CN106012081B - Hyperbranched compound is modified the preparation method that can contaminate polyimide fiber - Google Patents
Hyperbranched compound is modified the preparation method that can contaminate polyimide fiber Download PDFInfo
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- CN106012081B CN106012081B CN201610363527.XA CN201610363527A CN106012081B CN 106012081 B CN106012081 B CN 106012081B CN 201610363527 A CN201610363527 A CN 201610363527A CN 106012081 B CN106012081 B CN 106012081B
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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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
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to the preparation methods that a kind of modification of hyperbranched compound can contaminate polyimide fiber, are characterized in, include the following steps：（1）Aromatic diacid acid anhydride and binary or trihydroxylic or amino-compound in polymeric kettle are subjected to polymerisation, hyperbranched compound is prepared；（2）It is added in polyimides polymeric solution after hyperbranched compound is purified and carries out polymerisation；The polyimides polymeric solution is by 3,3 ', 4,4 ' bibenzene tetracarboxylic dianhydride of monomer（BPDA）And monomer p-phenylene diamine（PDA）Composition；（3）Using step（2）Obtained polymeric reaction product carries out spinning, and polyimide fiber is made.The present invention generates a large amount of active group, and change the accumulation mode of polyimides macromolecular by adding the method polyimide fiber that dissaving polymer is modified, and increases binding force and dye-uptake with dye molecule, acquisition can contaminate polyimide fiber.
Description
Technical field
The present invention relates to the preparation methods that a kind of modification of hyperbranched compound can contaminate polyimide fiber, belong to function weaving
Field of material technology.
Background technology
Polyimides satisfactory mechanical property, and 400 DEG C of temperature can have not only been withstood up to, but also can be below -200 DEG C
Ultralow temperature keeps normal performance, also possesses good insulation performance, it may be said that overall performance is very good.Since these are good
Performance, the development prospect of polyimides is also very considerable.
According to the difference of the monomer of composition polyimides, it is sub- that polyimides can be divided into the aliphatic polyamides without phenyl ring
Amine, a kind of monomer contain three kinds of the aromatic polyimide of the semi-aromatic polyimides and two kinds of monomers of phenyl ring containing phenyl ring.
And according to thermal property, then it can be divided into thermoplasticity and Thermocurable polyimide.
Polyimides is the polymer containing imide ring structure on molecule main chain (as shown in formula I).Fragrant adoption
Acid imide can be by diversified monomer composition, this makes its structure that diversification be presented.And polyimides simultaneously possess it is outstanding
Comprehensive performance, this is that many high molecular materials are too far behind to catch up.And diversified synthetic method and manufacturing process so that poly-
Acid imide can be with mass production without subject to conditions.Above a variety of advantages make polyimide material have broad application surface,
And in some high-tech areas such as aerospace, electronics industry, nanometer, laser etc., polyimides fabric is even more great Zhan brilliance.
Aromatic polyimide is mainly included due to its unique chemical constitution and with excellent comprehensive performance：(1) it is good
Good thermal stability, by the polyimides prepared by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA)
Heat decomposition temperature be up to 600 DEG C；(2) excellent resistance to low temperature, even if will not embrittlement in liquid helium；(3) good ruler
Very little stability and mechanical property；(4) excellent radiation resistance；(5) good insulating properties and dielectricity；(6) excellent anti-flammability
And less toxic and good biocompatibility.Excellent properties possessed by polyimides make it obtain the extensive concern of people,
Develop the polyimide of diversified forms.The polyimide successfully commercially produced at present has：Film, fiber and
Engineering plastics etc..
In field of textiles, polyimide fiber possesses good prospect, because it has preferable spinning property, with reference to the excellent of its own
Benign energy, can be applied to togs field.The good heat-proof quality of polyimides causes the heat-insulated protection made by it
Clothes are worn very comfortably, and skin and its conformability are preferable.Due to the stability of polyimides, by polyimides face
Clothing usage time is also grown made of material, is unlikely to deform, and very safe.Meanwhile polyimides fabric is in terms of industrial and protective clothing
Application amount, demand it is all very big, many special work positions in China are required for industrial and protective clothing, this respect at work
Demand per year over 350000 sets.Make so more industrial and protective clothing, what is needed every year has heat-resistant fireproof performance
Clothes are up to 300 tons or so with fiber.It may be said that application of the polyimides in terms of clothes has very big advantage.
In non-woven fabrics manufacture view, polyimide fiber also fully develops talents.The spies such as armoured force soldier, racing driver, pilot
Different industry needs the clothes that a large amount of fire-proof flame-retardant fibre makes at work, and the non-woven fabrics spinned by polyimides fabric is should
For the optimal material of this part.The non-woven fabrics of polyimide fiber manufacture often combines nanometer technology, forms high-tech nanometer
Product has thermal property, and very comfortable, can be used in military clothes, anti-chemical and biological weapons high-performance apparel, efficient smog protection face
The national defences such as cover, can also come into the life of the people, some, which are made, can eliminate the leisure type clothes savoured extremely.
But there is being difficult to dye, textile application is extremely restricted polyimide fiber at present.Therefore set about
The colouring problem for solving polyimide fiber has become an important technology for breaking polyimide fiber application field.
Invention content
The purpose of the present invention is overcoming the deficiencies in the prior art, provide a kind of hyperbranched compound modification can contaminate it is poly-
The preparation method of imide fiber, the method polyimide fiber being modified by adding dissaving polymer generate a large amount of
Active group, and change the accumulation mode of polyimides macromolecular, binding force and dye-uptake with dye molecule are increased, is obtained
Polyimide fiber can be contaminated.
According to technical solution provided by the invention, a kind of hyperbranched compound modification can contaminate the preparation side of polyimide fiber
Method is characterized in, includes the following steps：
(1) by aromatic diacid acid anhydride and binary or trihydroxylic or amino-compound by acid anhydrides and hydroxyl or amino molar ratio
1:2~2:1 mixing carries out polymerisation in polymeric kettle, and reaction temperature is 60~180 DEG C, and reaction vacuum degree is less than 0.1 big
Air pressure, reaction time are 3~9 hours, and hyperbranched compound is prepared；
(2) the filtered purification of hyperbranched compound for obtaining step (1), and add in polyimides polymeric solution and carry out
Polymerisation, polymerisation are protected using nitrogen, and polymerization temperature is -5~5 DEG C, and polymerization reaction time is 2~10 hours；It is described
Polyimides polymeric solution by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of monomer (BPDA) and monomer p-phenylene diamine (PDA) with mole
Than 1:2~2:1 composition, the mole of the hyperbranched compound account for the 1%~10% of monomer BPDA and PDA integral molar quantity；
(3) spinning is carried out using the polymeric reaction product that step (2) obtains, polyimide fiber is made.
Further, the binary or trihydroxylic or amino-compound use triaminobenzene, triethanolamine or diethanol
Amine.
Further, a concentration of the 15~30% of the polyimides polymeric solution, solvent use N, N dimethyl acetamide
(Dmac), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or N- methyl 2-Pyrrolidone (NMP).
Further, in the step (3), the spinning of polyimide fiber uses dry spinning equipment.
Further, the spinning technique of the polyimide fiber is：The solution that step (2) obtains is squeezed into air, so
Enter in coagulating bath afterwards, 1.5~3 times are stretched in stretch bath, winding obtains polyamic acid fiber；Then by polyamic acid fibre
It is 1 that dimension, which is immersed in mass ratio,:5~5:Chemical imidization is carried out in 1 acetic anhydride and the mixed liquor of pyridine, temperature is 20~70
DEG C, the time is 0.5~2h, obtains polyimide fiber；Polyimide fiber is handled into 2~10min at 450~600 DEG C again, together
When the stretching of small multiple is carried out to polyimide fiber, draw ratio is 1.5~3 times, obtains the polyimide fiber.
Further, the coagulating bath and stretch bath use mass ratio as 1:5~5:1 water-solvent mixed liquor, solvent are adopted
With methanol, Dmac, DMF, DMSO or NMP.
Hyperbranched compound modification of the present invention can contaminate the preparation method of polyimide fiber, for polyimide fiber
The problem that can not be contaminated proposes a practicable solution, is not damaging polyimide fiber physical and chemical properties
On the basis of not only solve the problem of polyimides is difficult to dye, more pass through the mode polyimide fiber of chemical modification
Antistatic property is promoted, and flame retardant effect is promoted, and causes anti-microbial property substantially due to increasing amino isoreactivity antibacterial group
Improve, fiber has better spinning and weaving performance, increase the cohesive force of yarn and reduction to should be electrostatic too big and generate
Filoplume is conducive to the raising of yarn and its fabric mechanical performance, improves the wearing comfort of fabric, has expanded it using model
It encloses.
Description of the drawings
Fig. 1 is hyperbranched compound infrared spectrum.
Fig. 2A is the electron microscope for the polyimide fiber for being not added with hyperbranched compound.
Fig. 2 B are the electron microscope of polyimide fiber that embodiment 1 obtains.
Fig. 2 C are the electron microscope of polyimide fiber that embodiment 2 obtains.
Fig. 2 D are the electron microscope of polyimide fiber that embodiment 3 obtains.
Specific embodiment
With reference to specific drawings and examples, the invention will be further described.
Embodiment 1：A kind of hyperbranched compound modification can contaminate the preparation method of polyimide fiber, include the following steps：
(1) 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) and triaminobenzene are pressed into acid anhydrides and amino molar ratio 1:2 is mixed
It closes, polymerisation is carried out in polymeric kettle, reaction temperature is 60 DEG C, and reaction vacuum degree is less than 0.1 atmospheric pressure to ensure to react
The water of generation is extracted, and is carried out conducive to reaction forward, and the reaction time is 9 hours, and hyperbranched compound is prepared；
(2) the filtered purification of hyperbranched compound for obtaining step (1), and add in polyimides polymeric solution and carry out
Polymerisation, polymerisation are protected using nitrogen, and polymerization temperature is -5 DEG C, and polymerization reaction time is 10 hours；The polyamides is sub-
Amine polymeric solution is by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of monomer (BPDA) and monomer p-phenylene diamine (PDA) with molar ratio 1:1
Composition, the mole of the hyperbranched compound account for the 2% of monomer BPDA and PDA integral molar quantity；The polyimides polymerization is molten
A concentration of the 15% of liquid, solvent use N, N dimethyl acetamide (Dmac)；
(3) spinning is carried out using the polymeric reaction product that step (2) obtains, polyimide fiber is made；
The spinning technique of the polyimide fiber is：The solution that step (2) obtains is squeezed into air, subsequently into solidification
In bath, 1.5 times are stretched in stretch bath, winding obtains polyamic acid fiber；The coagulating bath and stretch bath use mass ratio for
1:5 water-solvent mixed liquor, solvent use methanol；Then it is 1 polyamic acid fiber to be immersed in mass ratio:5 acetic anhydride and pyrrole
Chemical imidization is carried out in the mixed liquor of pyridine, temperature is 20 DEG C, and time 2h obtains polyimide fiber；Again by polyamides Asia
Amine fiber handles 10min at 450 DEG C, while the stretching of small multiple is carried out to polyimide fiber, and draw ratio is 1.5 times, is obtained
To the polyimide fiber.
(4) dyeing and evaluation of polyimide fiber, the polyimide fiber that step (3) is prepared can pass through dyeing
Dyeability of testing and assessing (using disperse dyes, dyes pressure 4Kg, 130 DEG C of dyeing temperature, 5 DEG C/min of heating rate, initial temperature
20 DEG C, it is warming up to 130 DEG C of holding 30min).
Embodiment 2：A kind of hyperbranched compound modification can contaminate the preparation method of polyimide fiber, include the following steps：
(1) 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) and triethanolamine are pressed into acid anhydrides and amino molar ratio 2:1 is mixed
It closes, polymerisation is carried out in polymeric kettle, reaction temperature is 180 DEG C, and reaction vacuum degree is less than 0.1 atmospheric pressure to ensure to react
The water of generation is extracted, and is carried out conducive to reaction forward, and the reaction time is 3 hours, and hyperbranched compound is prepared；
(2) the filtered purification of hyperbranched compound for obtaining step (1), and add in polyimides polymeric solution and carry out
Polymerisation, polymerisation are protected using nitrogen, and polymerization temperature is 5 DEG C, and polymerization reaction time is 2 hours；The polyimides
Polymeric solution is by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of monomer (BPDA) and monomer p-phenylene diamine (PDA) with molar ratio 1:1 group
Into the mole of the hyperbranched compound accounts for the 4% of monomer BPDA and PDA integral molar quantity；The polyimides polymeric solution
A concentration of 30%, solvent use dimethylformamide (DMF)；
(3) spinning is carried out using the polymeric reaction product that step (2) obtains, polyimide fiber is made；
The spinning technique of the polyimide fiber is：The solution that step (2) obtains is squeezed into air, subsequently into solidification
In bath, 3 times are stretched in stretch bath, winding obtains polyamic acid fiber；The coagulating bath and stretch bath use mass ratio as 5:
1 water-solvent mixed liquor, solvent use Dmac；Then it is 5 polyamic acid fiber to be immersed in mass ratio:1 acetic anhydride and pyridine
Mixed liquor in carry out chemical imidization, temperature is 70 DEG C, and time 0.5h obtains polyimide fiber；Again by polyamides Asia
Amine fiber handles 2min at 600 DEG C, while the stretching of small multiple is carried out to polyimide fiber, and draw ratio is 3 times, obtains institute
The polyimide fiber stated.
(4) dyeing and evaluation of polyimide fiber, the polyimide fiber that step (3) is prepared can pass through dyeing
Dyeability of testing and assessing (using disperse dyes, dyes pressure 4Kg, 130 DEG C of dyeing temperature, 5 DEG C/min of heating rate, initial temperature
20 DEG C, it is warming up to 130 DEG C of holding 30min).
Embodiment 3：A kind of hyperbranched compound modification can contaminate the preparation method of polyimide fiber, include the following steps：
(1) 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) and diethanol amine are pressed into acid anhydrides and amino molar ratio 1:1 is mixed
It closes, polymerisation is carried out in polymeric kettle, reaction temperature is 100 DEG C, and reaction vacuum degree is less than 0.1 atmospheric pressure to ensure to react
The water of generation is extracted, and is carried out conducive to reaction forward, and the reaction time is 6 hours, and hyperbranched compound is prepared；
(2) the filtered purification of hyperbranched compound for obtaining step (1), and add in polyimides polymeric solution and carry out
Polymerisation, polymerisation are protected using nitrogen, and polymerization temperature is 0 DEG C, and polymerization reaction time is 5 hours；The polyimides
Polymeric solution is by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of monomer (BPDA) and monomer p-phenylene diamine (PDA) with molar ratio 1:1 group
Into the mole of the hyperbranched compound accounts for the 8% of monomer BPDA and PDA integral molar quantity；The polyimides polymeric solution
A concentration of 20%, solvent use dimethyl sulfoxide (DMSO) (DMSO)；
(3) spinning is carried out using the polymeric reaction product that step (2) obtains, polyimide fiber is made；
The spinning technique of the polyimide fiber is：The solution that step (2) obtains is squeezed into air, subsequently into solidification
In bath, 2 times are stretched in stretch bath, winding obtains polyamic acid fiber；The coagulating bath and stretch bath use mass ratio as 1:
4 water-solvent mixed liquor, solvent use DMF；Then it is 1 polyamic acid fiber to be immersed in mass ratio:4 acetic anhydride and pyridine
Mixed liquor in carry out chemical imidization, temperature is 50 DEG C, and time 1h obtains polyimide fiber；Again by polyimides
Fiber handles 5min at 500 DEG C, while the stretching of small multiple is carried out to polyimide fiber, and draw ratio is 2 times, obtains described
Polyimide fiber.
(4) dyeing and evaluation of polyimide fiber, the polyimide fiber that step (3) is prepared can pass through dyeing
Dyeability of testing and assessing (using disperse dyes, dyes pressure 4Kg, 130 DEG C of dyeing temperature, 5 DEG C/min of heating rate, initial temperature
20 DEG C, it is warming up to 130 DEG C of holding 30min).
Performance test：
(1) examination of infrared spectrum super branched molecule structure structure：
The chemical constitution of hyperbranched compound prepared by 1~embodiment of embodiment 3 is as shown in Figure 1, wherein a is implementation
1 aromatic diacid acid anhydride of example and the hyperbranched compound of triaminobenzene synthesis, in infrared figure wave number 3400 or so there are one spike,
The peak of amino is should be, is influenced wave number increase (wavelength becomes smaller), therefore wave number exists by amino electron and the big conjugated system of phenyl ring
1700 and 1650 or so there is carbonyl and the absorption peak of double bond；B is 2 aromatic diacid acid anhydride of embodiment and triethanolamine synthesis over-expense
Fluidized polymer；C is 3 aromatic diacid acid anhydride of embodiment and diethanol amine synthesis of super branched polymer, b with c structures are similar, but by
Hydroxy radical content is more than c in b, therefore hydroxyl peaks of the b at wave number is 3500 is more than c.
(2) sem test fiber surface morphology changes：
Polyimide fiber passes through spinning, and significant change does not occur for the surface of fiber.As shown in Fig. 2A~Fig. 2 D, Tu2AWei
The electron microscope of the polyimide fiber of hyperbranched compound is not added with, Fig. 2 B are the electricity of polyimide fiber that embodiment 1 obtains
Mirror figure, Fig. 2 C are the electron microscope of polyimide fiber that embodiment 2 obtains, and Fig. 2 D are the polyimide fiber that embodiment 3 obtains
Electron microscope.Therefore addition hyperbranched compound does not interfere with the surface property of fiber, such as fiber surface friction, and smooth
The antistatic property that surface is conducive to fiber improves.
(3) the Washing inspection result after the dyeing fabric prepared to polyimide fiber is as shown in table 1.
Table 1
Upper table is analyzed, it is found that be added to the dyeability of polyimide fiber after hyperbranched compound
It is promoted, this is because the addition of hyperbranched compound improves reactivity of the polyimide fiber to dyestuff, and by
The accumulation mode of polyimides macromolecular structure is changed, therefore dyeability is promoted in the addition of hyperbranched system.
(3) in order to understand addition hyperbranched compound after polyimide fiber mechanical property variation, to polyimides fibre
Dimension has carried out the test of ultimate strength, intensity and elongation, and data are as shown in table 2.
Table 2
By comparing as can be seen that being added to after hyperbranched compound the strength of polyimide fiber and intensity all slightly
Decline, elongation at break increases, and mechanical property remains unchanged substantially compared with comparative sample.
Claims (6)
1. a kind of hyperbranched compound modification can contaminate the preparation method of polyimide fiber, it is characterized in that, include the following steps：
（1）By aromatic diacid acid anhydride and binary or trihydroxylic or amino-compound by acid anhydrides and hydroxyl or amino molar ratio 1:2
~2:1 mixing carries out polymerisation in polymeric kettle, and reaction temperature is 60~180 DEG C, and reaction vacuum degree is less than 0.1 air
Pressure, reaction time are 3~9 hours, and hyperbranched compound is prepared；
（2）By step（1）The obtained filtered purification of hyperbranched compound, and add in polyimides polymeric solution and polymerize
Reaction, polymerisation are protected using nitrogen, and polymerization temperature is -5~5 DEG C, and polymerization reaction time is 2~10 hours；The polyamides
Imines polymeric solution is by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of monomer（BPDA）And monomer p-phenylene diamine（PDA）With molar ratio 1:
2~2:1 composition, the mole of the hyperbranched compound account for the 1%~10% of monomer BPDA and PDA integral molar quantity；
（3）Using step（2）Obtained polymeric reaction product carries out spinning, and polyimide fiber is made.
2. hyperbranched compound modification as described in claim 1 can contaminate the preparation method of polyimide fiber, it is characterized in that：Institute
It states binary or trihydroxylic or amino-compound uses triaminobenzene, triethanolamine or diethanol amine.
3. hyperbranched compound modification as described in claim 1 can contaminate the preparation method of polyimide fiber, it is characterized in that：Institute
A concentration of the 15~30% of polyimides polymeric solution are stated, solvent uses N, N dimethyl acetamide（DMAC）, dimethylformamide
（DMF）, dimethyl sulfoxide (DMSO)（DMSO）Or n-methyl-2-pyrrolidone（NMP）.
4. hyperbranched compound modification as described in claim 1 can contaminate the preparation method of polyimide fiber, it is characterized in that：Institute
State step（3）In, the spinning of polyimide fiber uses dry spinning equipment.
5. hyperbranched compound modification as described in claim 1 can contaminate the preparation method of polyimide fiber, it is characterized in that：Institute
The spinning technique for stating polyimide fiber is：By step（2）Obtained solution squeezes into air, subsequently into coagulating bath, is drawing
It stretches and 1.5~3 times is stretched in bath, winding obtains polyamic acid fiber；Then it is 1 polyamic acid fiber to be immersed in mass ratio:5~
5:Chemical imidization is carried out in 1 acetic anhydride and the mixed liquor of pyridine, temperature is 20~70 DEG C, and the time is 0.5~2h, is obtained
Polyimide fiber；Polyimide fiber is handled into 2~10min at 450~600 DEG C, while polyimide fiber is carried out again
The stretching of small multiple, draw ratio are 1.5~3 times, obtain the polyimide fiber.
6. hyperbranched compound modification as claimed in claim 5 can contaminate the preparation method of polyimide fiber, it is characterized in that：Institute
It states coagulating bath and stretch bath uses mass ratio as 1:5~5:1 water-solvent mixed liquor, solvent using methanol, DMAC, DMF,
DMSO or NMP.
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| CN201610363527.XA CN106012081B (en) | 2016-05-27 | 2016-05-27 | Hyperbranched compound is modified the preparation method that can contaminate polyimide fiber |
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| CN201610363527.XA CN106012081B (en) | 2016-05-27 | 2016-05-27 | Hyperbranched compound is modified the preparation method that can contaminate polyimide fiber |
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| CN106012081A CN106012081A (en) | 2016-10-12 |
| CN106012081B true CN106012081B (en) | 2018-06-08 |
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