CN104878487B - Composite differential shrinkage yarn and preparation method thereof - Google Patents
Composite differential shrinkage yarn and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite differential shrinkage yarn and a preparation method thereof. The composite differential shrinkage yarn is formed by compositing of a POY (polyester pre-oriented yarn) body and an FDY (fully drawn yarn) body, both the POY body and the FDY body are made of modified polyester by means of spinning, the modified polyester is formed by polyester and amino fatty acid gylcol ester, the amino fatty acid gylcol ester is scattered among molecular chains of the polyester, and a hydrogen-bond interaction among the amino fatty acid gylcol ester and the molecular chains of the polyester enables opposite positions of the amino fatty acid gylcol ester and the molecular chains of the polyester to be fixed; in the condition with temperature ranging from 90 DEG C to 130 DEG C, free volume spaces among molecular chains inside a fiber of the composite differential shrinkage yarn are enlarged by 20-30v/v%. The composite differential shrinkage yarn has the advantages that the free volume of polyester fibers is increased by the aid of fatty acid ester, so that diffusing degree of dye is improved, dyeing property of the polyester fibers is improved, and the composite differential shrinkage yarn is applicable to fashion fabric, decorative fabric and the like formed by means of spinning, knitting and warp knitting.
Description
Technical field
The invention belongs to polyester modification technical field, is related to a kind of abnormal contraction composite filament and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) fiber since the advent of the world, has obtained rapidly because of its excellent performance
Development, its yield has become the hat of world's synthetic fibers.Polyester fiber has fracture strength and elastic modelling quantity height, and resilience is fitted
In, thermal finalization is excellent, and heat-resisting light resistance is good and a series of premium properties such as acid-fast alkali-proof corrosion resistant candle property, and fabric have it is crease-resistant
Exempt from money, the advantages of stiffness is good, so, polyester fiber is widely used in the fields such as clothing, home textile.
PET belongs to symmetric straight chain macromolecular, and strand does not contain side-chain radical, and regularity is very good, its main chain
Alkyl containing rigid phenyl ring and flexibility, and the ester group being directly connected with phenyl ring constitutes rigid conjugated body with phenyl ring
System, so as to constrain rotating freely for its soft segment.Impact of this structure to glass transition temperature is it will be evident that increasing
The wall ridge of molecule segment motion, the glass transition temperature of PET is higher, needs to dye at very high temperatures, promotes dyestuff
Diffusion of the molecule to fibrous inside.In addition, the strand of PET is regular, good crystallinity, molecule chain alignment is tight, and strand
Upper no polar group having an effect with dye molecule, makes the colouring of polyester fiber more difficult.
It is difficult to solve the problems, such as PET dyeing, now mainly connect by introducing dye molecule using techniques or methods
By base or the method for increasing polyester amorphous regions amount, although the dyeability of polyester can be improved, the segment rule of PET are destroyed
Whole property, with the raising for reducing the performance of polyester fiber to obtain dyeability.Do not destroying polyester fiber crystallinity and permutation degree
In the case of, the method for adopting at present has three kinds of colouring methods such as support methods, high temperature and high pressure method and high temperature thermosoling.
Abnormal contraction composite filament is the long filament with different potential shrinkages, i.e. high-shrinkage filament POY and lower shrinkage silk FDY Jing
The composite filament of mixed fine processing composition, the main feature of the different contraction mixed fiber composite silks of PET：The feel of high loft and softness.PET is different
Contraction composite filament it is outer existing similar with common long filament.Long filament with different potential shrinkages, i.e. high-shrinkage filament POY and low receipts
The composite filament of the mixed fine processing compositions of contracting silk FDY Jing, due to the difference of two component shrinkage factors, and produces the effect of different contraction.
The content of the invention
It is an object of the invention to provide a kind of abnormal contraction composite filament and preparation method thereof, the present invention is using amino fatty acid second
In uniform temperature condition, the increasing degree of free volume is far longer than the characteristic of polyester macromolecule chain to diol ester, by improving
Disperse dyes molecule improves the dyeability of polyester into the degree inside polyester；Simultaneously because amino fatty acid second
In the presence of the first amino in glycol ester molecule, increase itself and the hydrogen bond action between polyester macromolecule chain, increased it and gather
The compatibility of ester and dispersion in the polyester, reduce to greatest extent migration.Simultaneously to polyester construction regularity, crystallinity
Without destruction, the premium properties of polyester is maintained.
The present invention a kind of abnormal contraction composite filament, the long filament with different potential shrinkages, i.e. high-shrinkage filament POY with it is low
The composite filament of the mixed fine processing compositions of contractile filaments FDY Jing, due to the difference of two component shrinkage factors, and produces the effect of different contraction.Institute
State modified poly ester to be made up of with amino ethylene glycol fatty acid polyester, the amino ethylene glycol fatty acid is dispersed in the polyester
Molecule interchain, and the amino ethylene glycol fatty acid has hydrogen bond action with the molecule interchain of the polyester, makes the amino
Ethylene glycol fatty acid is fixed with the relative position of the strand of the polyester；The abnormal contraction composite filament polyester is 90 in temperature
Under the conditions of～130 DEG C, the free volume space of fibrous inside molecule interchain increases 20～30v/v%；The abnormal contraction composite filament
Fracture strength >=1.9cN/dtex, elongation at break be 30.0 ± 5.0%, crimp contraction be 2.50 ± 3.0%, internet pricing
For 20 ± 5/m.
The molecular structure of the amino ethylene glycol fatty acid is：
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
As preferred technical scheme：
A kind of described abnormal contraction composite filament, line density deviation ratio ± 2.5% of the abnormal contraction composite filament, fracture strength
CV value≤5.0%, extension at break CV value≤10.0%, boiling water shrinkage is 15.0 ± 1.0%, coefficient of variation CV value≤
10.0%, oil content is 1.0 ± 0.2%, fiber number：100-150dtex.
A kind of described abnormal contraction composite filament, the amino ethylene glycol fatty acid accounts for the weight of the abnormal contraction composite filament
Percentage ratio is 0.5～2.5%.
Present invention also offers a kind of preparation method of described abnormal contraction composite filament, modified poly ester presses respectively POY techniques
With FDY technique spinning, then plying and silk, through network combined, finally wind and form abnormal contraction composite filament；Its processing technique：
Spinning temperature：280～300 DEG C；
Pathogenic wind-warm：20～22 DEG C；
Plying network pressure：3.5～4.5bar；
GR1 speed：800～1000m/min；
SR1 speed：3000～4200m/min；
GR2 speed：3000～400m/min；
HT1 temperature：90～115 DEG C；
HT2 temperature：130～140 DEG C；
Winding speed：3000～4000m/min；
The preparation process of the modified poly ester includes：
(1) preparation of amino ethylene glycol fatty acid：
1) by binary of fatty acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid, plus
Heat to 80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；The binary of fatty acids is ten
Dioxane dicarboxylic acids are to the one kind in dopentacontane dicarboxylic acids；Reaction equation is：
HOOC(CH2)nCOOH+CH3OH→CH3OOC(CH2)nCOOH；
Wherein n is 10～50；
2) by the binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 is dissolved in benzene, wherein two
The concentration of first fatty acid mono-methyl is 0.05～0.1mol/L, under nitrogen atmosphere, in 80～90 DEG C of reactions, backflow, when no longer
When having gas to produce, add a certain amount of dilute sulfuric acid to react 2～3 hours, be washed out, purify and be dried, obtain product bromo
Fatty acid；Reaction equation is：
3) by the ammonia of bromo fatty acid and 15～25wt% in molar ratio 1:2 are added in reactor, stirring, in room temperature
Lower reaction, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is less than 70 DEG C, until nothing
Bubble is produced, that is, stop distillation, is then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, by product
Vacuum drying obtains product amino fatty acid；Vacuum drying temperature can adopt 60～70 DEG C；Reaction equation is：
HOOC(CH2)nBr+NH3→HOOC(CH2)nNH2+NH4Br；
4) it is in molar ratio 1.1 by ethylene glycol and amino fatty acid:2 stir, and by the hundred of amino fatty acid wt
It is catalyst that/mono- addition concentration is the sulphuric acid of 40～50wt%, carries out esterification, and esterification reaction temperature is 160～220
DEG C, it is esterification terminal that esterification water quantity of distillate reaches more than the 90% of theoretical value；The separated purification of product obtains amino
Ethylene glycol fatty acid；Reaction equation is：
HOOC(CH2)nNH2+HOCH2CH2OH→
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Using p-phthalic acid and ethylene glycol as raw material, being made into after uniform sizing material carries out esterification, obtains esterification and produces
Thing；Esterification is pressurizeed in nitrogen atmosphere, and in normal pressure～0.3MPa, at 250～260 DEG C, esterification water evaporates temperature Stress control
It is esterification terminal that output reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, catalyst and stabilizer are added in esterification products, under conditions of negative pressure
Start polycondensation reaction, the staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control at 260～270 DEG C,
Response time is 30～50 minutes；
Amino ethylene glycol fatty acid is added after the polycondensation reaction coarse vacuum stage terminates, and is stirred, generally stirring
15～20 minutes；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 275～280 DEG C, 50～90 minutes response time；
Prepared modified poly ester.
A kind of preparation method of abnormal contraction composite filament as above, the ethylene glycol and the p-phthalic acid mole
Than for 1.2～2.0:1.
A kind of preparation method of abnormal contraction composite filament as above, the catalyst is selected from antimony oxide, ethylene glycol
One kind in antimony and antimony acetate, catalyst amount is the 0.01%～0.05% of the p-phthalic acid weight.
A kind of preparation method of abnormal contraction composite filament as above, the stabilizer is selected from triphenyl phosphate, tricresyl phosphate
One kind in methyl ester and NSC 6513, stabilizing agent dosage is the 0.01%～0.05% of the p-phthalic acid weight.
A kind of preparation method of abnormal contraction composite filament as above, deionized water adopts nitre till being washed till without bromide ion
Sour silver solution detection.
A kind of preparation method of abnormal contraction composite filament as above, the concentrated sulphuric acid refers to that mass concentration is 70～80%
Sulphuric acid, concentrated sulphuric acid addition for binary of fatty acids 1～3wt%；A certain amount of dilute sulfuric acid refers to that mass concentration is 40
～50% sulphuric acid, dilute sulfuric acid addition is 1～3wt% of binary of fatty acids mono-methyl.
In dyeing, disperse dyes can be divided into the following four stage to polyester fiber to the upper dye process of polyester fiber：
1) disperse dyes move closer to fiber interface in dye liquor with the flowing of dye liquor；2) disperse dyes are near fiber interface
Adsorbed by fiber surface rapidly；3) disperse dyes are adsorbed to after fiber surface, and a concentration difference or inside and outside is produced in fiber
Dyestuff chemistry potential difference, dyestuff will spread to fibrous inside；4) disperse dyes diffusion velocity and fiber unformed area content, hole or
Free volume content is relevant, therefore the dyeing speed of disperse dyes is further depended in addition to dyestuff dissolubility in the solution
The degree of swelling of fiber is relevant when the structure of fiber is outer and dyes.
Polyster fibre is hydrophobic synthetic fibers, is lacked in terylene molecular structure as cellulose or protein fibre
Energy and dyestuff there is the active group that combines, terylene molecules align must compare closely, and less space is only existed in fiber,
In dyeing under the conditions of humidity, polyester fiber will not can be by acutely swelling and increase space, dyestuff point as cotton fiber
Son is difficult to see through fibrous inside.Therefore, the carrying out that will be helpful to dye the free volume between fiber molecule is improved.
The molecular chain structure of polyester is the linear macromolecule containing benzene ring structure, the functional group's marshalling on strand,
Unbranched, macromole chain flexibility is poor.Simultaneously the regularity of polyester is good and rigidity is all larger, and intermolecular active force is larger.
Compared with other macromolecular materials, the strand generation sliding of polyester, rotation are all more difficult, and these characteristics hinder dyestuff and enter
Enter inside polyester, thus dyeability is poor.
Amino ethylene glycol fatty acid mainly with C-C, based on C-O keys, while have certain molecular weight, i.e., with certain
The strand of length, strand flexibility is larger, and the amount of crimp of amino ethylene glycol fatty acid is linear big compared with benzene ring structure
Molecule is bigger, while strong compared with the linear macromolecule containing benzene ring structure to the sensitivity of temperature.When the temperature is changed, amino fatty acid
Glycol ester is moved prior to the linear macromolecule containing benzene ring structure, and the free volume produced by motion is far longer than containing phenyl ring
Produced by the linear macromolecule of structure.
The free volume of polyester fiber is increased by fatty acid ester to increase the diffusion of dyestuff, improve polyester fiber
Dyeability, make fiber obtain high dye-uptake.
Oxygen in fatty acid ester can form hydrogen bond, but oxygen is at centre position, due to space steric effect and fat
The factors such as the curling of fat acid ester molecules reduce it with polyester macromolecule chain in hydrogen evolution hydrogen bond quantity；If amino is in α positions
On, i.e. amino acidses, because amino and carbonyl interact, the hydrogen evolution hydrogen being also unfavorable in amino and polyester macromolecule chain
Key；When the end position of the amino in macromole of amino fatty acid ester, the curling of macromole affects less, to increased aminolipid on it
The formation of the hydrogen evolution hydrogen bond in amino and polyester macromolecule chain in fat acid esters, while improve amino fatty acid ester and polyester
Active force between macromolecular chain, reduces the sliding and migration of amino fatty acid ester.
The compatibility and dispersion in the polyester of amino fatty acid ester and polyester is increased, is reduced move to greatest extent
Move.Polyester construction regularity, crystallinity are not destroyed simultaneously, maintains the premium properties of polyester.
Beneficial effect：
1. the abnormal contraction composite filament obtained by the present invention, because amino ethylene glycol fatty acid is based on C-C, while having
Certain molecular weight, the i.e. strand with certain length, strand flexibility is larger, and amino increased the compatibility with polyester.
The fiber of gained is good with the compatibility of amino ethylene glycol fatty acid.
2., due to the presence in amino ethylene glycol fatty acid molecule in the first amino, increase with it with polyester macromolecule chain
Between hydrogen bond action, increased its compatibility and dispersion in the polyester with polyester, migration is reduced to greatest extent.
3. the abnormal contraction composite filament obtained by the present invention, because the content of amino ethylene glycol fatty acid is less, ties to polyester
Structure regularity, crystallinity are not destroyed, and maintain the premium properties of polyester.
4. the amount of crimp of amino ethylene glycol fatty acid is bigger compared with the linear macromolecule of benzene ring structure, while to temperature
It is sensitive strong compared with the linear macromolecule containing benzene ring structure.When the temperature is changed, transport prior to the linear macromolecule containing benzene ring structure
Dynamic, the free volume produced by the motion of amino ethylene glycol fatty acid is far longer than the institute of the linear macromolecule containing benzene ring structure
Produce, increase the diffusion of additive to improve the feature of polyester.
5. fatty acid ester increased the free volume of polyester fiber to increase the diffusion of dyestuff, improve polyester fiber
Dyeability.
6. the abnormal contraction composite filament evidence obtained by the present invention has excellent shading performance, excellent dyeability, high fluffy
With soft feel, simultaneously because the fiber surface there are many wire rings, therefore the aurora defect of chemical fiber wire thing is also eliminated.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
The present invention a kind of abnormal contraction composite filament, the long filament with different potential shrinkages, i.e. high-shrinkage filament POY with it is low
The composite filament of the mixed fine processing compositions of contractile filaments FDY Jing, due to the difference of two component shrinkage factors, and produces the effect of different contraction.Institute
State modified poly ester to be made up of with amino ethylene glycol fatty acid polyester, the amino ethylene glycol fatty acid is dispersed in the polyester
Molecule interchain, and the amino ethylene glycol fatty acid has hydrogen bond action with the molecule interchain of the polyester, makes the amino
Ethylene glycol fatty acid is fixed with the relative position of the strand of the polyester；The abnormal contraction composite filament polyester is 90 in temperature
Under the conditions of～130 DEG C, the free volume space of fibrous inside molecule interchain increases 20～30v/v%；The abnormal contraction composite filament
Fracture strength >=1.9cN/dtex, elongation at break be 30.0 ± 5.0%, crimp contraction be 2.50 ± 3.0%, internet pricing
For 20 ± 5/m.
The molecular structure of the amino ethylene glycol fatty acid is：
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
A kind of described abnormal contraction composite filament, line density deviation ratio ± 2.5% of the abnormal contraction composite filament, fracture strength
CV value≤5.0%, extension at break CV value≤10.0%, boiling water shrinkage is 15.0 ± 1.0%, coefficient of variation CV value≤
10.0%, oil content is 1.0 ± 0.2%, fiber number：100-150dtex.
A kind of described abnormal contraction composite filament, the amino ethylene glycol fatty acid accounts for the weight of the abnormal contraction composite filament
Percentage ratio is 0.5～2.5%.
Colouring method：Dyeing disperse dyes are Disperse Red 3B, and disperse blue SE-2R disperses bright blue S-GL, fiber to exist respectively
Dye in High Temperature High Pressure machine.Fiber nonionic surfactant is processed 30 minutes at 60 DEG C before dye.Dye dosage is 2.0%
(o.w.f)；Dispersant NNO1.2g/L, pH value is 5, and bath raio is 1:50,60 DEG C of people dye, be warming up to 90 DEG C, 100 DEG C, 110 DEG C,
120 DEG C of each constant temperature dyeing 1h.
Dye uptake adds N, N-2 first using the determination of residual liquid colorimetry, the appropriate dyeing stock solution of absorption and dyeing residual liquid
Base Methanamide (DMF) and distilled water, the ratio for being DMF in dye liquor to be measured and water is 70/30 (v/v), and dye liquor absorbance is adopted
Ultraviolet-visible spectrophotometer is determined, and with following formula dye uptake is calculated.
In above formula, A0 and A1 respectively dyes the absorbance of stock solution and dyeing residual liquid.
Embodiment 1
A kind of preparation method of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by dodecanedicarboxylic acid and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid,
80 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains dodecanedicarboxylic acid mono-methyl；The concentrated sulphuric acid refers to that quality is dense
The sulphuric acid for 70% is spent, concentrated sulphuric acid addition is the 3wt% of dodecanedicarboxylic acid；
2) the dodecanedicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), wherein
Dodecanedicarboxylic acid mono-methyl concentration is 0.05mol/L, under nitrogen atmosphere, in 80 DEG C of reactions, backflow, is produced when there is no longer gas
When raw, add a certain amount of dilute sulfuric acid to react 2 hours, be washed out, purify and be dried, obtain product bromoundecane carboxylic acid；
A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is dodecanedicarboxylic acid mono-methyl
3wt%；
3) by the ammonia of bromoundecane carboxylic acid and 15wt% in molar ratio 1:2 are added in reactor, stirring, in room temperature
Lower reaction, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 60 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using silver nitrate
Solution detects, product is vacuum dried and obtains product amino-undecanoic carboxylic acid；
4) it is in molar ratio 1.1 by ethylene glycol and amino-undecanoic carboxylic acid:2 stir, and by amino-undecanoic carboxylic acid
1% addition concentration of weight is the sulphuric acid of 40wt%, carries out esterification, and esterification reaction temperature is 160 DEG C, esterification water quantity of distillate
It is esterification terminal to reach more than the 90% of theoretical value；The separated purification of product obtains amino-undecanoic carboxylic acid ethylene glycol
Ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:1.2 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.3MPa, temperature is 250 DEG C to Stress control, esterification
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.01% of p-phthalic acid weight three oxidations are added in esterification products
The triphenyl phosphate of two antimony and p-phthalic acid weight 0.01%, starts polycondensation reaction under conditions of negative pressure, the staged pressure
Steadily it is evacuated to below absolute pressure 500Pa by normal pressure, at 260 DEG C, the response time is 50 minutes to temperature control；
Amino-undecanoic carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 15 points
Clock；The amino-undecanoic carboxylic acid glycol ester, addition is the 0.5wt% of modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 275 DEG C, 90 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 15000；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：280℃；
Pathogenic wind-warm：20℃；
Plying network pressure：3.5bar；
GR1 speed：800m/min；
SR1 speed：3000m/min；
GR2 speed：3000m/min；
HT1 temperature：90℃；
HT2 temperature：130℃；
Winding speed：3000m/min；
Under the conditions of temperature is for 90 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
20v/v%, line density deviation ratio 2.5%, fracture strength 1.9cN/dtex, fracture strength CV value 5.0%, elongation at break is
35.0%, extension at break CV value 10.0%, boiling water shrinkage is 16.0%, and crimp contraction is 5.5%, crimp contraction variation
Coefficient CV values 10.0%, oil content is 1.2%, internet pricing be 25/m, fiber number：100dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 50.2 | 83.4 | 91.8 | 92.9 | 91.6 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 53.7 | 87.3 | 92.7 | 93.8 | 94.8 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 46.8 | 75.4 | 87.3 | 88.6 | 90.2 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Embodiment 2
A kind of preparation of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by dopentacontane dicarboxylic acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, in the catalysis of concentrated sulphuric acid
Under, 110 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains dopentacontane mono methyl dicarboxylate；The concentrated sulphuric acid is referred to
Mass concentration is 70% sulphuric acid, and concentrated sulphuric acid addition is the 3wt% of dopentacontane dicarboxylic acids；
2) the dopentacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), its
Middle dopentacontane mono methyl dicarboxylate concentration is 0.07mol/L, under nitrogen atmosphere, in 85 DEG C of reactions, backflow, when there is no longer gas
When body is produced, add a certain amount of dilute sulfuric acid to react 3 hours, be washed out, purify and be dried, obtain product bromo henpentacontane
Carboxylic acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is dopentacontane dicarboxylic acids
The 3wt% of mono-methyl；
3) by the ammonia of bromo henpentacontane carboxylic acid and 25wt% in molar ratio 1:2 are added in reactor, stirring, in room
The lower reaction of temperature, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 62 DEG C, until depletion of QI
Bubble is produced, that is, stop distillation, is then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using nitric acid
Silver-colored solution detection, by product vacuum drying product amino henpentacontane carboxylic acid is obtained；
4) it is in molar ratio 1.1 by ethylene glycol and amino henpentacontane carboxylic acid:2 stir, and by amino henpentacontane
2% addition concentration of carboxylic acid weight is the sulphuric acid of 45wt%, carries out esterification, and esterification reaction temperature is 220 DEG C, and esterification water evaporates
It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino henpentacontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:2.0 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.2MPa, temperature is esterified Stress control at 260 DEG C
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.05% of p-phthalic acid weight three oxidations are added in esterification products
The triphenyl phosphate of two antimony and p-phthalic acid weight 0.05%, starts polycondensation reaction under conditions of negative pressure, the staged pressure
Steadily it is evacuated to below absolute pressure 500Pa by normal pressure, at 270 DEG C, the response time is 30 minutes to temperature control；
Amino henpentacontane carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 20 points
Clock；Institute
It is 2.5% to state the percentage by weight that amino henpentacontane carboxylic acid glycol ester addition is modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 280 DEG C, 50 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 30000；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：300℃；
Pathogenic wind-warm：22℃；
Plying network pressure：4.5bar；
GR1 speed：1000m/min；
SR1 speed：4200m/min；
GR2 speed：4000m/min；
HT1 temperature：115℃；
HT2 temperature：140℃；
Winding speed：4000m/min；
Under the conditions of temperature is for 100 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
Big 22v/v%, line density deviation ratio -2.5%, fracture strength 2.0cN/dtex, fracture strength CV value 4.9%, elongation at break
For 25.0%, extension at break CV values 9.8%, boiling water shrinkage is 14.0%, and crimp contraction is -0.5%, and crimp contraction becomes
Different coefficient CV values 9.1%, oil content is 0.8%, internet pricing be 15/m, fiber number：150dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 50.5 | 83.7 | 92.3 | 93.1 | 91.7 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 53.9 | 87.4 | 93.1 | 94.2 | 95.0 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 46.4 | 75.0 | 87.1 | 88.2 | 89.8 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Embodiment 3
A kind of preparation method of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by pentacosane dicarboxylic acid and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid,
85 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains pentacosane dicarboxylic acid mono-methyl；The concentrated sulphuric acid refers to that quality is dense
The sulphuric acid for 70% is spent, concentrated sulphuric acid addition is the 3wt% of pentacosane dicarboxylic acid；
2) the pentacosane dicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), wherein
Pentacosane dicarboxylic acid mono-methyl concentration is 0.08mol/L, under nitrogen atmosphere, in 90 DEG C of reactions, backflow, is produced when there is no longer gas
When raw, add a certain amount of dilute sulfuric acid to react 2.5 hours, be washed out, purify and be dried, obtain product bromotetradecane carboxylic
Acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 50%, and dilute sulfuric acid addition is pentacosane dicarboxylic acid list first
The 3wt% of ester；
3) by the ammonia of bromotetradecane carboxylic acid and 20wt% in molar ratio 1:2 are added in reactor, stirring, in room temperature
Lower reaction, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 60 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using silver nitrate
Solution detects, product is vacuum dried and obtains product amino tetradecane carboxylic acid；
4) it is in molar ratio 1.1 by ethylene glycol and amino tetradecane carboxylic acid:2 stir, and by amino tetradecane carboxylic acid
2% addition concentration of weight is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 190 DEG C, esterification water quantity of distillate
It is esterification terminal to reach more than the 90% of theoretical value；The separated purification of product obtains amino tetradecane carboxylic acid ethylene glycol
Ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:1.6 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.3MPa, temperature is esterified Stress control at 255 DEG C
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.03% of p-phthalic acid weight three oxidations are added in esterification products
The triphenyl phosphate of two antimony and p-phthalic acid weight 0.03%, starts polycondensation reaction under conditions of negative pressure, the staged pressure
Steadily it is evacuated to below absolute pressure 500Pa by normal pressure, at 265 DEG C, the response time is 40 minutes to temperature control；
Amino tetradecane carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 16 points
Clock；The amino tetradecane carboxylic acid glycol ester addition is 1.0% for the percentage by weight of modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 276 DEG C, 70 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 22500；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：290300℃；
Pathogenic wind-warm：21℃；
Plying network pressure：4.0bar；
GR1 speed：900m/min；
SR1 speed：3600m/min；
GR2 speed：3500m/min；
HT1 temperature：105℃；
HT2 temperature：135℃；
Winding speed：3500m/min；
Under the conditions of temperature is for 105 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
Big 22v/v%, line density deviation ratio 2.0%, fracture strength 2.1cN/dtex, fracture strength CV value 4.8%, elongation at break is
34.0%, extension at break CV value 9.8%, boiling water shrinkage is 15.5%, and crimp contraction is 5.0%, crimp contraction variation
Coefficient CV values 9.2%, oil content is 1.1%, internet pricing be 24/m, fiber number：130dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 49.5 | 83.0 | 91.5 | 92.5 | 91.2 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 53.3 | 87.0 | 92.5 | 93.3 | 94.4 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 47.3 | 76.7 | 87.6 | 88.9 | 90.5 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Embodiment 4
A kind of preparation method of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by eicosane dicarboxylic acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid,
85 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains eicosane mono methyl dicarboxylate；The concentrated sulphuric acid refers to that quality is dense
The sulphuric acid for 70% is spent, concentrated sulphuric acid addition is the 3wt% of eicosane dicarboxylic acids；
2) the eicosane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), wherein
Eicosane mono methyl dicarboxylate concentration is 0.09mol/L, under nitrogen atmosphere, in 80 DEG C of reactions, backflow, is produced when there is no longer gas
When raw, add a certain amount of dilute sulfuric acid to react 2.1 hours, be washed out, purify and be dried, obtain product bromo nonadecane carboxylic
Acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 43%, and dilute sulfuric acid addition is eicosane dicarboxylic acids list first
The 2wt% of ester；
3) by the ammonia of bromo nonadecane carboxylic acid and 16wt% in molar ratio 1:2 are added in reactor, stirring, in room temperature
Lower reaction, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 69 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using silver nitrate
Solution detects, product is vacuum dried and obtains product amino nonadecane carboxylic acid；
4) it is in molar ratio 1.1 by ethylene glycol and amino nonadecane carboxylic acid:2 stir, and by amino nonadecane carboxylic acid
2% addition concentration of weight is the sulphuric acid of 42wt%, carries out esterification, and esterification reaction temperature is 160 DEG C, esterification water quantity of distillate
It is esterification terminal to reach more than the 90% of theoretical value；The separated purification of product obtains amino nonadecane carboxylic acid ethylene glycol
Ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:1.2 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.15MPa, temperature is esterified Stress control at 251 DEG C
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.02% of p-phthalic acid weight three oxidations are added in esterification products
The triphenyl phosphate of two antimony and p-phthalic acid weight 0.02%, starts polycondensation reaction under conditions of negative pressure, the staged pressure
Steadily it is evacuated to below absolute pressure 500Pa by normal pressure, at 262 DEG C, the response time is 33 minutes to temperature control；
Amino nonadecane carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 17 points
Clock；The amino nonadecane carboxylic acid glycol ester addition is 1.5% for the percentage by weight of modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 277 DEG C, 55 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 16000；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：300℃；
Pathogenic wind-warm：20℃；
Plying network pressure：3.5bar；
GR1 speed：1000m/min；
SR1 speed：3000m/min；
GR2 speed：4000m/min；
HT1 temperature：90℃；
HT2 temperature：140℃；
Winding speed：3000m/min；
Under the conditions of temperature is for 120 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
Big 25v/v%, line density deviation ratio 2.0%, fracture strength 2.2cN/dtex, fracture strength CV value 4.7%, elongation at break is
33.0%, extension at break CV value 9.7%, boiling water shrinkage is 14.5%, and crimp contraction is 4.0%, crimp contraction variation
Coefficient CV values 9.3%, oil content is 0.9%, internet pricing be 16/m, fiber number：140dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 50.0 | 83.0 | 92.2 | 93.0 | 91.9 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 53.5 | 87.2 | 93.1 | 94.2 | 95.3 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 46.3 | 74.9 | 87.4 | 88.8 | 90.6 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Embodiment 5
A kind of preparation method of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by melissane dicarboxylic acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid,
90 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains melissane mono methyl dicarboxylate；The concentrated sulphuric acid refers to that quality is dense
The sulphuric acid for 70% is spent, concentrated sulphuric acid addition is the 3wt% of melissane dicarboxylic acids；
2) the melissane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), wherein
Melissane mono methyl dicarboxylate concentration under nitrogen atmosphere, in 85 DEG C of reactions, backflow, is produced for 0.10mol/L when there is no longer gas
When raw, add a certain amount of dilute sulfuric acid to react 2.3 hours, be washed out, purify and be dried, obtain product bromo nonacosane carboxylic
Acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is melissane dicarboxylic acids list first
The 3wt% of ester；
3) by the ammonia of bromo nonacosane carboxylic acid and 18wt% in molar ratio 1:2 are added in reactor, stirring, in room
The lower reaction of temperature, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 67 DEG C, until depletion of QI
Bubble is produced, that is, stop distillation, is then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using nitric acid
Silver-colored solution detection, by product vacuum drying product amino nonacosane carboxylic acid is obtained；
4) it is in molar ratio 1.1 by ethylene glycol and amino nonacosane carboxylic acid:2 stir, and by amino nonacosane
2% addition concentration of carboxylic acid weight is the sulphuric acid of 48wt%, carries out esterification, and esterification reaction temperature is 170 DEG C, and esterification water evaporates
It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino nonacosane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:1.5 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.3MPa, temperature is esterified Stress control at 254 DEG C
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.01% of p-phthalic acid weight ethylene glycol is added in esterification products
The trimethyl phosphate of antimony and p-phthalic acid weight 0.03%, starts polycondensation reaction under conditions of negative pressure, the staged pressure by
Normal pressure is steadily evacuated to below absolute pressure 500Pa, and at 266 DEG C, the response time is 39 minutes to temperature control；
Amino nonacosane carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 18 points
Clock；The amino nonacosane carboxylic acid glycol ester addition is 2.5% for the percentage by weight of modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 278 DEG C, 60 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 22000；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：280℃；
Pathogenic wind-warm：22℃；
Plying network pressure：4.5bar；
GR1 speed：800m/min；
SR1 speed：4200m/min；
GR2 speed：3000m/min；
HT1 temperature：115℃；
HT2 temperature：130℃；
Winding speed：4000m/min；
Under the conditions of temperature is for 130 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
Big 30v/v%, line density deviation ratio -1.8%, fracture strength 2.3cN/dtex, fracture strength CV value 4.6%, elongation at break
For 29.0%, extension at break CV values 9.3%, boiling water shrinkage is 15.8%, and crimp contraction is 3.0%, and crimp contraction becomes
Different coefficient CV values 9.8%, oil content is 1.1%, internet pricing be 23/m, fiber number：135dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 50.5 | 83.7 | 92.2 | 92.3 | 91.4 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 54.1 | 87.6 | 93.1 | 93.2 | 94.3 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 47.2 | 76.0 | 88.3 | 88.2 | 90.0 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Embodiment 6
A kind of preparation method of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by pentatriacontane dicarboxylic acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, in the catalysis of concentrated sulphuric acid
Under, 95 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains pentatriacontane mono methyl dicarboxylate；The concentrated sulphuric acid refers to matter
Amount concentration is 70% sulphuric acid, and concentrated sulphuric acid addition is the 2wt% of pentatriacontane dicarboxylic acids；
2) the pentatriacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), its
Middle pentatriacontane mono methyl dicarboxylate concentration be 0.09mol/L under nitrogen atmosphere, in 90 DEG C of reactions, backflow, when there is no longer gas
When body is produced, add a certain amount of dilute sulfuric acid to react 2.6 hours, be washed out, purify and be dried, obtain product bromo 34
Alkane carboxylic acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 45%, and dilute sulfuric acid addition is pentatriacontane dicarboxyl
The 1wt% of sour mono-methyl
3) by the ammonia of bromo tetratriacontane carboxylic acid and 20wt% in molar ratio 1:2 are added in reactor, stirring, in room
The lower reaction of temperature, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 69 DEG C, until depletion of QI
Bubble is produced, that is, stop distillation, is then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using nitric acid
Silver-colored solution detection, by product vacuum drying product amino tetratriacontane carboxylic acid is obtained；
4) it is in molar ratio 1.1 by ethylene glycol and amino tetratriacontane carboxylic acid:2 stir, and by amino tetratriacontane
1% addition concentration of carboxylic acid weight is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 180 DEG C, and esterification water evaporates
It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino tetratriacontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:1.6 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.4MPa, temperature is esterified Stress control at 256 DEG C
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.04% of p-phthalic acid weight antimony acetate is added in esterification products
With the NSC 6513 of p-phthalic acid weight 0.02%, polycondensation reaction is started under conditions of negative pressure, the staged pressure by
Normal pressure is steadily evacuated to below absolute pressure 500Pa, and at 267 DEG C, the response time is 40 minutes to temperature control；
Amino tetratriacontane carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 18 points
Clock；The amino tetratriacontane carboxylic acid glycol ester addition is 2.0% for the percentage by weight of modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 275 DEG C, 70 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 24000；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：285℃；
Pathogenic wind-warm：20℃；
Plying network pressure：4.5bar；
GR1 speed：900m/min；
SR1 speed：3400m/min；
GR2 speed：3800m/min；
HT1 temperature：100℃；
HT2 temperature：134℃；
Winding speed：4000m/min；
Under the conditions of temperature is for 110 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
Big 25v/v%, line density deviation ratio -0.5%, fracture strength 2.4cN/dtex, fracture strength CV value 4.9%, elongation at break
For 33.0%, extension at break CV values 9.5%, boiling water shrinkage is 14.0%, and crimp contraction is 4.8%, and crimp contraction becomes
Different coefficient CV values 9.7%, oil content is 0.9%, internet pricing be 21/m, fiber number：120dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 50.6 | 83.6 | 91.6 | 92.6 | 91.0 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 53.9 | 87.0 | 92.9 | 93.4 | 94.8 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 46.6 | 75.7 | 87.5 | 88.9 | 90.6 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Embodiment 7
A kind of preparation method of abnormal contraction composite filament, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by tetracontane dicarboxylic acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid,
100 DEG C are heated to, refuxing esterification, cooling, separating-purifying obtains tetracontane mono methyl dicarboxylate；The concentrated sulphuric acid refers to that quality is dense
The sulphuric acid for 70% is spent, concentrated sulphuric acid addition is the 3wt% of tetracontane dicarboxylic acids；
2) the tetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in in benzene (mol ratio 1:1:1), wherein
Tetracontane mono methyl dicarboxylate concentration under nitrogen atmosphere, in 80 DEG C of reactions, backflow, is produced for 0.06mol/L when there is no longer gas
When raw, add a certain amount of dilute sulfuric acid to react 2.7 hours, be washed out, purify and be dried, obtain product bromo nonatriacontane carboxylic
Acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 48%, and dilute sulfuric acid addition is tetracontane dicarboxylic acids list first
The 2wt% of ester；
3) by the ammonia of bromo nonatriacontane carboxylic acid and 22wt% in molar ratio 1:2 are added in reactor, stirring, in room
The lower reaction of temperature, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is 60 DEG C, until depletion of QI
Bubble is produced, that is, stop distillation, is then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, using nitric acid
Silver-colored solution detection, by product vacuum drying product amino nonatriacontane carboxylic acid is obtained；
4) it is in molar ratio 1.1 by ethylene glycol and amino nonatriacontane carboxylic acid:2 stir, and by amino nonatriacontane
2% addition concentration of carboxylic acid weight is the sulphuric acid of 46wt%, carries out esterification, and esterification reaction temperature is 190 DEG C, and esterification water evaporates
It is esterification terminal that output reaches more than the 90% of theoretical value；The separated purification of product obtains amino nonatriacontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Mol ratio is adopted for 1:1.8 p-phthalic acid and ethylene glycol are made into after uniform sizing material and are esterified as raw material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.2MPa, temperature is esterified Stress control at 258 DEG C
It is esterification terminal that water quantity of distillate reaches more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, the 0.05% of p-phthalic acid weight antimony acetate is added in esterification products
With the trimethyl phosphate of p-phthalic acid weight 0.03%, polycondensation reaction is started under conditions of negative pressure, the staged pressure is by normal
Pressing is surely evacuated to below absolute pressure 500Pa, and at 268 DEG C, the response time is 45 minutes to temperature control；
Amino nonatriacontane carboxylic acid glycol ester is added after the polycondensation reaction coarse vacuum stage terminates, and stirs 16 points
Clock；The amino nonatriacontane carboxylic acid glycol ester addition is 1.5% for the percentage by weight of modified poly ester；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, makes reaction pressure
Power is down to absolute pressure less than 100Pa, reaction temperature control at 275 DEG C, 75 minutes response time；
Prepared modified poly ester, viscosity-average molecular weight is 25000；
(3) preparation of abnormal contraction composite filament：
Modified poly ester is pressed respectively POY techniques and FDY technique spinning, then plying and silk, through network combined, finally roll up
Around formation abnormal contraction composite filament；Processing technique is：
Spinning temperature：288℃；
Pathogenic wind-warm：22℃；
Plying network pressure：3.9bar；
GR1 speed：950m/min；
SR1 speed：3900m/min；
GR2 speed：3700m/min；
HT1 temperature：95℃；
HT2 temperature：136℃；
Winding speed：3900m/min；
Under the conditions of temperature is for 120 DEG C, the free volume space of fibrous inside molecule interchain increases gained abnormal contraction composite filament
Big 27v/v%, line density deviation ratio 1.0%, fracture strength 2.0cN/dtex, fracture strength CV value 4.9%, elongation at break is
34.0%, extension at break CV value 9.4%, boiling water shrinkage is 15.0%, and crimp contraction is 4.0%, crimp contraction variation
Coefficient CV values 9.6%, oil content is 1.0%, internet pricing be 19/m, fiber number：135dtex.
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 50.4 | 83.1 | 91.5 | 93.5 | 91.7 |
| General fibre | 28.6 | 47.3 | 79.9 | 83.7 | 90.0 | |
| Disperse blue SE-2R | Modified fibre | 53.6 | 87.5 | 93.0 | 94.2 | 95.1 |
| General fibre | 15.3 | 37.2 | 76.8 | 89.9 | 92.1 | |
| Disperse bright blue S-GL | Modified fibre | 46.0 | 75.9 | 87.5 | 88.9 | 90.5 |
| General fibre | 13.8 | 38.2 | 72.9 | 76.2 | 84.7 |
Claims (9)
1. a kind of abnormal contraction composite filament, is characterized in that：POY silks that the abnormal contraction composite filament is spun into by modified poly ester and by being modified
The FDY silks that polyester is spun into are combined and obtain；The modified poly ester is made up of polyester with amino ethylene glycol fatty acid, the aminolipid
Fat acid glycol ester is dispersed in the molecule interchain of the polyester, and the molecule of the amino ethylene glycol fatty acid and the polyester
Interchain has hydrogen bond action, the amino ethylene glycol fatty acid is fixed with the relative position of the strand of the polyester；It is described
Abnormal contraction composite filament is under the conditions of 90～130 DEG C in temperature, the free volume space of fibrous inside molecule interchain increase 20～
30v/v%；Fracture strength >=the 1.9cN/dtex of the abnormal contraction composite filament, elongation at break is 30.0 ± 5.0%, and curling is received
Shrinkage is 2.50 ± 3.0%, and internet pricing is 20 ± 5/m；
The molecular structure of the amino ethylene glycol fatty acid is：
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
2. a kind of abnormal contraction composite filament according to claim 1, it is characterised in that the line density of the abnormal contraction composite filament
Deviation ratio ± 2.5%, extension at break CV value≤10.0%, coefficient of variation CV value≤10.0%, oil content is 1.0 ± 0.2%, fine
Degree：100-150dtex.
3. a kind of abnormal contraction composite filament according to claim 1, it is characterised in that the amino ethylene glycol fatty acid is accounted for
The percentage by weight of the abnormal contraction composite filament is 0.5～2.5%.
4. a kind of preparation method of abnormal contraction composite filament as claimed in claim 1, is characterized in that：Modified poly ester presses respectively POY
Technique and FDY technique spinning, then plying and silk, through network combined, finally wind and form abnormal contraction composite filament；Processing technique
For：
Spinning temperature：280～300 DEG C；
Pathogenic wind-warm：20～22 DEG C；
Plying network pressure：3.5～4.5bar；
GR1 speed：800～1000m/min；
SR1 speed：3000～4200m/min；
GR2 speed：3000～400m/min；
HT1 temperature：90～115 DEG C；
HT2 temperature：130～140 DEG C；
Winding speed：3000～4000m/min；
The preparation process of the modified poly ester is as follows：
(1) preparation of amino ethylene glycol fatty acid：
1) by binary of fatty acids and methanol with 1:The amount of 1.5 mol ratios is added in reactor, under the catalysis of concentrated sulphuric acid, is heated to
80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；The binary of fatty acids is dodecane two
Carboxylic acid is to the one kind in dopentacontane dicarboxylic acids；The concentrated sulphuric acid refers to the sulphuric acid that mass concentration is 70～80%, and concentrated sulphuric acid adds
Enter 1～3wt% that amount is binary of fatty acids；
2) by the binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 is dissolved in benzene, wherein binary fat
The concentration of fat acid mono-methyl is 0.05～0.1mol/L, under nitrogen atmosphere, in 80～90 DEG C of reactions, backflow, when there is no longer gas
When body is produced, add a certain amount of dilute sulfuric acid to react 2～3 hours, be washed out, purify and be dried, obtain product bromo fat
Acid；A certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40～50%, and dilute sulfuric acid addition is binary of fatty acids list
1～3wt% of methyl ester；
3) by the ammonia of bromo fatty acid and 15～25wt% in molar ratio 1:2 are added in reactor, stirring, at room temperature instead
Should, then product is added into thermal distillation, and ammonia is absorbed with cold water, plus the temperature of thermal distillation is less than 70 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and sucking filtration, till filter cake deionized water is washed till without bromide ion, by product vacuum
It is dried to obtain product amino fatty acid；
4) it is in molar ratio 1.1 by ethylene glycol and amino fatty acid:2 stir, and by the 1～3% of amino fatty acid wt
The sulphuric acid for adding concentration to be 40～50wt%, carries out esterification, and esterification reaction temperature is 160～220 DEG C, esterification water quantity of distillate
It is esterification terminal to reach more than the 90% of theoretical value；The separated purification of product obtains amino ethylene glycol fatty acid；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
The esterification：
Using p-phthalic acid and ethylene glycol as raw material, being made into after uniform sizing material carries out esterification, obtains esterification products；Ester
Change reaction to pressurize in nitrogen atmosphere, in normal pressure～0.3MPa, at 250～260 DEG C, esterification water quantity of distillate reaches temperature Stress control
It is esterification terminal to more than the 90% of theoretical value；
The polycondensation reaction：
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction coarse vacuum stage, catalyst and stabilizer are added in esterification products, started under conditions of negative pressure
Polycondensation reaction, the staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature control is reacted at 260～270 DEG C
Time is 30～50 minutes；
Amino ethylene glycol fatty acid is added after the polycondensation reaction coarse vacuum stage terminates, and is stirred；
The polycondensation reaction high vacuum stage of Fig, after the polycondensation reaction coarse vacuum stage described in, continues evacuation, drops reaction pressure
Be less than 100Pa to absolute pressure, reaction temperature control at 275～280 DEG C, 50～90 minutes response time；
Prepared modified poly ester.
5. the preparation method of a kind of abnormal contraction composite filament according to claim 4, it is characterised in that the ethylene glycol and institute
The mol ratio for stating p-phthalic acid is 1.2～2.0:1.
6. the preparation method of a kind of abnormal contraction composite filament according to claim 4, it is characterised in that the catalyst is selected from
One kind in antimony oxide, antimony glycol and antimony acetate, catalyst amount be the p-phthalic acid weight 0.01%～
0.05%.
7. the preparation method of a kind of abnormal contraction composite filament according to claim 4, it is characterised in that the stabilizer is selected from
One kind in triphenyl phosphate, trimethyl phosphate and NSC 6513, stabilizing agent dosage is the p-phthalic acid weight
0.01%～0.05%.
8. the preparation method of a kind of abnormal contraction composite filament according to claim 4, it is characterised in that add amino fatty acid
Stirring after glycol ester, the time is 15～20 minutes.
9. the preparation method of a kind of abnormal contraction composite filament according to claim 4, it is characterised in that deionized water is washed till
Till without bromide ion, detected using silver nitrate solution.
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| CN105506774B (en) * | 2015-12-29 | 2017-12-12 | 江苏恒力化纤股份有限公司 | A kind of low aberration polyester abnormal contraction composite filament and preparation method thereof |
| CN105648570B (en) * | 2015-12-29 | 2017-12-15 | 江苏恒力化纤股份有限公司 | A kind of low aberration polyester Wool-Like abnormal contraction composite filament and preparation method thereof |
| CN105648594B (en) * | 2015-12-29 | 2018-01-19 | 江苏恒力化纤股份有限公司 | A kind of low aberration polyester imitates linen look abnormal contraction composite filament and preparation method thereof |
| CN105671675B (en) * | 2015-12-29 | 2017-12-12 | 江苏恒力化纤股份有限公司 | A kind of low aberration polyester imitates cotton abnormal contraction composite filament and preparation method thereof |
| CN106381558B (en) * | 2016-08-31 | 2018-09-14 | 江苏恒力化纤股份有限公司 | A kind of abnormal contraction composite filament and preparation method thereof |
| CN110004547B (en) * | 2018-02-08 | 2021-07-09 | 嘉兴市佳峰贝纺织股份有限公司 | Method for forming composite filament |
| CN109402762A (en) * | 2018-10-19 | 2019-03-01 | 新凤鸣集团湖州中石科技有限公司 | A kind of preparation method of NEW TYPE OF COMPOSITE one step sprinning |
| CN110747556B (en) * | 2019-11-06 | 2022-03-08 | 江苏恒科新材料有限公司 | Different-shrinkage composite yarn and preparation method thereof |
| CN116288840B (en) * | 2023-02-28 | 2023-10-10 | 桐昆集团浙江恒通化纤有限公司 | Production process of high-shrinkage polyester wool-like fiber |
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