CN104480563A - Low-shrinkage type activated polyester industrial filament and preparation method thereof - Google Patents
Low-shrinkage type activated polyester industrial filament and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-shrinkage type activated polyester industrial filament and a preparation method thereof. The low-shrinkage type activated polyester industrial filament is made of modified polyester; the modified polyester consists of polyester and amino fatty acid gylcol ester; the amino fatty acid gylcol ester is dispersed among molecular chains of the polyester and has hydrogen-bond interaction to the polyester, so that the relative positions of the molecular chain of the amino fatty acid gylcol ester and the polyester are fixed; under the condition of 70-80 DEG C, the free volume space of a part of the molecular chains inside the low-shrinkage type activated polyester industrial filament is increased by 10-15v/v%, the breaking strength of the low-shrinkage type activated polyester industrial filament is greater than or equal to 7.6 cN/dtex, and the core absorption height is less than or equal to 5 mm. A part of molecules of an activating agent are diffused and enter fiber gaps, and more -OH and -NH with relatively high activity are introduced into polyester molecules, so that the reactivity of the polyester fiber is improved. The low-shrinkage type activated polyester industrial filament can be used in apron fabrics, radial tire builder fabrics, and the like.
Description
Technical field
The invention belongs to polyester fiber technical field, relate to a kind of low miniature activated polyester industrial yarn and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) fiber is since appearance, and obtain because of the performance of its excellence and rapidly develop, its output has become the hat of world's synthetic fiber.Polyester fiber has fracture strength and elastic modelling quantity is high, resilience is moderate, HEAT SETTING is excellent, a series of premium properties such as heat-resisting light resistance good and acid-fast alkali-proof corrosion resistant candle property, and fabric have crease-resistant exempt from money, the advantages such as stiffness is good, so polyester fiber is widely used in the field such as clothes, industrial yarn.
PET belongs to symmetric straight chain macromolecular, strand is not containing side-chain radical, regularity is very good, its main chain contains the phenyl ring of rigidity and flexible alkyl, and the ester group be directly connected with phenyl ring and phenyl ring constitute the conjugated system of rigidity, thus constrain rotating freely of its soft segment.The impact of this structure on glass transition temperature is obvious, and add the wall ridge of molecule segment motion, the glass transition temperature of PET is higher, when temperature reaches more than vitrification point, there is strenuous exercise in fiber macromolecular chain segment, 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, and dry-hot shrinkage is stablized; But compare with nylon with viscose glue, its bond properties is poor.Therefore, in process of production, generally will first carry out preliminary treatment makes polyester industrial fiber activate.Possess the feature high with rubber bonding force after activated, maturation operation, can overcome that polyester causes due to molecular structure with shortcoming that is rubber adhesion power difference.Can improve with the bonding force of rubber high.To be mainly used on dipped type cord fabric, canvas apron and as the main raw material of automobile tire cord fabric.
Activator and the main reaction of polyester industrial fiber react between the epoxide group of epoxy resin and the end carboxyl of polyester to introduce active hydroxyl, blocked isocyanate at high temperature deblocking produce active very strong-NCO group ,-NCO and the-OH in polyester industrial fiber react or resterification directly reacts.In polyester molecule, introduce active stronger-OH and-NH by reaction, and form resinoid coating on polyester industrial fiber surface, the polarity of polyester is strengthened, improves the reactivity with RFL.Because surface of polyester is smooth, surface active groups is little, though activation is effective, there is serious delamination, and the life-span is short between polyester industrial fiber and rubber.
The present invention makes the space of polyester fiber at a certain temperature between fiber molecule increase, in activation process, make partial activation agents molecular diffusion enter into fiber gap, improve the service efficiency of activator, stronger-the OH of more activity and-NH is introduced in polyester molecule, and form firmly resinoid coating on polyester cord surface, the polarity of polyester is strengthened, further increases the reactivity with RFL.
Summary of the invention
The object of this invention is to provide a kind of low miniature activated polyester industrial yarn and preparation method thereof, the present invention utilizes amino ethylene glycol fatty acid when uniform temperature condition, the increasing degree of free volume is far longer than the characteristic of polyester macromolecule chain, improve the degree that activator enters polyester inside, improve the modification performance of polyester fiber; Simultaneously due in amino ethylene glycol fatty acid molecule in the first amino existence, increase the hydrogen bond action between itself and polyester macromolecule chain, add compatibility and the dispersion in the polyester of it and polyester, decrease migration to greatest extent.Polyester construction regularity, crystallinity are not destroyed simultaneously, maintain the premium properties of polyester.
One of the present invention low miniature activated polyester industrial yarn, the material of described low miniature activated polyester industrial yarn is modified poly ester, obtained by modified poly ester spinning, described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described amino ethylene glycol fatty acid is dispersed between the strand of described polyester, and have hydrogen bond action between the strand of described amino ethylene glycol fatty acid and described polyester, the relative position of the strand of described amino ethylene glycol fatty acid and described polyester is fixed; Described low miniature activated polyester industrial yarn is under temperature is 70 ~ 80 DEG C of conditions, and the free volume space between fibrous inside strand increases 10 ~ 15v/v%; Described low miniature activated polyester industrial yarn fracture strength >=7.6cN/dtex, elongation at break is 19.0 ± 2.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.0 ± 0.8%, measure wicking height≤5mm.
The molecular structure of described amino ethylene glycol fatty acid is:
H
2N(CH
2)
nCOOCH
2CH
2OOC(CH
2)
nNH
2；
Wherein, n=10-50.
As preferred technical scheme:
One as above low miniature activated polyester industrial yarn, the percentage by weight that described amino ethylene glycol fatty acid accounts for described low miniature activated polyester industrial yarn is 0.5 ~ 2.5%.
One as above low miniature activated polyester industrial yarn, line density deviation ratio≤1.4% of described low miniature activated polyester industrial yarn, fracture strength CV value≤3.0%, extension at break CV value≤8.0%.
Present invention also offers a kind of preparation method of low miniature activated polyester industrial yarn, by sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn;
The described temperature extruded is 290 ~ 320 DEG C;
The wind-warm syndrome 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 of described pre-activate process is: temperature 70 ~ 80 DEG C, and standing time is 20 ~ 30h; Described pre-activate process, refer to the soak time for shortening described low miniature activated polyester industrial yarn, reach optimum adhesion power simultaneously, activation effect can not be affected because of seasonal temperature change again, increase and build greenhouse, activation silk is placed 20 ~ 30h under the environment of temperature 70 ~ 80 DEG C, carry out pre-activate process, and then packaging is dispatched from the factory, and substantially improves the activation effect of activated form polyester industrial filament like this, enhances the bonding force of activated form polyester industrial filament and rubber;
The preparation process that the height of described modified poly ester glues section comprises:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by binary of fatty acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric 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 the one in dopentacontane dicarboxylic acids; Reaction equation is:
HOOC(CH
2)
nCOOH+CH
3OH→CH
3OOC(CH
2)
nCOOH；
Wherein n=10 ~ 50.
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 be dissolved in benzene, 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 including gas and producing, adds a certain amount of dilute sulfuric acid reaction 2 ~ 3 hours, then wash, purify and drying, obtain product bromo aliphatic acid; Reaction equation is:
3) by the ammoniacal liquor of bromo aliphatic acid and 15 ~ 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is no more than 70 DEG C, until bubble-free produces, namely stop distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, product vacuumize is obtained the amino aliphatic acid of product; Vacuum drying temperature can adopt 60 ~ 70 DEG C; Reaction equation is:
HOOC(CH
2)
nBr+NH
3→HOOC(CH
2)
nNH
2+NH
4Br；
4) by ethylene glycol and amino aliphatic acid in molar ratio for 1.1:2 stirs, and by one of the percentage of amino fatty acid wt, to add concentration be the sulfuric acid of 40 ~ 50wt% is catalyst, carry out esterification, esterification reaction temperature is 160 ~ 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino ethylene glycol fatty acid through separating-purifying; Reaction equation is:
HOOC(CH
2)
nNH
2+HOCH
2CH
2OH→
H
2N(CH
2)
nCOOCH
2CH
2OOC(CH
2)
nNH
2；
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt terephthalic acid (TPA) 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 esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, in esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction time is 30 ~ 50 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino ethylene glycol fatty acid, and stir, usually stir 15 ~ 20 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 ~ 280 DEG C, 50 ~ 90 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.9 ~ 1.2dL/g.
The preparation method of a kind of low miniature activated polyester industrial yarn as above, the mol ratio of described ethylene glycol and described terephthalic acid (TPA) is 1.2 ~ 2.0:1.
The preparation method of a kind of low miniature activated polyester industrial yarn as above, described catalyst is selected from the one in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight.
The preparation method of a kind of low miniature activated polyester industrial yarn as above, described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight.
The preparation method of a kind of low miniature activated polyester industrial yarn as above, is washed till without adopting liquor argenti nitratis ophthalmicus to detect till bromide ion with deionized water.
The preparation method of a kind of low miniature activated polyester industrial yarn as above, the described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70 ~ 80%, and concentrated sulfuric acid addition is 1 ~ 3wt% of binary of fatty acids; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40 ~ 50%, and dilute sulfuric acid addition is 1 ~ 3wt% of binary of fatty acids mono-methyl.
Amino ethylene glycol fatty acid is mainly with C-C, C-O key is main, there is certain molecular weight simultaneously, namely there is the strand of certain length, strand flexibility is larger, the amount of crimp of amino ethylene glycol fatty acid is larger compared with the linear macromolecule of benzene ring structure, simultaneously strong to the linear macromolecule of sensitivity comparatively containing benzene ring structure of temperature.When the temperature is changed, amino ethylene glycol fatty acid moves prior to the linear macromolecule containing benzene ring structure, and the free volume linear macromolecule be far longer than containing benzene ring structure that motion produces produces.
Added the free volume of polyester fiber by fatty acid ester, improve the degree that activator enters polyester fiber inside.The present invention makes the space of polyester fiber at a certain temperature between fiber molecule increase, in activation process, make partial activation agents molecular diffusion enter into fiber gap, improve the service efficiency of activator, stronger-the OH of more activity and-NH is introduced in polyester molecule, and form firmly resinoid coating on polyester cord surface, the polarity of polyester is strengthened, further increases the reactivity with RFL.
Oxygen in fatty acid ester can form hydrogen bond, but oxygen is when centre position, and the factor hydrogen reduced in itself and polyester macromolecule chain such as curling due to space steric effect and fatty acid ester molecules forms the quantity of hydrogen bond; If amino is on α position, i.e. amino acids, because amino and carbonyl interact, be also unfavorable for that the hydrogen in amino and polyester macromolecule chain forms hydrogen bond; When the amino of amino fatty acid ester is in macromolecular end position, macromolecular curling little on its impact, add the formation that the amino in amino fatty acid ester and the hydrogen in polyester macromolecule chain form hydrogen bond, improve the active force between amino fatty acid ester and polyester macromolecule chain simultaneously, decrease slippage and the migration of amino fatty acid ester.
Add compatibility and the dispersion in the polyester of amino fatty acid ester and polyester, decrease migration to greatest extent.Polyester construction regularity, crystallinity are not destroyed simultaneously, maintain the premium properties of polyester.
Beneficial effect:
1. the low miniature activated polyester industrial yarn of gained of the present invention, because amino ethylene glycol fatty acid is based on C-C, there is certain molecular weight simultaneously, namely there is the strand of certain length, strand flexibility is comparatively large, and amino adds the compatibility of amino ethylene glycol fatty acid and polyester.The fiber of gained and the compatibility of amino ethylene glycol fatty acid good.
2. due to existence the first amino in amino ethylene glycol fatty acid molecule, increase and hydrogen bond action between it and polyester macromolecule chain, add compatibility and the dispersion in the polyester of it and polyester, decrease migration to greatest extent.
3. the low miniature activated polyester industrial yarn of gained of the present invention, because the content of amino ethylene glycol fatty acid is less, does not destroy polyester construction regularity, crystallinity, maintains the premium properties of polyester.
4. the amount of crimp of amino ethylene glycol fatty acid is larger compared with the linear macromolecule of benzene ring structure, simultaneously strong to the linear macromolecule of sensitivity comparatively containing benzene ring structure of temperature.When the temperature is changed, move prior to the linear macromolecule containing benzene ring structure, the free volume linear macromolecule be far longer than containing benzene ring structure that the motion of amino ethylene glycol fatty acid produces produces, and increases the diffusion of additive, improves the functional of polyester.
5. in activation process because the increase of the free volume of fiber makes partial activation agents molecular diffusion enter into fiber gap, improve the service efficiency of activator, stronger-the OH of more activity and-NH is introduced in polyester molecule, and form firmly resinoid coating on polyester cord surface, the polarity of polyester is strengthened, further increases the reactivity with RFL.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
One of the present invention low miniature activated polyester industrial yarn, material is modified poly ester, described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described amino ethylene glycol fatty acid is dispersed between the strand of described polyester, and have hydrogen bond action between the strand of described amino ethylene glycol fatty acid and described polyester, the relative position of the strand of described amino ethylene glycol fatty acid and described polyester is fixed; Described low miniature activated polyester industrial yarn is under temperature is 70 ~ 80 DEG C of conditions, and the free volume space between fibrous inside strand increases 10 ~ 15v/v%; Described low miniature activated polyester industrial yarn fracture strength >=7.6cN/dtex, elongation at break is 19.0 ± 2.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.0 ± 0.8%, measure wicking height≤5mm.
The molecular structure of described amino ethylene glycol fatty acid is:
H
2N(CH
2)
nCOOCH
2CH
2OOC(CH
2)
nNH
2；
Wherein, n=10-50.
One as above low miniature activated polyester industrial yarn, the percentage by weight that described amino ethylene glycol fatty acid accounts for described low miniature activated polyester industrial yarn is 0.5 ~ 2.5%.
One as above low miniature activated polyester industrial yarn, line density deviation ratio≤1.4% of described low miniature activated polyester industrial yarn, fracture strength CV value≤3.0%, extension at break CV value≤8.0%.
Embodiment 1
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by dodecanedicarboxylic acid and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 80 DEG C, refuxing esterification, cooling, separating-purifying obtains dodecanedicarboxylic acid mono-methyl; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of dodecanedicarboxylic acid;
2) described dodecanedicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein dodecanedicarboxylic acid mono-methyl concentration is 0.05mol/L, under nitrogen atmosphere, 80 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2 hours, then wash, purify and drying, obtain product bromoundecane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40%, and dilute sulfuric acid addition is the 3wt% of dodecanedicarboxylic acid mono-methyl;
3) by the ammoniacal liquor of bromoundecane carboxylic acid and 15wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, product vacuumize is obtained product amino-undecanoic carboxylic acid;
4) by ethylene glycol and amino-undecanoic carboxylic acid in molar ratio for 1.1:2 stirs, and add by 1% of amino-undecanoic carboxylic acid weight the sulfuric acid that concentration is 40wt%, carry out esterification, esterification reaction temperature is 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino-undecanoic carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.2 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 0.3MPa, and temperature is 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.01% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.01% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 DEG C, and the reaction time is 50 minutes;
After the described polycondensation reaction low 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 low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 90 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.9dL/g.The preparation of low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 290 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 40wt%, closure polyisocyanates 5wt%;
The speed of described winding is 2600m/min;
The condition of described pre-activate process is: temperature 70 C, and standing time is 20h.
Gained low miniature activated polyester industrial yarn is under temperature is 70 DEG C of conditions, free volume space between fibrous inside strand increases 10v/v%, line density deviation ratio 1.0%, fracture strength 8.0cN/dtex, fracture strength CV value 2.5%, elongation at break is 19.0%, extension at break CV value 7.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.7%.Measure wicking height 4mm.
Embodiment 2
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by dopentacontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains dopentacontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of dopentacontane dicarboxylic acids;
2) described dopentacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein dopentacontane mono methyl dicarboxylate concentration is 0.07mol/L, under nitrogen atmosphere, 85 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 3 hours, then wash, purify and drying, obtain product bromo henpentacontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40%, and dilute sulfuric acid addition is the 3wt% of dopentacontane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo henpentacontane carboxylic acid and 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 62 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino henpentacontane carboxylic acid of product;
4) by ethylene glycol and amino henpentacontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino henpentacontane carboxylic acid weight the sulfuric acid that concentration is 45wt%, carry out esterification, esterification reaction temperature is 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino henpentacontane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:2.0 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 0.2MPa, and temperature is at 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.05% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.05% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 270 DEG C, and the reaction time is 30 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino henpentacontane carboxylic acid glycol ester, and stir 20 minutes; Described amino henpentacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 50 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 1.2dL/g.The preparation of low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 320 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 40wt%, closure polyisocyanates 5wt%;
The speed of described winding is 3400m/min;
The condition of described pre-activate process is: temperature 80 DEG C, and standing time is 30h.
Gained low miniature activated polyester industrial yarn is under temperature is 80 DEG C of conditions, free volume space between fibrous inside strand increases 15v/v%, line density deviation ratio 1.2%, fracture strength 7.4cN/dtex, fracture strength CV value 7.5%, elongation at break is 20.0, extension at break CV value 8.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.8%.Measure wicking height 3.5mm.
Embodiment 3
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by pentacosane dicarboxylic acid and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains pentacosane dicarboxylic acid mono-methyl; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of pentacosane dicarboxylic acid;
2) described pentacosane dicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein pentacosane dicarboxylic acid mono-methyl concentration is 0.08mol/L, under nitrogen atmosphere, 90 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2.5 hours, then wash, purify and drying, obtain product bromotetradecane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 50%, and dilute sulfuric acid addition is the 3wt% of pentacosane dicarboxylic acid mono-methyl;
3) by the ammoniacal liquor of bromotetradecane carboxylic acid and 20wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino tetradecane carboxylic acid of product;
4) by ethylene glycol and amino tetradecane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of the amino tetradecane carboxylic acid weight sulfuric acid that concentration is 50wt%, carry out esterification, esterification reaction temperature is 190 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino tetradecane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.6 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 0.3MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.03% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.03% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 265 DEG C, and the reaction time is 40 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino tetradecane carboxylic acid glycol ester, and stir 16 minutes; Described amino tetradecane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.0%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 276 DEG C, 70 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 1.0dL/g.Low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 310 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 40wt%, closure polyisocyanates 5wt%;
The speed of described winding is 3000m/min;
The condition of described pre-activate process is: temperature 75 DEG C, and standing time is 25h.
Gained low miniature activated polyester industrial yarn is under temperature is 75 DEG C of conditions, free volume space between fibrous inside strand increases 12v/v%, line density deviation ratio 1.3%, fracture strength 8.0cN/dtex, fracture strength CV value 2.6%, elongation at break is 21.0%, extension at break CV value 7.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.5%.Measure wicking height 4.7mm.
Embodiment 4
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by eicosane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains eicosane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of eicosane dicarboxylic acids;
2) described eicosane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein eicosane mono methyl dicarboxylate concentration is 0.09mol/L, under nitrogen atmosphere, 80 DEG C of reactions, backflow, when no longer including gas and producing, adds a certain amount of dilute sulfuric acid and reacts 2.1 hours, then wash, purify and drying, obtain product bromo nonadecane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 43%, and dilute sulfuric acid addition is the 2wt% of eicosane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo nonadecane carboxylic acid and 16wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino nonadecane carboxylic acid of product;
4) by ethylene glycol and amino nonadecane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino nonadecane carboxylic acid weight the sulfuric acid that concentration is 42wt%, carry out esterification, esterification reaction temperature is 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino nonadecane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.2 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 0.15MPa, and temperature is at 251 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimonous oxide of 0.02% of terephthalic acid (TPA) weight and the triphenyl phosphate of terephthalic acid (TPA) weight 0.02% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 262 DEG C, and the reaction time is 33 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino nonadecane carboxylic acid glycol ester, and stir 17 minutes; Described amino nonadecane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 277 DEG C, 55 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 1.2dL/g.The preparation of low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 300 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 40wt%, closure polyisocyanates 5wt%;
The speed of described winding is 3200m/min;
The condition of described pre-activate process is: temperature 72 DEG C, and standing time is 22h.
Gained low miniature activated polyester industrial yarn is under temperature is 72 DEG C of conditions, free volume space between fibrous inside strand increases 12v/v%, line density deviation ratio 1.3%, fracture strength 10.0cN/dtex, fracture strength CV value 2.9%, elongation at break is 17.0%, extension at break CV value 7.9%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.0%.Measure wicking height 3.6mm.
Embodiment 5
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by melissane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 90 DEG C, refuxing esterification, cooling, separating-purifying obtains melissane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of melissane dicarboxylic acids;
2) described melissane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein melissane mono methyl dicarboxylate concentration be 0.10mol/L under nitrogen atmosphere, 85 DEG C of reactions, backflow, when no longer including gas and producing, add a certain amount of dilute sulfuric acid and react 2.3 hours, then wash, purify and drying, obtain product bromo nonacosane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40%, and dilute sulfuric acid addition is the 3wt% of melissane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo nonacosane carboxylic acid and 18wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 67 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino nonacosane carboxylic acid of product;
4) by ethylene glycol and amino nonacosane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino nonacosane carboxylic acid weight the sulfuric acid that concentration is 48wt%, carry out esterification, esterification reaction temperature is 170 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino nonacosane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.5 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 0.3MPa, and temperature is at 254 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony glycol of 0.01% of terephthalic acid (TPA) weight and the trimethyl phosphate of terephthalic acid (TPA) weight 0.03% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 266 DEG C, and the reaction time is 39 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino nonacosane carboxylic acid glycol ester, and stir 18 minutes; Described amino nonacosane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 278 DEG C, 60 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 1.0dL/g.The preparation of low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 320 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 35wt%, closure polyisocyanates 5wt%;
The speed of described winding is 2600m/min;
The condition of described pre-activate process is: temperature 70 C, and standing time is 28h.
Gained low miniature activated polyester industrial yarn is under temperature is 70 DEG C of conditions, free volume space between fibrous inside strand increases 11v/v%, line density deviation ratio 1.1%, fracture strength 8.3cN/dtex, fracture strength CV value 2.5%, elongation at break is 21.0%, extension at break CV value 7.6%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.3%.Measure wicking height 2.8mm.
Embodiment 6
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by pentatriacontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 95 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatriacontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 2wt% of pentatriacontane dicarboxylic acids;
2) described pentatriacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein pentatriacontane mono methyl dicarboxylate concentration be 0.09mol/L under nitrogen atmosphere, 90 DEG C of reactions, backflow, when no longer including gas and producing, add a certain amount of dilute sulfuric acid and react 2.6 hours, then wash, purify and drying, obtain product bromo tetratriacontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 45%, and dilute sulfuric acid addition is the 1wt% of pentatriacontane mono methyl dicarboxylate
3) by the ammoniacal liquor of bromo tetratriacontane carboxylic acid and 20wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 69 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino tetratriacontane carboxylic acid of product;
4) by ethylene glycol and amino tetratriacontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 1% of amino tetratriacontane carboxylic acid weight the sulfuric acid that concentration is 50wt%, carry out esterification, esterification reaction temperature is 180 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino tetratriacontane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.6 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 0.4MPa, and temperature is at 256 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony acetate of 0.04% of terephthalic acid (TPA) weight and the Trimethyl phosphite of terephthalic acid (TPA) weight 0.02% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 267 DEG C, and the reaction time is 40 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino tetratriacontane carboxylic acid glycol ester, and stir 18 minutes; Described amino tetratriacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.0%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 70 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 1.0dL/g.The preparation of low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 290 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 35wt%, closure polyisocyanates 5wt%;
The speed of described winding is 3100m/min;
The condition of described pre-activate process is: temperature 80 DEG C, and standing time is 25h.
Gained low miniature activated polyester industrial yarn is under temperature is 80 DEG C of conditions, free volume space between fibrous inside strand increases 13v/v%, line density deviation ratio 1.0%, fracture strength 8.7cN/dtex, fracture strength CV value 2.7%, elongation at break is 17.0%, extension at break CV value 7.5%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.7%.Measure wicking height 3.6mm.
Embodiment 7
A preparation method for low miniature activated polyester industrial yarn, comprises the following steps:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by tetracontane dicarboxylic acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric acid, be heated to 100 DEG C, refuxing esterification, cooling, separating-purifying obtains tetracontane mono methyl dicarboxylate; The described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70%, and concentrated sulfuric acid addition is the 3wt% of tetracontane dicarboxylic acids;
2) described tetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in (mol ratio 1:1:1) in benzene, wherein tetracontane mono methyl dicarboxylate concentration be 0.06mol/L under nitrogen atmosphere, 80 DEG C of reactions, backflow, when no longer including gas and producing, add a certain amount of dilute sulfuric acid and react 2.7 hours, then wash, purify and drying, obtain product bromo nonatriacontane carboxylic acid; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 48%, and dilute sulfuric acid addition is the 2wt% of tetracontane mono methyl dicarboxylate;
3) by the ammoniacal liquor of bromo nonatriacontane carboxylic acid and 22wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is 60 DEG C, until bubble-free produces, namely stops distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, adopts liquor argenti nitratis ophthalmicus to detect, and product vacuumize is obtained the amino nonatriacontane carboxylic acid of product;
4) by ethylene glycol and amino nonatriacontane carboxylic acid in molar ratio for 1.1:2 stirs, and add by 2% of amino nonatriacontane carboxylic acid weight the sulfuric acid that concentration is 46wt%, carry out esterification, esterification reaction temperature is 190 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino nonatriacontane carboxylic acid glycol ester through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification:
Adopt mol ratio be the terephthalic acid (TPA) of 1:1.8 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 0.2MPa, and temperature is at 258 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the antimony acetate of 0.05% of terephthalic acid (TPA) weight and the trimethyl phosphate of terephthalic acid (TPA) weight 0.03% is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 268 DEG C, and the reaction time is 45 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino nonatriacontane carboxylic acid glycol ester, and stir 16 minutes; Described amino nonatriacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.5%;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 75 minutes reaction time;
Obtained modified poly ester;
(3) solid phase polycondensation thickening after granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 1.1dL/g.The preparation of low miniature activated polyester industrial yarn:
By sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn; Technological parameter is:
The described temperature extruded is 300 DEG C;
The wind-warm syndrome 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%;
Described activating finish is the polyoxyether solution containing fatty alcohol ethoxylate 35wt%, closure polyisocyanates 5wt%;
The speed of described winding is 2800m/min;
The condition of described pre-activate process is: temperature 74 DEG C, and standing time is 27h.
Gained low miniature activated polyester industrial yarn is under temperature is 74 DEG C of conditions, free volume space between fibrous inside strand increases 13v/v%, line density deviation ratio 1.3%, fracture strength 7.9cN/dtex, fracture strength CV value 2.8%, elongation at break is 20.0%, extension at break CV value 8.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.5%.Measure wicking height 4.1mm.
Claims (10)
1. one kind low miniature activated polyester industrial yarn, it is characterized in that: the material of described low miniature activated polyester industrial yarn is modified poly ester, described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described amino ethylene glycol fatty acid is dispersed between the strand of described polyester, and have hydrogen bond action between the strand of described amino ethylene glycol fatty acid and described polyester, the relative position of the strand of described amino ethylene glycol fatty acid and described polyester is fixed; Described low miniature activated polyester industrial yarn is under temperature is 70 ~ 80 DEG C of conditions, and the free volume space between fibrous inside strand increases 10 ~ 15v/v%; Described low miniature activated polyester industrial yarn fracture strength >=7.6cN/dtex, elongation at break is 19.0 ± 2.0%, 177 DEG C, dry-hot shrinkage under the test condition of 0.05cN/dtex is 2.0 ± 0.8%, measure wicking height≤5mm;
The molecular structural formula of described amino ethylene glycol fatty acid is:
H
2N(CH
2)
nCOOCH
2CH
2OOC(CH
2)
nNH
2；
Wherein, n=10 ~ 50.
2. one according to claim 1 low miniature activated polyester industrial yarn, is characterized in that, line density deviation ratio≤1.4% of described low miniature activated polyester industrial yarn, fracture strength CV value≤3.0%, extension at break CV value≤8.0%.
3. one according to claim 1 low miniature activated polyester industrial yarn, is characterized in that, the percentage by weight that described amino ethylene glycol fatty acid accounts for described low miniature activated polyester industrial yarn is 0.5 ~ 2.5%.
4. the preparation method of a kind of low miniature activated polyester industrial yarn as claimed in claim 1, it is characterized in that: by sticky for the height of modified poly ester section through measure, extruding, cool, oil, stretch, HEAT SETTING, activating finish oil, reel and pre-activate treatment step, obtains low miniature activated polyester industrial yarn;
The described temperature extruded is 290 ~ 320 DEG C;
The wind-warm syndrome 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 of described pre-activate process is: temperature 70 ~ 80 DEG C, and standing time is 20 ~ 30h;
The preparation process that the height of described modified poly ester glues section comprises:
(1) preparation of amino ethylene glycol fatty acid:
1) add in reactor by binary of fatty acids and methyl alcohol with the amount of 1:1.5 mol ratio, under the catalysis of the concentrated sulfuric 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 the one in dopentacontane dicarboxylic acids;
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 be dissolved in benzene, 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 including gas and producing, adds a certain amount of dilute sulfuric acid reaction 2 ~ 3 hours, then wash, purify and drying, obtain product bromo aliphatic acid;
3) by the ammoniacal liquor of bromo aliphatic acid and 15 ~ 25wt% in molar ratio 1:2 join in reactor, stir, at room temperature react, then product is added thermal distillation, and absorb ammonia with cold water, the temperature adding thermal distillation is no more than 70 DEG C, until bubble-free produces, namely stop distillation, then carry out cooling and suction filtration, filter cake deionized water is washed till without till bromide ion, product vacuumize is obtained the amino aliphatic acid of product;
4) by ethylene glycol and amino aliphatic acid in molar ratio for 1.1:2 stirs, and add by 1 ~ 3% of amino fatty acid wt the sulfuric acid that concentration is 40 ~ 50wt%, carry out esterification, esterification reaction temperature is 160 ~ 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal; Product obtains amino ethylene glycol fatty acid through separating-purifying;
(2) preparation of modified poly ester, comprises esterification and polycondensation reaction:
Described esterification: adopt terephthalic acid (TPA) 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 esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, in esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction time is 30 ~ 50 minutes;
After the described polycondensation reaction low vacuum stage terminates, add amino ethylene glycol fatty acid, and stir;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 ~ 280 DEG C, 50 ~ 90 minutes reaction time; Obtained modified poly ester;
(3) solid phase polycondensation thickening after described modified poly ester granulation, obtain the sticky section of height of modified poly ester, inherent viscosity is 0.9 ~ 1.2dL/g.
5. the preparation method of a kind of low miniature activated polyester industrial yarn according to claim 4, it is characterized in that, the mol ratio of described ethylene glycol and described terephthalic acid (TPA) is 1.2 ~ 2.0:1.
6. the preparation method of a kind of low miniature activated polyester industrial yarn according to claim 4, it is characterized in that, described catalyst is selected from the one in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight.
7. the preparation method of a kind of low miniature activated polyester industrial yarn according to claim 4, it is characterized in that, described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of described terephthalic acid (TPA) weight.
8. the preparation method of a kind of low miniature activated polyester industrial yarn according to claim 4, it is characterized in that, add the stirring after amino ethylene glycol fatty acid, the time is 15 ~ 20 minutes.
9. the preparation method of a kind of low miniature activated polyester industrial yarn according to claim 4, is characterized in that, being washed till without adopting liquor argenti nitratis ophthalmicus to detect till bromide ion with deionized water.
10. the preparation method of a kind of low miniature activated polyester industrial yarn according to claim 4, it is characterized in that, the described concentrated sulfuric acid refers to that mass concentration is the sulfuric acid of 70 ~ 80%, and concentrated sulfuric acid addition is 1 ~ 3wt% of binary of fatty acids; Described a certain amount of dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 40 ~ 50%, and dilute sulfuric acid addition is 1 ~ 3wt% of binary of fatty acids mono-methyl.
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| CN105506772A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester activated industrial yarn and preparation method thereof |
| CN105646858A (en) * | 2015-12-29 | 2016-06-08 | 江苏恒力化纤股份有限公司 | Ultra-low shrinkage polyester industrial yarn and preparation method thereof |
| WO2017113622A1 (en) * | 2015-12-29 | 2017-07-06 | 江苏恒力化纤股份有限公司 | High-modulus low-shrinkage polyester industrial yarn and preparation method therefor |
| CN107326456A (en) * | 2017-08-22 | 2017-11-07 | 无锡索力得科技发展有限公司 | It is a kind of to be used as the activation silk production method oiled for first by the use of basic finish |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105506772A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester activated industrial yarn and preparation method thereof |
| CN105646858A (en) * | 2015-12-29 | 2016-06-08 | 江苏恒力化纤股份有限公司 | Ultra-low shrinkage polyester industrial yarn and preparation method thereof |
| WO2017113622A1 (en) * | 2015-12-29 | 2017-07-06 | 江苏恒力化纤股份有限公司 | High-modulus low-shrinkage polyester industrial yarn and preparation method therefor |
| 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 |
| CN107326456A (en) * | 2017-08-22 | 2017-11-07 | 无锡索力得科技发展有限公司 | It is a kind of to be used as the activation silk production method oiled for first by the use of basic finish |
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