CN105504243B - A kind of heat-resistance polyester nonferrous industry silk and preparation method thereof - Google Patents
A kind of heat-resistance polyester nonferrous industry silk and preparation method thereof Download PDFInfo
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- CN105504243B CN105504243B CN201511018195.3A CN201511018195A CN105504243B CN 105504243 B CN105504243 B CN 105504243B CN 201511018195 A CN201511018195 A CN 201511018195A CN 105504243 B CN105504243 B CN 105504243B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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Abstract
The present invention relates to a kind of heat-resistance polyester nonferrous industry silk and preparation method thereof, the heat-resistance polyester nonferrous industry silk refers to the polyester industrial fiber for adding black agglomerate, by containing spinning after unsaturated double-bond polyester solid-phase tack producing and being obtained through ultraviolet light；The gel content of the heat-resistance polyester nonferrous industry silk is more than 10%, and melting temperature is more than 275 DEG C；The heat-resistance polyester nonferrous industry silk is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage 2.5 ± 0.5% of fiber.The addition of Masterbatch can make the thermal efficiency of fiber change, and due to the effect of carbon black, the heating rate of fiber can increase, higher requirement is proposed to the thermal stability of fiber, double bond introduces to form crosslinking points, forms a certain amount of network structure, improves the heat resisting temperature of poly- fiber.
Description
Technical field
The invention belongs to polyester industrial fiber preparing technical fields, are related to a kind of heat-resistance polyester nonferrous industry silk and its preparation side
Method, particularly a kind of polyester for the mixture for using ethylene glycol magnesium and antimony glycol containing unsaturated double-bond and polycondensation catalyst with
And heat-resistance polyester nonferrous industry silk and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, PET with its modulus is high, intensity is high,
It is well-pressed, conformality is good, pure health, barrier property are good etc., be widely used in fiber, the fields such as bottle is packed, film and sheet material,
Yield cumulative year after year, position in industry are obviously improved.
PET belongs to the straight chain macromolecular of symmetry, and strand does not contain side-chain radical, and regularity is very good, its main chain
Containing rigid phenyl ring and flexible alkyl, and the ester group being directly connected with phenyl ring constitutes rigid conjugated body with phenyl ring
System makes polyester have higher fusing point, and the fusing point of general polyester is at 260 DEG C or so.With the one step expansion of carry out of production application,
Higher requirement is proposed to the heat resistance of polyester.Unsaturated double-bond is introduced in the polyester, and is completed during fibre spinning
Cross-linking reaction makes fiber have raising by a relatively large margin in terms of heat resistance.Unsaturated double-bond is introduced in polyester fiber, and is had
Effect safely controls its crosslinking, will have the mechanical property of polyester fiber, heat resistance, chemical-resistance, flame retardant property compared with width
How the raising of degree is highly important problem in polyester fiber production technology with good unsaturated double-bond.
Influence of the polyester construction to glass transition temperature be it will be evident that add molecule segment movement wall ridge, PET's
Glass transition temperature is higher, it is necessary to dye at very high temperatures, promotion diffusion of the dye molecule to fibrous inside.In addition,
The strand of PET is regular, good crystallinity, and strand arrangement is close, and do not have an effect on strand with dye molecule
Polar group, the colouring for making polyester fiber are more difficult.
Polyester industrial fiber is painted according to colouring method, on the one hand need to be dyed at high temperature under high pressure, fiber is deposited
In a certain amount of boiling shrinkage, the quality decline of fiber is caused；On the other hand dye black mostly makes dyestuff, and the weatherability of dyestuff
It is poor, the service life of fiber will be influenced.
The present invention introduces unsaturated double-bond in the polyester, and cross-linking reaction is completed during fibre spinning, and fiber is made to exist
There is raising by a relatively large margin in terms of heat resistance, while by the way of Masterbatch addition, fiber is made both to have kept higher strength
There is good color and luster again.
The content of the invention
The object of the present invention is to provide a kind of heat-resistance polyester nonferrous industry silks and preparation method thereof, are that one kind contains unsaturation
Double bond and polycondensation catalyst are using ethylene glycol magnesium and the polyester of mixture and heat-resistance polyester nonferrous industry of antimony glycol
Silk and preparation method thereof.The present invention uses the mixture of ethylene glycol magnesium and antimony glycol, and for polycondensation catalyst, important is heat drops
Coefficient very little is solved, thermal degradation is reduced to the shadow minimum, reduction end carboxyl, oligomer, diethylene glycol content process Direct-spinning of PET Fiber
It rings, while also ensures the stability of unsaturated double-bond in polyester production process.
A kind of heat-resistance polyester nonferrous industry silk of the present invention, the heat-resistance polyester nonferrous industry silk refer to that surface coats
There is the polyester industrial fiber of toner coating, by containing spinning after unsaturated double-bond polyester solid-phase tack producing and being obtained through ultraviolet light；Institute
The gel content for stating heat-resistance polyester nonferrous industry silk is more than 10%, and melting temperature is more than 275 DEG C；The heat-resistance polyester has
Color industrial yarn in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage 2.5 of fiber ±
0.5%.Polyester containing unsaturated double-bond is terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol through esterification and in ethylene glycol magnesium and second
The lower polycondensation of mixture through catalytic effect of glycol antimony is made, then obtains polyester slice through pelletizing；
In the polyester slice containing unsaturated double-bond, content of carboxyl end group is less than 20mol/t, oligomer mass percentage content
Less than 1.0%, the mass percentage content of diethylene glycol (DEG) is less than 1.0%；In one macromolecular chain of the polyester containing unsaturated double-bond
The average unsaturated double-bond provided containing 1~6 by unsaturated dibasic acid molecule.
The molecular formula of the ethylene glycol magnesium is Mg (OCH2CH2OH)2。
Polyester industrial fiber is painted according to colouring method, on the one hand need to be dyed at high temperature under high pressure, fiber is deposited
In a certain amount of boiling shrinkage, the quality decline of fiber is caused；On the other hand dye black mostly makes dyestuff, and the weatherability of dyestuff
It is poor, the service life of fiber will be influenced, Masterbatch coloring mode has well solved problem above.But the addition meeting of Masterbatch
The thermal efficiency of fiber is made to change, due to the effect of carbon black, the heating rate of fiber can increase, and be carried to the thermal stability of fiber
Higher requirement is gone out, double bond introduces to form crosslinking points, forms a certain amount of network structure, improves the heat-resisting temperature of poly- fiber
Degree.
Unsaturated polyester (UP) is the unsaturated bond containing non-aromatic in molecular structure for saturated polyester,
Unsaturated polyester (UP) molecule is generally long chain type molecular structure.Reaction can be crosslinked between the long-chain molecule of unsaturated polyester (UP) to be formed
Complicated huge network molecule.The structure of network molecule is probably divided into three classes：Uniform continuous net-shaped structure；It is uneven
Continuous net-shaped structure, i.e., the larger net structure of density is interconnected by density smaller chain molecule；Discontinuously
Net structure, highdensity continuous net-shaped structure disperses are among the component not being bonded.Common unsaturated polyester (UP) is handed over
After connection reaction, to generate based on non-uniform continuous net-shaped structure.Its mechanical property after unsaturated polyester cross-linking, heat resistance,
Chemical-resistance, flame retardant property will have raising compared with amplitude.Selective cross-linking is after the completion of fiber preparation, by ultraviolet light-initiated
Mode carry out, ensure that stabilization of the double bond in process of polyester.
Mainly in esterification and polycondensation phase, the main side reaction in polycondensation process is for the generation of end carboxyl in polyester
Thermal degradation increases with response intensity, and thermal degradation accelerates, and degradation causes PET conglutination to decline, carboxyl end group value rise.Content of carboxyl end group
Height, the thermal stability of polyester resin is poor, and end carboxyl can carry out acidolysis reaction to ester group, can accelerate the hydrolysis of ester group, simultaneously
It can make the reduction of the electrical insulation capabilities such as the volume resistance of polyester.The carboxylic acid of polyester and the polyester macromolecule chain of carboxylic acid reactant salt generation
Salt consists of nucleus, and polyester is made to accelerate heterogeneous nucleation.Diethylene glycol (DEG) (DEG) directly influences the fusing point of polyester slice, and polyester is cut
The fusing point of piece can drastically decline with the increase of the wherein content of DEG, so it not only reflects the quality of production status, also directly
Influence the quality of post-processing-spinning technique and silk.Diethylene glycol (DEG) is the ehter bond for being very easy to oxidation, and drop is easily generated when heated
Solution.In the synthesis and process of polyester, the generation of oligomer is mainly closely bound up with PET thermal degradations and thermal oxidative degradation,
Oligomer is mainly concerned with heterogeneous nucleation, spinning processing etc., and the performance and the processing of rear road to polyester cause certain harmful effect.
A kind of heat-resistance polyester nonferrous industry silk as described above, the line line density of the heat-resistance polyester nonferrous industry silk
Deviation ratio≤1.5%, fracture strength >=7.0cN/dtex, fracture strength CV value≤2.5%, extension at break are 12.0 ± 1.5%,
Extension at break CV value≤7.0%.
In the mixture of a kind of heat-resistance polyester nonferrous industry silk as described above, the ethylene glycol magnesium and antimony glycol,
Ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1.
The present invention also provides a kind of preparation methods of heat-resistance polyester nonferrous industry silk, are terephthalic acid (TPA), unsaturation
Polyester is made in polycondensation through esterification and under the effect of the mixture through catalytic of ethylene glycol magnesium and antimony glycol for binary acid and ethylene glycol, then passes through
Pelletizing obtains polyester slice.Then viscosified by solid phase polycondensation；It adds, squeeze out, cool down, oil, draw through metering, black agglomerate again
Stretch, thermal finalization, winding, ultraviolet light, heat-resistance polyester nonferrous industry silk is made.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, main technique are：
(1) preparation of catalyst glycol magnesium：
In single-cell for electrolyzation plus ethylene glycol, supporting electrolyte are magnesium chloride, and metal MAG block is anode, and cathode is graphite；
Logical direct current, 6~10V of starting voltage, cathode-current density are 150~200mA, when electrolysis 10~12 is small at 50~60 DEG C, electricity
Electrode is taken out after solution, obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and second two is obtained after dry
Magnesium alkoxide；
(2) preparation of polyester, including esterification and polycondensation reaction：
The esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol as raw material, after being made into uniform sizing material be esterified instead
Should, obtain esterification products；Esterification is pressurizeed in nitrogen atmosphere, pressure control in normal pressure~0.3MPa, temperature 250~
260 DEG C, esterification water quantity of distillate reaches more than the 90% of theoretical value for esterification terminal；
The polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst, stabilizer and ultraviolet initiator in esterification products,
Start polycondensation reaction under conditions of negative pressure, which is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature control exists
260~270 DEG C, the reaction time is 30~50 minutes；The catalyst is ethylene glycol magnesium and the mixture of antimony glycol；
The polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure less than 100Pa, and reaction temperature control is at 275~280 DEG C, 50~90 minutes reaction time；
(3) solid phase polycondensation：
The polyester slice is viscosified by solid phase polycondensation, and the inherent viscosity of polyester slice is made to be increased to 0.9~1.2dL/g,
The as high viscous section of polyester containing unsaturated double-bond；
(4) spinning main technologic parameters：
The temperature of the extrusion is 290~320 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The speed of the winding is 2600~3000m/min；
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the ethylene glycol and the terephthaldehyde
The molar ratio of acid is 1.2~2.0:1.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the ethylene glycol magnesium and antimony glycol
In mixture, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is the terephthalic acid (TPA) quality
0.01%~0.05%.Using ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium, which belongs to, to be compared
Mild one kind, thermal degradation coefficient very little, the side reaction triggered during the reaction is less, reduces and holds in process
The generation of carboxyl and oligomer, while also ensure the stability of unsaturated double-bond in polyester production process.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the stabilizer are selected from phosphoric acid triphen
One kind in ester, trimethyl phosphate and Trimethyl phosphite, stabilizing agent dosage for the terephthalic acid (TPA) weight 0.01%~
0.05%.For stabilizer mainly based on phosphate, main function is the free radical that catching reaction generates in the course of the polymerization process, is reduced
Side reaction, while also protect unsaturated double-bond.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the unsaturated dibasic acid with to benzene
Dioctyl phthalate molar ratio is 1~5:100.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the unsaturated dibasic acid are maleic
One kind in diacid, fumaric acid, muconic acid.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the black agglomerate additive amount is described
The 0.01%~0.03% of polyester slice quality.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, the ultraviolet initiator are aphthenic acids
One kind in cobalt, cobalt acetate, zinc naphthenate, zinc stearate, zinc acetate, addition for terephthalic acid (TPA) weight 0.03%~
0.05%.
A kind of preparation method of heat-resistance polyester nonferrous industry silk as described above, which is characterized in that the ultraviolet lighting
The intensity for the ultraviolet light penetrated is 100-120mj/cm2。
Photoinitiator is the key component of cross-linking system, and initiator molecule (250~420nm) between ultraviolet region has centainly
Absorbing ability, initiator molecule can also continue to transit to three lines of excitation from ground state transition to active excitation state after absorbing luminous energy
State；In its excited singlet, it is also possible to which after excited triplet state undergoes unimolecule or bimolecular chemical action, generation can draw
The biologically active fragment of monomer polymerization is sent out, these biologically active fragments can be free radical, trigger cross-linking reaction.
Metal salt is selected to be primarily due to it with higher thermal stability as initiator, i.e., in polymerization, spinning process
It is middle to keep stablizing, while cobalt salt does not generate negative impact with zinc salt to polyester reaction, cobalt salt also can be as the tune of polyester
Toner.
Since, there are unsaturated double-bond, under the conditions of existing for initiator, unsaturation is poly- in unsaturated polyester (UP) molecular structure
Reaction can be crosslinked between the long-chain molecule of ester and forms complicated huge network molecule.Crosslinking is that raising is polymer
Can one of most direct most efficient method, by crosslinking the degree of cross linking of system can be made raise, relative molecular mass increases, and
So that the physical and chemical performance of polymer significantly improves.
Polyester fondant degradation has two aspects to product quality influence, i.e., viscosity reduces and relative molecular mass distribution broadens,
Degradation reaction is small on PET conglutination drop influence, but its influence to relative molecular mass distribution is bigger, makes molecular mass point
Cloth broadens.The principal element for causing thermal degradation is high mild catalyst, and high temperature is that response intensity is excessively high, and degradation is caused to accelerate, production
End carboxyl has been given birth to, while has also increased cyclic oligomer；Catalyst is then related to the degradation reaction constant of catalyst, in polycondensation
Cheng Zhong, the effect of catalyst, which is not only in that, can be catalyzed generation main reaction, so as to influence the rate and yield of reaction, while can also urge
Thermal degradation and ehter bond generation increase the content of diethylene glycol (DEG), so as to increase the content of end carboxyl.
It is characteristic of the invention that the opening of double bond, crosslinking just occur after polyester fiber stretching, thermal finalization, complete.
Polyester fiber, which will obtain high intensity and modulus, to carry out the stretching of high power, and an important factor for influencing drawn polyester performance is
The entanglement density of polyester in drawing process, the point that tangles enable the drawability of polyester fiber to decline.Unsaturation in the present invention is double
Key introduces in the course of the polymerization process, with addition stabilizer is crossed, reduces the generation of free radical, and photoinitiator is spun in entire polymerization
It keeps stablizing during silk, which ensures that the stabilization of polymerization, spinning process is normal.
The object of the present invention is to provide a kind of heat-resistance polyester nonferrous industry silk, polyester is using relatively mild a kind of contracting
Poly- catalyst glycol magnesium, the less side reaction triggered during the reaction is less, efficiently controlled the content of end carboxyl with
And the less thermal degradation in process, reduce the generation of oligomer in process, while also ensure production of polyester
The stability of unsaturated double-bond in the process.Unsaturated double-bond is introduced in polyester fiber, and effectively and safely controls its crosslinking,
The gel content of fiber after crosslinking will roll up, by the mechanical property of polyester fiber, heat resistance, chemical-resistance,
Flame retardant property has the raising compared with amplitude.The addition of Masterbatch can make the thermal efficiency of fiber change, fine due to the effect of carbon black
The heating rate of dimension can increase, and higher requirement is proposed to the thermal stability of fiber, and double bond introduces to form crosslinking points, form one
Quantitative network structure improves the heat resisting temperature of poly- fiber.
Advantageous effect：
● using ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to comparatively gentle one
Class, thermal degradation coefficient very little, the side reaction triggered during the reaction is less, reduces end carboxyl in process and low
The generation of polymers, while also ensure the stability of unsaturated double-bond in polyester production process.
● the content of carboxyl end group of polyester slice is less than 20mol/t, and oligomer mass percentage content is less than 1.0%, and two is sweet
The mass percentage content of alcohol is less than 1.0%, is conducive to further improve the quality of fiber.In described one macromolecular chain of polyester
The average unsaturated double-bond provided containing 1~6 by unsaturated dibasic acid molecule.
● the thermal contraction of polyester fiber is reduced, improves heat resisting temperature, the gel content of polyester industrial fiber can reach
10%, melting temperature is more than 275 DEG C.
● unsaturated double-bond is introduced in polyester, and its crosslinking is effectively and safely controlled after the completion of prepared by polyester fiber, is handed over
The gel content of fiber after connection will roll up, will be to the mechanical property of polyester fiber, heat resistance, chemical-resistance, resistance
Combustion performance has the raising compared with amplitude.
● the addition of Masterbatch can make the thermal efficiency of fiber change, due to the effect of carbon black, the heating rate of fiber
It can increase, higher requirement is proposed to the thermal stability of fiber, double bond introduces to form crosslinking points, forms a certain amount of network knot
Structure improves the heat resisting temperature of poly- fiber.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed scope.
A kind of heat-resistance polyester nonferrous industry silk of the present invention, heat-resistance polyester nonferrous industry silk refer to add black agglomerate
Polyester industrial fiber, by containing spinning after unsaturated double-bond polyester solid-phase tack producing and being obtained through ultraviolet light；The heat resistant poly
The gel content of ester nonferrous industry silk is more than 10%, and melting temperature is more than 275 DEG C；The heat-resistance polyester nonferrous industry silk exists
Temperature is the dry-hot shrinkage 2.5 ± 0.5% of fiber under the test condition of 177 DEG C × 10min × 0.05cN/dtex.It is described to contain
Unsaturated double-bond polyester is terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol through esterification and in ethylene glycol magnesium and antimony glycol
The lower polycondensation of mixture through catalytic effect is made, then obtains polyester slice through pelletizing；In polyester slice, content of carboxyl end group is less than 20mol/
T, oligomer mass percentage content are less than 1.0%, and the mass percentage content of diethylene glycol (DEG) is less than 1.0%；Containing unsaturated double-bond
The average unsaturated double-bond provided containing 1~6 by unsaturated dibasic acid molecule in one macromolecular chain of polyester；Ethylene glycol
The molecular formula of magnesium is Mg (OCH2CH2OH)2。
Wherein, line density deviation ratio≤1.5% of heat-resistance polyester nonferrous industry silk, fracture strength >=7.0cN/dtex,
Fracture strength CV value≤2.5%, extension at break are 12.0 ± 1.5%, extension at break CV value≤7.0%.
Wherein, in the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1.
Wherein, terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol are through esterification and in the mixed of ethylene glycol magnesium and antimony glycol
It closes polycondensation under object catalytic action and polyester is made, then polyester slice is obtained through pelletizing；Then viscosified by solid phase polycondensation；Again through meter
Amount, black agglomerate are added, squeezed out, cooling down, oiling, stretching, thermal finalization, winding and ultraviolet light, obtained heat-resistance polyester have
Color industrial yarn.
Embodiment 1
A kind of preparation method of heat-resistance polyester nonferrous industry silk, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 6V, cathode-current density 150mA when electrolysis 10 is small at 50 DEG C, take out electricity after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid maleic acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The molar ratio of formic acid is 1.2:1, unsaturated dibasic acid is 1 with terephthalic acid (TPA) molar ratio:100, it is carried out after being made into uniform sizing material
Esterification obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is in normal pressure, and temperature is at 250 DEG C, ester
Change water quantity of distillate and reach the 92% of theoretical value for esterification terminal；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer triphenyl phosphate and ultraviolet light draw in esterification products
Agent cobalt naphthenate is sent out, catalyst amount is the 0.01% of terephthalic acid (TPA) quality, and the addition of cobalt naphthenate is terephthalic acid (TPA)
The 0.03% of weight, triphenyl phosphate dosage are the 0.01% of terephthalic acid (TPA) weight, the intensity of the ultraviolet light of ultraviolet light
For 100mj/cm2, start polycondensation reaction under conditions of negative pressure, which is steadily evacuated to absolute pressure 498Pa by normal pressure,
At 260 DEG C, the reaction time is 30 minutes for temperature control；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium
It is 2 with antimony glycol mass ratio:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
To absolute pressure 98Pa, reaction temperature control is at 275 DEG C, 50 minutes reaction time；Polyester is made, obtains polyester through pelletizing and cuts
Piece；
(3) solid phase polycondensation：
Polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 0.9dL/g, as containing insatiable hunger
With the high viscous section of double bond polyester；
(4) spinning main technologic parameters：
The temperature of extrusion is 290 DEG C；
The wind-warm syndrome of cooling is 20 DEG C；
The speed of winding is 2600m/min, and black agglomerate additive amount is the 0.01% of polyester slice quality.
The gel content of heat-resistance polyester nonferrous industry silk obtained is 18%, 277 DEG C of melting temperature；Heat-resistance polyester
Nonferrous industry silk is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage of fiber
2.7%；The line line density deviation ratio 1.4% of heat-resistance polyester nonferrous industry silk, fracture strength 7.2cN/dtex, fracture strength CV
Value 2.2%, extension at break 12.3%, extension at break CV values 6.7%.
Embodiment 2
A kind of preparation method of heat-resistance polyester nonferrous industry silk, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 10V, cathode-current density 200mA when electrolysis 12 is small at 60 DEG C, take out electricity after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid fumaric acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The molar ratio of formic acid is 2.0:1, unsaturated dibasic acid is 5 with terephthalic acid (TPA) molar ratio:100, it is carried out after being made into uniform sizing material
Esterification obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, pressure control in 0.3MPa, temperature at 260 DEG C,
Esterification water quantity of distillate reaches the 95% of theoretical value for esterification terminal；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer trimethyl phosphate and ultraviolet light draw in esterification products
Agent cobalt acetate is sent out, catalyst amount is the 0.05% of terephthalic acid (TPA) quality, and the addition of cobalt acetate is terephthalic acid (TPA) weight
0.05%, trimethyl phosphate dosage is the 0.05% of terephthalic acid (TPA) weight, and the intensity of the ultraviolet light of ultraviolet light is
120mj/cm2, start polycondensation reaction under conditions of negative pressure, which is steadily evacuated to absolute pressure 496Pa by normal pressure, temperature
At 270 DEG C, the reaction time is 50 minutes for degree control；The catalyst is the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol
Magnesium is 3 with antimony glycol mass ratio:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
To absolute pressure 97Pa, reaction temperature control is at 280 DEG C, 90 minutes reaction time；Polyester is made, obtains polyester through pelletizing and cuts
Piece；
(3) solid phase polycondensation：
Polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.2dL/g, as containing insatiable hunger
With the high viscous section of double bond polyester；
(4) spinning main technologic parameters：
The temperature of extrusion is 320 DEG C；
The wind-warm syndrome of cooling is 30 DEG C；
The speed of winding is 3200m/min；Black agglomerate additive amount is the 0.03% of polyester slice quality.
The gel content of heat-resistance polyester nonferrous industry silk obtained is 12%, 278 DEG C of melting temperature；Heat-resistance polyester
Nonferrous industry silk is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage of fiber
2.6%；The line line density deviation ratio 1.3% of heat-resistance polyester nonferrous industry silk, fracture strength 8.2cN/dtex, fracture strength CV
Value 2.3%, extension at break 10.9%, extension at break CV values 6.7%.
Embodiment 3
A kind of preparation method of heat-resistance polyester nonferrous industry silk, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 8V, cathode-current density 160mA when electrolysis 11 is small at 55 DEG C, take out electricity after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid muconic acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The molar ratio of formic acid is 1.5:1, unsaturated dibasic acid is 2 with terephthalic acid (TPA) molar ratio:100, it is carried out after being made into uniform sizing material
Esterification obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, pressure control in 0.2MPa, temperature at 255 DEG C,
Esterification water quantity of distillate reaches the 94% of theoretical value for esterification terminal；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst, stabilizer Trimethyl phosphite and ultraviolet light in esterification products
Initiator zinc naphthenate, catalyst amount are the 0.02% of terephthalic acid (TPA) quality, and the addition of zinc naphthenate is terephthaldehyde
The 0.04% of sour weight, Trimethyl phosphite dosage are the 0.02% of terephthalic acid (TPA) weight, the ultraviolet light of ultraviolet light
Intensity is 110mj/cm2, start polycondensation reaction under conditions of negative pressure, which is steadily evacuated to absolute pressure by normal pressure
495Pa, at 265 DEG C, the reaction time is 35 minutes for temperature control；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, second
Two magnesium alkoxides are 2 with antimony glycol mass ratio:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
To absolute pressure 96Pa, reaction temperature control is at 278 DEG C, 55 minutes reaction time；Polyester is made, obtains polyester through pelletizing and cuts
Piece；
(3) solid phase polycondensation：
Polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.2dL/g, as containing insatiable hunger
With the high viscous section of double bond polyester；
(4) spinning main technologic parameters：
The temperature of extrusion is 295 DEG C；
The wind-warm syndrome of cooling is 25 DEG C；
The speed of winding is 2700m/min；Black agglomerate additive amount is the 0.02% of polyester slice quality.
The gel content 22% of heat-resistance polyester nonferrous industry silk obtained, 279 DEG C of melting temperature；Heat-resistance polyester has
Color industrial yarn is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage 2.6% of fiber；
The line line density deviation ratio 1.1% of heat-resistance polyester nonferrous industry silk, fracture strength 8.1cN/dtex, fracture strength CV values
2.2%, extension at break 12.2%, extension at break CV values 7.0%.
Embodiment 4
A kind of preparation method of heat-resistance polyester nonferrous industry silk, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 8V, cathode-current density 180mA when electrolysis 11 is small at 55 DEG C, take out electricity after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid maleic acid and ethylene glycol as raw material, ethylene glycol with it is described right
The molar ratio of phthalic acid is 1.5:1, unsaturated dibasic acid is 2 with terephthalic acid (TPA) molar ratio:100, after being made into uniform sizing material
Esterification is carried out, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled in 0.3MPa, and temperature is 250
DEG C, esterification water quantity of distillate reaches the 93% of theoretical value for esterification terminal；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer triphenyl phosphate and ultraviolet light draw in esterification products
Agent zinc stearate is sent out, catalyst amount is the 0.01% of terephthalic acid (TPA) quality, and the addition of zinc stearate is terephthalic acid (TPA)
The 0.05% of weight, triphenyl phosphate dosage are the 0.01% of terephthalic acid (TPA) weight, the intensity of the ultraviolet light of ultraviolet light
For 110mj/cm2, start polycondensation reaction under conditions of negative pressure, which is steadily evacuated to absolute pressure 492Pa by normal pressure,
At 262 DEG C, the reaction time is 34 minutes for temperature control；Catalyst is the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium
It is 2 with antimony glycol mass ratio:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, reaction pressure is made to be down to absolutely
To pressure 95Pa, reaction temperature control is at 276 DEG C, 80 minutes reaction time；Polyester is made, polyester slice is obtained through pelletizing；
(3) solid phase polycondensation：
Polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.1dL/g, as containing insatiable hunger
With the high viscous section of double bond polyester；
(4) spinning main technologic parameters：
The temperature of extrusion is 300 DEG C；
The wind-warm syndrome of cooling is 25 DEG C；
The speed of winding is 2900m/min；Black agglomerate additive amount is the 0.03% of polyester slice quality.
The gel content 14% of heat-resistance polyester nonferrous industry silk obtained, 277 DEG C of melting temperature；Heat-resistance polyester has
Color industrial yarn is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage 2.8% of fiber；
The line line density deviation ratio 1.3% of heat-resistance polyester nonferrous industry silk, fracture strength 7.5cN/dtex, fracture strength CV values
2.2%, extension at break 13.3%, extension at break CV values 6.7%.
Embodiment 5
A kind of preparation method of heat-resistance polyester nonferrous industry silk, main technique are：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is stone
Ink；Logical direct current, starting voltage 6V, cathode-current density 200mA when electrolysis 10 is small at 60 DEG C, take out electricity after electrolysis
Pole obtains white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol magnesium is obtained after dry；
(2) preparation of polyester, including esterification and polycondensation reaction：
Esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid fumaric acid and ethylene glycol as raw material, ethylene glycol and to benzene two
The molar ratio of formic acid is 1.6:1, unsaturated dibasic acid is 2 with terephthalic acid (TPA) molar ratio:100, it is carried out after being made into uniform sizing material
Esterification obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and pressure control is in normal pressure, and temperature is at 250 DEG C, ester
Change water quantity of distillate and reach the 92% of theoretical value for esterification terminal；
Polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the polycondensation reaction low vacuum stage, addition catalyst, stabilizer triphenyl phosphate and ultraviolet light draw in esterification products
Agent zinc acetate is sent out, catalyst amount is the 0.01% of terephthalic acid (TPA) quality, and the addition of zinc acetate is terephthalic acid (TPA) weight
0.05%, triphenyl phosphate dosage is the 0.05% of terephthalic acid (TPA) weight, and the intensity of the ultraviolet light of ultraviolet light is
100mj/cm2, start polycondensation reaction under conditions of negative pressure, which is steadily evacuated to absolute pressure 495Pa by normal pressure, temperature
At 260 DEG C, the reaction time is 30 minutes for degree control；Catalyst for ethylene glycol magnesium and antimony glycol mixture, ethylene glycol magnesium with
Antimony glycol mass ratio is 3:1；
Polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
To absolute pressure 96Pa, reaction temperature control is at 277 DEG C, 50 minutes reaction time；Polyester is made, obtains polyester through pelletizing and cuts
Piece；
(3) solid phase polycondensation：
Polyester slice is viscosified by solid phase polycondensation, the inherent viscosity of polyester slice is made to be increased to 1.2dL/g, as containing insatiable hunger
With the high viscous section of double bond polyester；
(4) spinning main technologic parameters：
The temperature of extrusion is 320 DEG C；
The wind-warm syndrome of cooling is 20 DEG C；
The speed of winding is 2600m/min；Black agglomerate additive amount is the 0.01% of polyester slice quality.
The gel content 15% of heat-resistance polyester nonferrous industry silk obtained, 275 DEG C of melting temperature；Heat-resistance polyester has
Color industrial yarn is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage 2.9% of fiber；
The line line density deviation ratio 1.1% of heat-resistance polyester nonferrous industry silk, fracture strength 7.7cN/dtex, fracture strength CV values
2.5%, extension at break 12.6%, extension at break CV values 6.7%.
Claims (9)
1. a kind of heat-resistance polyester nonferrous industry silk, it is characterized in that：The heat-resistance polyester nonferrous industry silk refers to add black
The polyester industrial fiber of master batch, by containing spinning after unsaturated double-bond polyester solid-phase tack producing and being obtained through ultraviolet light；It is described heat-resisting
Property polyester colored industrial yarn gel content be more than 10%, melting temperature be more than 275 DEG C；The heat-resistance polyester nonferrous industry
Silk is in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the dry-hot shrinkage 2.5 ± 0.5% of fiber；Institute
State polyester containing unsaturated double-bond for terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol through esterification and in ethylene glycol magnesium and ethylene glycol
The lower polycondensation of mixture through catalytic effect of antimony is made, then obtains polyester slice through pelletizing；
In the polyester slice, content of carboxyl end group is less than 20mol/t, and oligomer mass percentage content is less than 1.0%, diethylene glycol (DEG)
Mass percentage content be less than 1.0%；Averagely contain 1~6 in one macromolecular chain of the polyester containing unsaturated double-bond
The unsaturated double-bond provided by unsaturated dibasic acid molecule；
The molecular formula of the ethylene glycol magnesium is Mg (OCH2CH2OH)2；
In the mixture of the ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1.
2. a kind of heat-resistance polyester nonferrous industry silk according to claim 1, which is characterized in that the heat-resistance polyester has
Line density deviation ratio≤1.5% of color industrial yarn, fracture strength >=7.0cN/dtex, fracture strength CV value≤2.5%, fracture are stretched
Long rate is 12.0 ± 1.5%, elongation at break CV value≤7.0%.
3. such as a kind of preparation method of heat-resistance polyester nonferrous industry silk according to any one of claims 1 to 2, feature
It is：Terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol are made through esterification and in the mixture through catalytic of ethylene glycol magnesium and antimony glycol
Polyester is made with lower polycondensation, then polyester slice is obtained through pelletizing；Then viscosified by solid phase polycondensation；Again through metering, black agglomerate
Add, squeeze out, cooling down, oiling, stretching, thermal finalization, winding and ultraviolet light, heat-resistance polyester nonferrous industry silk is made.
A kind of 4. preparation method of heat-resistance polyester nonferrous industry silk according to claim 3, which is characterized in that main work
Skill is：
(1) preparation of catalyst glycol magnesium：
Ethylene glycol is added in single-cell for electrolyzation, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and cathode is graphite；It is logical
Direct current, 6~10V of starting voltage, cathode-current density are 150~200mA, when electrolysis 10~12 is small at 50~60 DEG C, electrolysis
After take out electrode, obtain white suspension；It is filtered under diminished pressure, white solid is washed with absolute ethyl alcohol, and ethylene glycol is obtained after dry
Magnesium；
(2) preparation of polyester, including esterification and polycondensation reaction：
The esterification：
Using terephthalic acid (TPA), unsaturated dibasic acid and ethylene glycol as raw material, esterification is carried out after being made into uniform sizing material, is obtained
To esterification products；Esterification is pressurizeed in nitrogen atmosphere, pressure control in normal pressure~0.3MPa, temperature at 250~260 DEG C,
Esterification water quantity of distillate reaches more than the 90% of theoretical value for esterification terminal；
The polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
The polycondensation reaction low vacuum stage adds in catalyst, stabilizer and ultraviolet initiator, in negative pressure in esterification products
Under conditions of start polycondensation reaction, which is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control 260
~270 DEG C, the reaction time is 30~50 minutes；The catalyst is ethylene glycol magnesium and the mixture of antimony glycol；
The polycondensation reaction high vacuum stage of Fig after the polycondensation reaction low vacuum stage, continues to vacuumize, drops reaction pressure
It is less than 100Pa to absolute pressure, reaction temperature control is at 275~280 DEG C, 50~90 minutes reaction time；
Polyester is made, polyester slice is obtained through pelletizing；
(3) solid phase polycondensation：
The polyester slice is viscosified by solid phase polycondensation, and the inherent viscosity of polyester slice is made to be increased to 0.9~1.2dL/g, is
The high viscous section of polyester containing unsaturated double-bond；
(4) spinning main technologic parameters：
The temperature of the extrusion is 290~320 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The speed of the winding is 2600~3200m/min.
A kind of 5. preparation method of heat-resistance polyester nonferrous industry silk according to claim 3 or 4, which is characterized in that institute
The molar ratio for stating ethylene glycol and the terephthalic acid (TPA) is 1.2~2.0:1.
A kind of 6. preparation method of heat-resistance polyester nonferrous industry silk according to claim 4, which is characterized in that the second
In the mixture of two magnesium alkoxides and antimony glycol, ethylene glycol magnesium is 2~3 with antimony glycol mass ratio:1；The catalyst amount is
The 0.01%~0.05% of the terephthalic acid (TPA) quality；The stabilizer is selected from triphenyl phosphate, trimethyl phosphate and phosphorous
One kind in sour trimethyl, stabilizing agent dosage are the 0.01%~0.05% of terephthalic acid (TPA) weight.
7. the preparation method of a kind of heat-resistance polyester nonferrous industry silk according to claim 4, which is characterized in that described
Unsaturated dibasic acid is 1~5 with terephthalic acid (TPA) molar ratio:100；The unsaturated dibasic acid is maleic acid, anti-butylene
One kind in diacid, muconic acid；The black agglomerate additive amount is the 0.01%~0.03% of the polyester slice quality.
A kind of 8. preparation method of heat-resistance polyester nonferrous industry silk according to claim 4, which is characterized in that the purple
Outer photoinitiator is cobalt naphthenate, one kind in cobalt acetate, zinc naphthenate, zinc stearate, zinc acetate, and addition is terephthaldehyde
The 0.03%~0.05% of sour weight.
A kind of 9. preparation method of heat-resistance polyester nonferrous industry silk according to claim 3, which is characterized in that the purple
The intensity of the ultraviolet light of outer light irradiation is 100-120mj/cm2。
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