CN104499081B - A kind of HMLS type activated polyester industrial yarn and preparation method thereof - Google Patents
A kind of HMLS type activated polyester industrial yarn and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of HMLS type activated polyester industrial yarn and preparation method thereof, the material of described HMLS type activated polyester industrial yarn is modified poly ester, described modified poly ester is made up of with amino ethylene glycol fatty acid polyester, described amino ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and the molecule interchain of described amino ethylene glycol fatty acid and described polyester has hydrogen bond action, described amino ethylene glycol fatty acid is made to fix with the relative position of the strand of described polyester；Described HMLS type activated polyester industrial yarn is under the conditions of temperature is 70～80 DEG C, and the free volume space of fibrous inside molecule interchain increases 10～15v/v%.Partial activation agent molecule diffuses in fiber gap, introduces OH and NH that more activity is stronger, improves the reactivity of polyester fiber.Described HMLS type activated polyester industrial yarn is applied to gently to block, canvas apron etc..
Description
Technical field
The invention belongs to polyester fiber technical field, relate to a kind of HMLS type activated polyester industrial yarn and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) fiber, since coming out, has obtained because of the performance of its excellence rapidly developing, its
Yield has become as the hat of world's synthetic fibers.Polyester fiber has fracture strength and elastic modelling quantity is high, and resilience is moderate, and heat is fixed
Type 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 has crease-resistant money of exempting from, and endures
The advantages such as including property is good, so, polyester fiber is widely used in the field such as clothing, industrial yarn.
PET belongs to symmetric straight chain macromolecular, and strand does not contains side-chain radical, and regularity is the best, and its main chain contains
The phenyl ring of rigidity and flexible alkyl, and the ester group being directly connected with phenyl ring and phenyl ring constitute the conjugated system of rigidity, from
And constrain rotating freely of its soft segment.This structure is it will be evident that add molecule on the impact of glass transition temperature
The wall ridge of sub-chain motion, the glass transition temperature of PET is higher, when temperature reaches more than vitrification point, fiber macromolecular chain
Duan Fasheng strenuous exercise, between polymer molecule, space increases, and free volume increases.
Activated form polyester industrial filament has all features of polyester industrial filament: fracture strength is high, and elongation at break is little, xeothermic
Stable contraction rate；But compared with viscose glue and nylon, its bond properties is poor.Therefore, in process of production, typically want
First carrying out pretreatment makes polyester industrial fiber activate.The feature high with rubber bonding force is possessed after activated, maturation operation, can
With the shortcoming poor with rubber adhesion power overcoming polyester to cause due to molecular structure.The bonding force with rubber can be improved high.Main
Apply on dipped type cord fabric, canvas apron and as the primary raw material of automobile tire cord fabric.
Activator and the main reaction of polyester industrial fiber are to react between the epoxide group of epoxy resin and the end carboxyl of polyester to draw
Enter the hydroxyl of activity, blocked isocyanate at high temperature unseal produce activity the strongest-NCO group ,-NCO and polyester industrial fiber
In-OH react or resterification direct reaction.In polyester molecule, activity stronger-OH and-NH is introduced by reaction, and
Form resinoid coating on polyester industrial fiber surface, make the polarity of polyester strengthen, improve the reactivity with RFL.Due to poly-
Ester smooth surface, surface active groups is little, though activation is effective, but there is serious delamination between polyester industrial fiber and rubber
Phenomenon, and the life-span is short.
The present invention makes the space between polyester fiber fiber molecule at a certain temperature increase, and makes partial activation agents divide in activation process
Son diffuses in fiber gap, improves the service efficiency of activator, introduces-the OH that more activity is stronger in polyester molecule
With-NH, and form firm resinoid coating on polyester cord surface, make the polarity of polyester strengthen, further increase with
The reactivity of RFL.
Summary of the invention
It is an object of the invention to provide a kind of HMLS type activated polyester industrial yarn polyester and preparation method thereof, the present invention utilizes ammonia
Base ethylene glycol fatty acid is when uniform temperature condition, and the increasing degree of free volume is far longer than the characteristic of polyester macromolecule chain,
Improve activator and enter the degree within polyester, improve the modified performance of polyester fiber；Simultaneously because amino fatty acid second two
In the existence of the first amino in alcohol ester molecule, increase the hydrogen bond action between itself and polyester macromolecule chain, add it and polyester
The compatibility and dispersion in the polyester, decrease migration to greatest extent.Polyester construction regularity, crystallinity are not had simultaneously
Destroy, maintain the premium properties of polyester.
A kind of HMLS type activated polyester industrial yarn of the present invention, the material of described HMLS type activated polyester industrial yarn is for changing
Property polyester, described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, and described amino ethylene glycol fatty acid is dispersed in
The molecule interchain of described polyester, and the molecule interchain of described amino ethylene glycol fatty acid and described polyester has hydrogen bond action, makes institute
State amino ethylene glycol fatty acid to fix with the relative position of the strand of described polyester；The industry of described HMLS type activated polyester
Silk is under the conditions of temperature is 70～80 DEG C, and the free volume space of fibrous inside molecule interchain increases 10～15v/v%；Described Gao Mo
Low miniature activated polyester industrial yarn fracture strength >=7.0cN/dtex, elongation at break is 12.0 ± 1.5%, 177 DEG C, 0.05
Dry-hot shrinkage under the test condition of cN/dtex is 2.5 ± 0.5%, measure wicking height≤5mm.
The molecular structure of described amino ethylene glycol fatty acid is:
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
As preferred technical scheme:
A kind of HMLS type activated polyester industrial yarn as above, described amino ethylene glycol fatty acid accounts for described HMLS
The percentage by weight of type activated polyester industrial yarn is 0.5～2.5%.
A kind of HMLS type activated polyester industrial yarn as above, the line density of described HMLS type activated polyester industrial yarn
Deviation ratio≤1.5%, fracture strength CV value≤2.5%, extension at break CV value≤7.0%.
The preparation method of a kind of HMLS type activated polyester industrial yarn as above, by viscous for the height of modified poly ester section through metering,
Extrude, cool down, oil, stretch, thermal finalization, activating finish oil, wind and pre-activate processes step, prepare HMLS
Type activated polyester industrial yarn；Its technological parameter is as follows:
The temperature of described extrusion is 290～320 DEG C；
The pathogenic wind-warm of described cooling is 20～25 DEG C；
The described oil applying rate oiled is 0.4～0.6wt%；
The oil applying rate that described activating finish oils is 0.4～0.5wt%；
The speed of described winding is 2600～3400m/min；
The condition that described pre-activate processes is: temperature 70～80 DEG C, standing time is 20～30h；Described pre-activate processes, and refers to
For shortening the soak time of described HMLS type activated polyester industrial yarn, reach optimum adhesion power simultaneously, again will not Yin Jijiewen
Degree changes and affects activation effect, increases and builds greenhouse, activation silk is placed in the environment of temperature 70～80 DEG C 20～30h, carries out pre-
Activation processing, packaging is dispatched from the factory the most again, so substantially improves the activation effect of activated form polyester industrial filament, enhances activation
Type polyester industrial filament and the bonding force of rubber；
The height of described modified poly ester glues the preparation process of section and includes:
(1) preparation of amino ethylene glycol fatty acid:
1) binary of fatty acids is added in reactor with the amount of 1:1.5 mol ratio with methanol, under the catalysis of concentrated sulphuric acid, be heated to
80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；Described binary of fatty acids is dodecane two
Carboxylic acid is to the one in dopentacontane dicarboxylic acids；Reaction equation is:
HOOC(CH2)nCOOH+CH3OH→CH3OOC(CH2)nCOOH；
Wherein n=10～50.
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide during 1:1:1 is dissolved in benzene in molar ratio, wherein binary fat
The concentration of fat acid mono-methyl is 0.05～0.1mol/L, and under nitrogen atmosphere, 80～90 DEG C of reactions, backflow, when no longer there being gas
During generation, add a certain amount of dilute sulfuric acid and react 2～3 hours, be washed out, purify and be dried, obtain product bromo fatty acid；
Instead
The equation is answered to be:
CH3OOC(CH2)nBr+CO2+LiAc+Pb(OAc)2+HOAe；
3) by the ammonia of bromo fatty acid and 15～25wt% during 1:2 joins reactor in molar ratio, stirring, the most instead
Should, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is less than 70 DEG C, until bubble-free
Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, by product vacuum
It is dried to obtain product amino fatty acid；Vacuum drying temperature can use 60～70 DEG C；Reaction equation is:
HOOC(CH2)nBr+NH3→HOCO(CH2)nNH2+NH4Br；
4) ethylene glycol and amino fatty acid are stirred for 1.1:2 in molar ratio, and one of press the percentage of amino fatty acid wt
Adding the sulphuric acid that concentration is 40～50wt% is catalyst, carries out esterification, and esterification reaction temperature is 160～220 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；The separated purification of product obtains amino fatty acid ethylene glycol
Ester；Reaction equation is:
HOOC(CH2)nNH2+HOCH2CH2OH→
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
(2) preparation of modified poly ester, including esterification and polycondensation reaction:
Described esterification:
Use p-phthalic acid and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products；Ester
Changing reaction to pressurize in nitrogen atmosphere, Stress control is at normal pressure～0.3MPa, and temperature is at 250～260 DEG C, and esterification water quantity of distillate reaches
More than the 90% of theoretical value is esterification terminal；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
In the described polycondensation reaction coarse vacuum stage, esterification products adds catalyst and stabilizer, under conditions of negative pressure, starts contracting
Poly-reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, during reaction
Between be 30～50 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino ethylene glycol fatty acid, and stir, generally stirring 15～20
Minute；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 275～280 DEG C, response time 50～90 minutes；
Prepare modified poly ester；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.9～1.2dL/g.
The preparation method of a kind of HMLS type activated polyester industrial yarn as above, described ethylene glycol and described p-phthalic acid
Mol ratio be 1.2～2.0:1.
The preparation method of a kind of HMLS type activated polyester industrial yarn as above, described catalyst selected from antimony oxide,
One in antimony glycol and antimony acetate, catalyst amount is the 0.01%～0.05% of described p-phthalic acid weight.
The preparation method of a kind of HMLS type activated polyester industrial yarn as above, described stabilizer selected from triphenyl phosphate,
One in trimethyl phosphate and NSC 6513, stabilizing agent dosage is the 0.01%～0.05% of described p-phthalic acid weight.
The preparation method of a kind of HMLS type activated polyester industrial yarn as above, is washed with deionized water to without bromide ion
Employing silver nitrate solution detects.
The preparation method of a kind of HMLS type activated polyester industrial yarn as above, described concentrated sulphuric acid refers to that mass concentration is
70～the sulphuric acid of 80%, concentrated sulphuric acid addition is the 1～3wt% of binary of fatty acids；Described a certain amount of dilute sulfuric acid refers to mass concentration
Being the sulphuric acid of 40～50%, dilute sulfuric acid addition is the 1～3wt% of binary of fatty acids mono-methyl.
It is main that amino ethylene glycol fatty acid is mainly with C-C, C-O key, has certain molecular weight simultaneously, i.e. has a fixed length
The strand of degree, strand flexibility is relatively big, and the amount of crimp of amino ethylene glycol fatty acid is compared with the linear macromolecule of benzene ring structure
Bigger, simultaneously strong compared with the linear macromolecule containing benzene ring structure to the sensitivity of temperature.When the temperature is changed, amino fatty acid second two
Alcohol ester moves prior to the linear macromolecule containing benzene ring structure, and the produced free volume of motion is far longer than containing benzene ring structure
Produced by linear macromolecule.
Added the free volume of polyester fiber by fatty acid ester, improve activator and enter the degree within polyester fiber.This
Invention makes the space between polyester fiber fiber molecule at a certain temperature increase, and makes partial activation agent molecule spread in activation process
Enter in fiber gap, improve the service efficiency of activator, introduce in polyester molecule the stronger-OH of more activity and
-NH, and firm resinoid coating is formed on polyester cord surface, make the polarity of polyester strengthen, further increase and RFL
Reactivity.
Oxygen in fatty acid ester can form hydrogen bond, but oxygen is when centre position, due to space steric effect and fatty acid ester
The factors such as the curling of molecule reduce the quantity of itself and the hydrogen evolution hydrogen bond in polyester macromolecule chain；If amino is on α position, i.e. ammonia
Base acids, owing to amino and carbonyl interact, is also unfavorable for amino and the hydrogen evolution hydrogen bond in polyester macromolecule chain；Work as amino
The amino of fatty acid ester is when the end position of macromole, and the curling of macromole is little on its impact, adds in amino fatty acid ester
Amino and the formation of the hydrogen evolution hydrogen bond in polyester macromolecule chain, improve between amino fatty acid ester and polyester macromolecule chain simultaneously
Active force, decrease sliding and the migration of amino fatty acid ester.
Add amino fatty acid ester and the compatibility of polyester and dispersion in the polyester, decrease migration to greatest extent.With
Time polyester construction regularity, crystallinity are not destroyed, maintain the premium properties of polyester.
Beneficial effect:
The HMLS type activated polyester industrial yarn of gained the most of the present invention, owing to amino ethylene glycol fatty acid is based on C-C, with
Time there is certain molecular weight, i.e. there is the strand of certain length, strand flexibility is relatively big, and amino adds and polyester
The compatibility.The fiber of gained is good with the compatibility of amino ethylene glycol fatty acid.
2. due in amino ethylene glycol fatty acid molecule in the existence of the first amino, increase the hydrogen between it and polyester macromolecule chain
Key effect, adds its compatibility with polyester and dispersion in the polyester, decreases migration to greatest extent.
The HMLS type activated polyester industrial yarn of gained the most of the present invention, owing to the content of amino ethylene glycol fatty acid is less, to poly-
Ester 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, relatively contains the sensitivity of temperature simultaneously
The linear macromolecule having benzene ring structure is strong.When the temperature is changed, move prior to the linear macromolecule containing benzene ring structure, ammonia
The linear macromolecule that the produced free volume of motion of base ethylene glycol fatty acid is far longer than containing benzene ring structure is produced
, increase the diffusion of additive, improve the functional of polyester.
5. make partial activation agent molecule diffuse in fiber gap due to the increase of the free volume of fiber in activation process, carry
The high service efficiency of activator, introduces the stronger-OH of more activity and-NH in polyester molecule, and at polyester cord table
Face forms firm resinoid coating, makes the polarity of polyester strengthen, further increases the reactivity with RFL.
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 be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art
Can make various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally
Enclose.
The material of a kind of HMLS type activated polyester industrial yarn of the present invention is modified poly ester, and described modified poly ester is by polyester and ammonia
Base ethylene glycol fatty acid is constituted, and described amino ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and described amino
Ethylene glycol fatty acid has hydrogen bond action with the molecule interchain of described polyester, makes described amino ethylene glycol fatty acid and described polyester
The relative position of strand fix；Described HMLS type activated polyester industrial yarn under the conditions of temperature is 70～80 DEG C, fiber
The free volume space of interior molecules interchain increases 10～15v/v%；Described HMLS type activated polyester industrial yarn fracture strength >=
7.0cN/dtex, elongation at break is 12.0 ± 1.5%, at 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex
It is 2.5 ± 0.5%.Measure wicking height≤5mm.
The molecular structure of described amino ethylene glycol fatty acid is:
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
A kind of HMLS type activated polyester industrial yarn as above, described amino ethylene glycol fatty acid accounts for described HMLS
The percentage by weight of type activated polyester industrial yarn is 0.5～2.5%.
A kind of HMLS type activated polyester industrial yarn as above, the line density of described HMLS type activated polyester industrial yarn
Deviation ratio≤1.5%, fracture strength CV value≤2.5%, extension at break CV value≤7.0%.
Embodiment 1
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) dodecanedicarboxylic acid is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, heating
To 80 DEG C, refuxing esterification, cooling, separating-purifying obtains dodecanedicarboxylic acid mono-methyl；Described concentrated sulphuric acid refers to that quality is dense
Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of dodecanedicarboxylic acid；
2) described dodecanedicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein 12
Alkane mono methyl dicarboxylate's concentration is 0.05mol/L, under nitrogen atmosphere, in 80 DEG C of reactions, backflow, produces when no longer there being gas
Time raw, add a certain amount of dilute sulfuric acid and react 2 hours, be washed out, purify and be dried, obtain product bromoundecane
Carboxylic acid；Described 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
The 3wt% of mono-methyl；
3) by the ammonia of bromoundecane carboxylic acid Yu 15wt% during 1:2 joins reactor in molar ratio, stirring, the most instead
Should, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free
Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, uses nitre
Acid silver solution detection, obtains product amino-undecanoic carboxylic acid by product vacuum drying；
4) ethylene glycol and amino-undecanoic carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino-undecanoic carboxylic acid weight
1% addition concentration is the sulphuric acid of 40wt%, carries out esterification, and esterification reaction temperature is 160 DEG C, and esterification water quantity of distillate reaches
It is esterification terminal to 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:1.2 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is 250 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
In the described polycondensation reaction coarse vacuum stage, esterification products adds the antimony oxide of 0.01% of p-phthalic acid weight and right
The triphenyl phosphate of phthalic acid weight 0.01%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is put down by normal pressure
Surely being evacuated to below absolute pressure 500Pa, temperature controls at 260 DEG C, and the response time is 50 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino-undecanoic carboxylic acid glycol ester, and stir 15 minutes；Described
Amino-undecanoic carboxylic acid glycol ester, addition is the 0.5wt% of modified poly ester；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 275 DEG C, 90 minutes response time；
Preparing modified poly ester, viscosity-average molecular weight is 15000；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.9dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 290 DEG C；
The pathogenic wind-warm of described cooling is 20 DEG C；
The described oil applying rate oiled is 0.4wt%；
The oil applying rate that described activating finish oils is 0.4wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 2600m/min；
The condition that described pre-activate processes is: temperature 70 C, standing time is 20h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 70 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 10v/v%, line density deviation ratio 1.0%, fracture strength 7.0cN/dtex, fracture strength CV value 2.5%, fracture is stretched
Long rate is 13.5%, extension at break CV value 7.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be
2.5%.Measure wicking height 5.0mm.
Embodiment 2
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) dopentacontane dicarboxylic acids is added in reactor with the amount of 1:1.5 mol ratio with methanol, under the catalysis of concentrated sulphuric acid, add
Heat is to 110 DEG C, and refuxing esterification, cooling, separating-purifying obtains dopentacontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to matter
Amount concentration is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of dopentacontane dicarboxylic acids；
2) described dopentacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), Qi Zhongwu
Dodecanedicarboxylic acid mono-methyl concentration is 0.07mol/L, and under nitrogen atmosphere, 85 DEG C of reactions, backflow, when no longer there being gas
When body produces, add a certain amount of dilute sulfuric acid and react 3 hours, be washed out, purify and be dried, obtain product bromo five
Hendecane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is 52
The 3wt% of alkane mono methyl dicarboxylate；
3) by the ammonia of bromo henpentacontane carboxylic acid Yu 25wt% during 1:2 joins reactor in molar ratio, stirring, at room temperature
Reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 62 DEG C, until depletion of QI
Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses
Silver nitrate solution detects, and product vacuum drying is obtained product amino henpentacontane carboxylic acid；
4) ethylene glycol and amino henpentacontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino henpentacontane carboxylic acid weight
2% addition concentration of amount is the sulphuric acid of 45wt%, carries out esterification, and esterification reaction temperature is 220 DEG C, and esterification water distillates
It is esterification terminal that amount 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:2.0 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control at 0.2MPa, temperature at 260 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
In the described polycondensation reaction coarse vacuum stage, esterification products adds the antimony oxide of 0.05% of p-phthalic acid weight and right
The triphenyl phosphate of phthalic acid weight 0.05%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is put down by normal pressure
Surely being evacuated to below absolute pressure 500Pa, temperature controls at 270 DEG C, and the response time is 30 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino henpentacontane carboxylic acid glycol ester, and stir 20 minutes；Institute
Stating the percentage by weight that amino henpentacontane carboxylic acid glycol ester addition is modified poly ester is 2.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 280 DEG C, 50 minutes response time；
Preparing modified poly ester, viscosity-average molecular weight is 30000；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 1.2dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 320 DEG C；
The pathogenic wind-warm of described cooling is 25 DEG C；
The described oil applying rate oiled is 0.6wt%；
The oil applying rate that described activating finish oils is 0.5wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 3400m/min；
The condition that described pre-activate processes is: temperature 80 DEG C, standing time is 30h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 80 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 10v/v%, line density deviation ratio 0.8%, fracture strength 8.0cN/dtex, fracture strength CV value 2.0%, fracture is stretched
Long rate is 13.0%, extension at break CV value 6.7%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be
3.0%.Measure wicking height 4.9mm.
Embodiment 3
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) pentacosane dicarboxylic acid is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, heating
To 85 DEG C, refuxing esterification, cooling, separating-purifying obtains pentacosane dicarboxylic acid mono-methyl；Described concentrated sulphuric acid refers to that quality is dense
Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of pentacosane dicarboxylic acid；
2) described pentacosane dicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein 15
Alkane mono methyl dicarboxylate's concentration is 0.08mol/L, under nitrogen atmosphere, in 90 DEG C of reactions, backflow, produces when no longer there being gas
Time raw, add a certain amount of dilute sulfuric acid and react 2.5 hours, be washed out, purify and be dried, obtain product bromotetradecane
Carboxylic acid；Described 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
The 3wt% of mono-methyl；
3) by the ammonia of bromotetradecane carboxylic acid Yu 20wt% during 1:2 joins reactor in molar ratio, stirring, the most instead
Should, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free
Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, uses nitre
Acid silver solution detection, obtains product amino tetradecane carboxylic acid by product vacuum drying；
4) ethylene glycol and amino tetradecane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino tetradecane carboxylic acid weight
2% addition concentration is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 190 DEG C, and esterification water quantity of distillate reaches
It is esterification terminal to 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:1.6 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control at 0.3MPa, temperature at 255 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
In the described polycondensation reaction coarse vacuum stage, esterification products adds the antimony oxide of 0.03% of p-phthalic acid weight and right
The triphenyl phosphate of phthalic acid weight 0.03%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is put down by normal pressure
Surely being evacuated to below absolute pressure 500Pa, temperature controls at 265 DEG C, and the response time is 40 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino tetradecane carboxylic acid glycol ester, and stir 16 minutes；Described
Amino tetradecane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 1.0%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 276 DEG C, 70 minutes response time；
Preparing modified poly ester, viscosity-average molecular weight is 22500；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 1.0dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 310 DEG C；
The pathogenic wind-warm of described cooling is 23 DEG C；
The described oil applying rate oiled is 0.5wt%；
The oil applying rate that described activating finish oils is 0.4wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 3000m/min；
The condition that described pre-activate processes is: temperature 75 DEG C, standing time is 25h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 75 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 11v/v%, line density deviation ratio 1.2%, fracture strength 8.0.0cN/dtex, fracture strength CV value 2.6%, fracture is stretched
Long rate is 13.2%, extension at break CV value 6.9%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be
2.0%.Measure wicking height 4.8mm.
Embodiment 4
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) eicosane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, heating
To 85 DEG C, refuxing esterification, cooling, separating-purifying obtains eicosane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to that quality is dense
Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of eicosane dicarboxylic acids；
2) described eicosane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein 20
Alkane mono methyl dicarboxylate's concentration is 0.09mol/L, under nitrogen atmosphere, in 80 DEG C of reactions, backflow, produces when no longer there being gas
Time raw, add a certain amount of dilute sulfuric acid and react 2.1 hours, be washed out, purify and be dried, obtain product bromo nonadecane
Carboxylic acid；Described 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
The 2wt% of mono-methyl；
3) by the ammonia of bromo nonadecane carboxylic acid Yu 16wt% during 1:2 joins reactor in molar ratio, stirring, the most instead
Should, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until bubble-free
Producing, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, uses nitre
Acid silver solution detection, obtains product amino nonadecane carboxylic acid by product vacuum drying；
4) ethylene glycol and amino nonadecane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino nonadecane carboxylic acid weight
2% addition concentration is the sulphuric acid of 42wt%, carries out esterification, and esterification reaction temperature is 160 DEG C, and esterification water quantity of distillate reaches
It is esterification terminal to 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:1.2 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control at 0.15MPa, temperature at 251 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
In the described polycondensation reaction coarse vacuum stage, esterification products adds the antimony oxide of 0.02% of p-phthalic acid weight and right
The triphenyl phosphate of phthalic acid weight 0.02%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is put down by normal pressure
Surely being evacuated to below absolute pressure 500Pa, temperature controls at 262 DEG C, and the response time is 33 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino nonadecane carboxylic acid glycol ester, and stir 17 minutes；Described
Amino nonadecane carboxylic acid glycol ester addition be the percentage by weight of modified poly ester be 1.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 277 DEG C, 55 minutes response time；
Preparing modified poly ester, viscosity-average molecular weight is 16000；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 1.2dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 300 DEG C；
The pathogenic wind-warm of described cooling is 24 DEG C；
The described oil applying rate oiled is 0.4wt%；
The oil applying rate that described activating finish oils is 0.4wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 3200m/min；
The condition that described pre-activate processes is: temperature 80 DEG C, standing time is 22h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 80 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 15v/v%, line density deviation ratio 1.3%, fracture strength 8.0cN/dtex, fracture strength CV value 2.5%, extension at break
Rate is 13.1%, extension at break CV value 6.5%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be 2.8%,
Measure wicking height 4.8mm.
Embodiment 5
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) melissane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, heating
To 90 DEG C, refuxing esterification, cooling, separating-purifying obtains melissane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to that quality is dense
Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of melissane dicarboxylic acids；
2) described melissane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein 30
Alkane mono methyl dicarboxylate's concentration be 0.10mol/L under nitrogen atmosphere, 85 DEG C of reactions, backflow, produce when no longer there being gas
Time raw, add a certain amount of dilute sulfuric acid and react 2.3 hours, be washed out, purify and be dried, obtain product bromo 29
Alkane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40%, and dilute sulfuric acid addition is melissane dicarboxyl
The 3wt% of acid mono-methyl；
3) by the ammonia of bromo nonacosane carboxylic acid Yu 18wt% during 1:2 joins reactor in molar ratio, stirring, at room temperature
Reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 67 DEG C, until depletion of QI
Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses
Silver nitrate solution detects, and product vacuum drying is obtained product amino nonacosane carboxylic acid；
4) ethylene glycol and amino nonacosane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino nonacosane carboxylic acid weight
2% addition concentration of amount is the sulphuric acid of 48wt%, carries out esterification, and esterification reaction temperature is 170 DEG C, and esterification water distillates
It is esterification terminal that amount 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:1.5 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control at 0.3MPa, temperature at 254 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction coarse vacuum stage, in esterification products add p-phthalic acid weight 0.01% antimony glycol and to benzene
The trimethyl phosphate of dioctyl phthalate weight 0.03%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is steady by normal pressure
Being evacuated to below absolute pressure 500Pa, temperature controls at 266 DEG C, and the response time is 39 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino nonacosane carboxylic acid glycol ester, and stir 18 minutes；Institute
Stating the percentage by weight that amino nonacosane carboxylic acid glycol ester addition is modified poly ester is 2.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 278 DEG C, 60 minutes response time；
Prepare modified poly ester；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 1.0dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 320 DEG C；
The pathogenic wind-warm of described cooling is 20 DEG C；
The described oil applying rate oiled is 0.5wt%；
The oil applying rate that described activating finish oils is 0.5wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 2600m/min；
The condition that described pre-activate processes is: temperature 73 DEG C, standing time is 28h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 73 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 14v/v%, line density deviation ratio 1.0%, fracture strength 7.3cN/dtex, fracture strength CV value 2.2%, fracture is stretched
Long rate is 13.5%, extension at break CV value 6.5%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be
3.0%.Measure wicking height 5.0mm.
Embodiment 6
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) pentatriacontane dicarboxylic acids is added in reactor with the amount of 1:1.5 mol ratio with methanol, under the catalysis of concentrated sulphuric acid, add
Heat is to 95 DEG C, and refuxing esterification, cooling, separating-purifying obtains pentatriacontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to matter
Amount concentration is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 2wt% of pentatriacontane dicarboxylic acids；
2) described pentatriacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), Qi Zhongsan
Pentacosane dicarboxylic acid mono-methyl concentration be 0.09mol/L under nitrogen atmosphere, 90 DEG C of reactions, backflow, when no longer there being gas
When body produces, add a certain amount of dilute sulfuric acid and react 2.6 hours, be washed out, purify and be dried, obtain product bromo three
Tetradecane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 45%, and dilute sulfuric acid addition is 35
The 1wt% of alkane mono methyl dicarboxylate
3) by the ammonia of bromo tetratriacontane carboxylic acid Yu 20wt% during 1:2 joins reactor in molar ratio, stirring, at room temperature
Reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until depletion of QI
Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses
Silver nitrate solution detects, and product vacuum drying is obtained product amino tetratriacontane carboxylic acid；
4) ethylene glycol and amino tetratriacontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino tetratriacontane carboxylic acid weight
1% addition concentration of amount is the sulphuric acid of 50wt%, carries out esterification, and esterification reaction temperature is 180 DEG C, and esterification water distillates
It is esterification terminal that amount 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:1.6 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control at 0.4MPa, temperature at 256 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction coarse vacuum stage, in esterification products add p-phthalic acid weight 0.04% antimony acetate and to benzene two
The NSC 6513 of formic acid weight 0.02%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is steady by normal pressure
Being evacuated to below absolute pressure 500Pa, temperature controls at 267 DEG C, and the response time is 40 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino tetratriacontane carboxylic acid glycol ester, and stir 18 minutes；Institute
Stating the percentage by weight that amino tetratriacontane carboxylic acid glycol ester addition is modified poly ester is 2.0%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 275 DEG C, 70 minutes response time；
Prepare modified poly ester；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 1.0dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 290 DEG C；
The pathogenic wind-warm of described cooling is 25 DEG C；
The described oil applying rate oiled is 0.5wt%；
The oil applying rate that described activating finish oils is 0.5wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 3100m/min；
The condition that described pre-activate processes is: temperature 80 DEG C, standing time is 25h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 80 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 13v/v%, line density deviation ratio 1.0%, fracture strength 8.7cN/dtex, fracture strength CV value 1.9%, fracture is stretched
Long rate is 10.5%, extension at break CV value 6.5%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be
2.7%.Measure wicking height 4.6mm.
Embodiment 7
The preparation method of a kind of HMLS type activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) tetracontane dicarboxylic acids is added in reactor with methanol with the amount of 1:1.5 mol ratio, under the catalysis of concentrated sulphuric acid, heating
To 100 DEG C, refuxing esterification, cooling, separating-purifying obtains tetracontane mono methyl dicarboxylate；Described concentrated sulphuric acid refers to that quality is dense
Degree is the sulphuric acid of 70%, and concentrated sulphuric acid addition is the 3wt% of tetracontane dicarboxylic acids；
2) described tetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein 40
Alkane mono methyl dicarboxylate's concentration be 0.06mol/L under nitrogen atmosphere, 80 DEG C of reactions, backflow, produce when no longer there being gas
Time raw, add a certain amount of dilute sulfuric acid and react 2.7 hours, be washed out, purify and be dried, obtain product bromo 39
Alkane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 48%, and dilute sulfuric acid addition is tetracontane dicarboxyl
The 2wt% of acid mono-methyl；
3) by the ammonia of bromo nonatriacontane carboxylic acid Yu 22wt% during 1:2 joins reactor in molar ratio, stirring, at room temperature
Reaction, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until depletion of QI
Bubble produces, and i.e. stops distillation, then carries out cooling down and sucking filtration, and filter cake is washed with deionized water to without bromide ion, uses
Silver nitrate solution detects, and product vacuum drying is obtained product amino nonatriacontane carboxylic acid；
4) ethylene glycol and amino nonatriacontane carboxylic acid are stirred for 1.1:2 in molar ratio, and press amino nonatriacontane carboxylic acid weight
2% addition concentration of amount is the sulphuric acid of 46wt%, carries out esterification, and esterification reaction temperature is 190 DEG C, and esterification water distillates
It is esterification terminal that amount 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:
Described esterification:
The p-phthalic acid using mol ratio to be 1:1.8 and ethylene glycol, as raw material, carry out esterification after being made into uniform sizing material,
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, Stress control at 0.2MPa, temperature at 258 DEG C, esterification water
It is esterification terminal that quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction coarse vacuum stage, in esterification products add p-phthalic acid weight 0.05% antimony acetate and to benzene two
The trimethyl phosphate of formic acid weight 0.03%, starts polycondensation reaction under conditions of negative pressure, and this staged pressure is steadily taken out by normal pressure
To absolute pressure 500Pa, temperature controls at 268 DEG C, and the response time is 45 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino nonatriacontane carboxylic acid glycol ester, and stir 16 minutes；Institute
Stating the percentage by weight that amino nonatriacontane carboxylic acid glycol ester addition is modified poly ester is 1.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure drop
To absolute pressure less than 100Pa, reaction temperature controls at 275 DEG C, 75 minutes response time；
Prepare modified poly ester；
(3) solid phase polycondensation thickening after pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 1.1dL/g.HMLS type
The preparation of activated polyester industrial yarn:
By viscous for the height of modified poly ester section through measuring, extrude, cool down, oil, stretching, thermal finalization, activating finish oil, roll up
Process step around with pre-activate, prepare HMLS type activated polyester industrial yarn；Technological parameter is:
The temperature of described extrusion is 300 DEG C；
The pathogenic wind-warm of described cooling is 20 DEG C；
The described oil applying rate oiled is 0.4wt%；
The oil applying rate that described activating finish oils is 0.4wt%；
Activating finish is containing fatty alcohol ethoxylate 40wt%, the polyoxyether solution of closure polyisocyanates 5wt%；
The speed of described winding is 2800m/min；
The condition that described pre-activate processes is: temperature 77 DEG C, standing time is 27h.
Gained HMLS type activated polyester industrial yarn is under the conditions of temperature is 77 DEG C, and the free volume of fibrous inside molecule interchain is empty
Between increase 10v/v%, line density deviation ratio 1.3%, fracture strength 7.2cN/dtex, fracture strength CV value 1.8%, fracture is stretched
Long rate is 11.0%, extension at break CV value 7.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be
2.2%.Measure wicking height 4.7mm.
Claims (10)
1. a HMLS type activated polyester industrial yarn, it is characterized in that: the material of described HMLS type activated polyester industrial yarn is modified poly ester, described modified poly ester is made up of with amino ethylene glycol fatty acid polyester, described amino ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and the molecule interchain of described amino ethylene glycol fatty acid and described polyester has hydrogen bond action, described amino ethylene glycol fatty acid is made to fix with the relative position of the strand of described polyester；Described HMLS type activated polyester industrial yarn is under the conditions of temperature is 70～80 DEG C, and the free volume space of fibrous inside molecule interchain increases 10～15v/v%；Described HMLS type activated polyester industrial yarn fracture strength >=7.0cN/dtex, elongation at break is 12.0 ± 1.5%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex be 2.5 ± 0.5%, measure wicking height≤5mm；
The molecular structural formula of described amino ethylene glycol fatty acid is:
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10～50.
A kind of HMLS type activated polyester industrial yarn the most according to claim 1, it is characterised in that line density deviation ratio≤1.5% of described HMLS type activated polyester industrial yarn, fracture strength CV value≤2.5%, extension at break CV value≤7.0%.
A kind of HMLS type activated polyester industrial yarn the most according to claim 1, it is characterised in that it is 0.5～2.5% that described amino ethylene glycol fatty acid accounts for the percentage by weight of described HMLS type activated polyester industrial yarn.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most as claimed in claim 1, it is characterized in that: by viscous for the height of modified poly ester section through measure, extrudes, cool down, oil, stretching, thermal finalization, activating finish oil, wind and pre-activate processes step, prepared HMLS type activated polyester industrial yarn；
The temperature of described extrusion is 290～320 DEG C；
The pathogenic wind-warm of described cooling is 20～25 DEG C；
The described oil applying rate oiled is 0.4～0.6wt%；
The oil applying rate that described activating finish oils is 0.4～0.5wt%；
The speed of described winding is 2600～3400m/min；
The condition that described pre-activate processes is: temperature 70～80 DEG C, standing time is 20～30h；
The height of described modified poly ester glues the preparation process of section and includes:
(1) preparation of amino ethylene glycol fatty acid:
1) being added in reactor with the amount of 1:1.5 mol ratio with methanol by binary of fatty acids, under the catalysis of concentrated sulphuric acid, be heated to 80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；Described binary of fatty acids is that dodecanedicarboxylic acid is to dopentacontane dicarboxylic acids；
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide during 1:1:1 is dissolved in benzene in molar ratio, wherein the concentration of binary of fatty acids mono-methyl is 0.05～0.1mol/L, under nitrogen atmosphere, 80～90 DEG C of reactions, backflow, when no longer there being gas to produce, adds a certain amount of dilute sulfuric acid and reacts 2～3 hours, it is washed out, purifies and is dried, obtain product bromo fatty acid；Described a certain amount of dilute sulfuric acid refers to the sulphuric acid that mass concentration is 40～50%, and dilute sulfuric acid addition is the 1～3wt% of binary of fatty acids mono-methyl；
3) by the ammonia of bromo fatty acid and 15～25wt% during 1:2 joins reactor in molar ratio, stirring, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, add the temperature of thermal distillation less than 70 DEG C, until bubble-free produces, i.e. stop distillation, then carry out cooling down and sucking filtration, filter cake is washed with deionized water to without bromide ion, and product vacuum drying is obtained product amino fatty acid；
4) ethylene glycol and amino fatty acid are stirred for 1.1:2 in molar ratio, and add, by the 1～3% of amino fatty acid wt, the sulphuric acid that concentration is 40～50wt%, carry out esterification, esterification reaction temperature is 160～220 DEG C, and 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；
(2) preparation of modified poly ester, including esterification and polycondensation reaction:
Described esterification:
Use p-phthalic acid and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at normal pressure～0.3MPa, and temperature is at 250～260 DEG C, and it is esterification terminal that esterification water quantity of distillate reaches more than the 90% of theoretical value；
Described polycondensation reaction:
Including polycondensation reaction coarse vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction coarse vacuum stage, adding catalyst and stabilizer in esterification products, start polycondensation reaction under conditions of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260～270 DEG C, and the response time is 30～50 minutes；
After the described polycondensation reaction coarse vacuum stage terminates, add amino ethylene glycol fatty acid, and stir；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction coarse vacuum stage, continues evacuation, makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275～280 DEG C, response time 50～90 minutes；
Prepare modified poly ester；
(3) solid phase polycondensation thickening after modified poly ester pelletize, it is thus achieved that the viscous section of the height of modified poly ester, intrinsic viscosity is 0.9～1.2dL/g.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most according to claim 4, it is characterised in that described ethylene glycol is 1.2～2.0:1 with the mol ratio of described p-phthalic acid.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most according to claim 4, it is characterized in that, described catalyst one in antimony oxide, antimony glycol and antimony acetate, catalyst amount is the 0.01%～0.05% of described p-phthalic acid weight.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most according to claim 4, it is characterized in that, described stabilizer one in triphenyl phosphate, trimethyl phosphate and NSC 6513, stabilizing agent dosage is the 0.01%～0.05% of described p-phthalic acid weight.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most according to claim 4, it is characterised in that adding the stirring after amino ethylene glycol fatty acid, the time is 15～20 minutes.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most according to claim 4, it is characterised in that be washed with deionized water to without bromide ion, uses silver nitrate solution detection.
The preparation method of a kind of HMLS type activated polyester industrial yarn the most according to claim 4, it is characterised in that described concentrated sulphuric acid refers to the sulphuric acid that mass concentration is 70～80%, and concentrated sulphuric acid addition is the 1～3wt% of binary of fatty acids.
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| CN105603563B (en) * | 2015-12-29 | 2017-11-17 | 江苏恒力化纤股份有限公司 | A kind of corrosion-resistant polyester industrial fiber and preparation method thereof |
| CN105504241B (en) * | 2015-12-29 | 2018-06-12 | 江苏恒力化纤股份有限公司 | A kind of high mode and low mode polyester industrial fiber and preparation method thereof |
| CN105603562B (en) * | 2015-12-29 | 2017-12-12 | 江苏恒力化纤股份有限公司 | A kind of heat-resistance polyester industrial yarn and preparation method thereof |
| CN105646858B (en) * | 2015-12-29 | 2018-07-27 | 江苏恒力化纤股份有限公司 | A kind of ultralow contractive polyester industrial yarn and preparation method thereof |
| CN105506772B (en) * | 2015-12-29 | 2017-11-17 | 江苏恒力化纤股份有限公司 | A kind of heat-resistance polyester activated industrial silk and preparation method thereof |
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