the Mole percent ratio of p-phthalic acid BDO ester ～5%；Described catalyst is butyl titanate, metatitanic acid four isopropyl ester, tetraethyl titanate, stannous acetate or two acetic acid dibutyl Stannum, catalyst charge is the 0.01%～0.05% of p-phthalic acid gross weight；Described stabilizer is triphenyl phosphate, phosphoric acid Trimethyl or NSC 6513, stabilizer addition is the 0.01%～0.05% of described p-phthalic acid gross weight；
The number-average molecular weight of described modified PBT polyester is 15000～30000.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that described containing side chain Dihydroxylic alcohols be 2-amyl group-1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 the third two Alcohol, 2-nonyl-1,3 propylene glycol, 2-decyl-1,3 propylene glycol, 2-amyl group-1,4 butanediol, 2-hexyl-1,4 butanediol, 2-heptan Base-1,4 butanediol, 2-octyl group-1,4 butanediol, 2-nonyl-1,4 butanediol, 2-decyl-1,4 butanediol, 2-amyl group-1,5 penta Glycol, 2-hexyl-1,5 pentanediol, 2-heptyl-1,5 pentanediol, 2-octyl group-1,5 pentanediol, 2-nonyl-1,5 pentanediol, 2-last of the ten Heavenly stems Base-1,5 pentanediol, 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 are own Glycol, 2-nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol base-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group- More than one in 1,6 hexanediol, 2-nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that described spinneret orifice Be arranged as major axis and/or short axial symmetry.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that oval major axis It is 1.3～1.8 with the ratio of minor axis length；The spacing of adjacent spinneret orifice adds 1.5mm more than or equal to the guide hole diameter of spinneret orifice.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that described spinneret For circular jetting filament plate or elliptical spinneret plate；The difference of the long axis length that the diameter of described circular jetting filament plate is maximum with series ellipse More than 10mm, the difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is more than 10mm.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that described spinneret orifice Guide hole a diameter of 1.5～2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192.
The preparation method of a kind of porous PBT fiber HOY silk the most according to claim 2, it is characterised in that described spray webbing The shape of cross section of the spinneret orifice of plate is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or flat Type.
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