CN109575279A - A kind of aromatic polyamide class high polymer and its preparation method and application - Google Patents

A kind of aromatic polyamide class high polymer and its preparation method and application Download PDF

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Publication number
CN109575279A
CN109575279A CN201811456317.0A CN201811456317A CN109575279A CN 109575279 A CN109575279 A CN 109575279A CN 201811456317 A CN201811456317 A CN 201811456317A CN 109575279 A CN109575279 A CN 109575279A
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CN
China
Prior art keywords
aromatic polyamide
high polymer
class high
polyamide class
aromatic
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Pending
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CN201811456317.0A
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Chinese (zh)
Inventor
于俊荣
李娜
胡祖明
王彦
诸静
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Donghua University
National Dong Hwa University
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Donghua University
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Priority to CN201811456317.0A priority Critical patent/CN109575279A/en
Publication of CN109575279A publication Critical patent/CN109575279A/en
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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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides

Abstract

The present invention relates to a kind of aromatic polyamide class high polymer and its preparation method and application, be added chlorobenzoyl chloride in the aromatic polyamide class high polymer system that terminad contains amido, carry out blocking modification to get.The aromatic polyamide class high polymer of obtained chlorobenzoyl chloride sealing end has preferable solubility property in organic solvent, has preferable spinning property, fiber or resin can further be made.The method of the present invention is simple, at low cost, and manufactured fiber or resin can realize anti-oxidation discoloration jaundice at normal temperature, and have excellent dyeability, solves the problems, such as aromatic polyamide quasi polymer product oxidation stain.

Description

A kind of aromatic polyamide class high polymer and its preparation method and application
Technical field
The invention belongs to aromatic polyamide class high polymer technical field, in particular to a kind of aromatic polyamide class height is poly- Object and its preparation method and application.
Background technique
Aromatic polyamide class high polymer is because it is with excellent comprehensive performance, including heat resistance, flame-proofness, electrical isolation Property, outstanding high temperature resistant acid-base property and good textile process performance, can be good in wider temperature range and longer time These performances are kept well, to be used widely in protective garment, high-temperature filter material, electrical equipment industry and field of compound material.So And the fiber yellowing that aromatic amides quasi polymer is obtained by spinning is more serious, it is this general especially after high-temperature process Yellow phenomenon obviously aggravates, the colour brightness after having seriously affected the quality of fiber, and dyeing.The study found that aromatic series polyamides The main reason for amine high polymer product oxidation stain is caused by being present in the amido of end.In long-term storage and transportational process In, exposure easily aoxidizes in air；Either during by preliminary treatment (thermal finalization or molding), meeting accelerated oxidation Degree, so that the yellowish of product deepens and cause the loss of dyeability, dyeing uniformity, color depth.
For these problems, Recent study scholar provides different solutions, such as in patent CN102108564A In, the method for solving anti-yellowing polyamide fiber is in the inlet of screw extruder, continuously into conventional polyamide polymer The acid anhydrides for adding binary acid is comonomer, can effectively inhibit xanthochromia to a certain extent and have good dyeability Can, but the heat resistance of acid anhydrides is poor, the whiteness of obtained anti-xanthochromia fiber is poor after end blockade.In patent It is to be comonomer and the polyamide that is formed to aromatic acid in the inlet of screw extruder in CN103122492A C is continuously added in polymer2~C20Carboxylic acid, oxidation can be inhibited to turn yellow to a certain extent, but C2~C20Carboxylic acid Additive amount is more stringent by the control of polymer ends amino content, in terminal amino group content when higher, C2~C20Carboxylic acid adds After adding, it is unable to control the terminal amino group content of fibre-forming polymer and achievees the effect that inhibit xanthochromia in a certain range.Patent CN1422296A, which is then used, to be contacted by polyamide with rhodanate to improve dyeing colour saturation, dye uniformity and protection end Amido prevents degradation, oxidation stain, and still, rhodanate may resolve into non-required dangerous by-product in excessive heating Object, such as hydrogen cyanide and hydrogen sulfide, and operating method is complicated, it is clear that is unfavorable.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of aromatic polyamide class high polymer and preparation method thereof and Using overcoming the defect of existing aromatic polyamide quasi polymer product easy oxidation discoloration.
A kind of aromatic polyamide class high polymer of the invention, chemical structural formula are as follows:
Wherein Ar1、Ar2For aromatic rings or aromatic heterocycle, 120<n<230。
The aromatic polyamide class high polymer is aromatic polyamide or heterocyclic polyamide.
The aromatic polyamide is poly or polysulfonamides.
The heterocyclic polyamide is polyamide, piperazine aromatic polyamide or the poly- quinoline of the heterocycle structure containing triazineQuinoline two Keto-amide.
The present invention also provides the preparation methods of above-mentioned aromatic polyamide class high polymer, comprising:
Chlorobenzoyl chloride is added in the aromatic polyamide class high polymer system that terminad contains amido, carries out blocking modification system ?；Wherein, the terminal amido molar content of aromatic polyamide class high polymer is 4.348*10-3~8.196*10-3mol/L；Benzene The additive amount of formyl chloride is the 130~200% of aromatic polyamide class high polymer terminal amido molar content.
The present invention further provides using above-mentioned aromatic polyamide class high polymer as raw material, through spinning, washing, drying, heat Aromatic polyamide class high polymer fibre obtained after stretching.
The present invention further provides using above-mentioned aromatic polyamide class high polymer as raw material, it is precipitated, repeatedly through deionized water Washing, dry aromatic polyamide class polymeric resin obtained.
The present invention also provides above-mentioned aromatic polyamide class high polymers in protective garment, high-temperature filter material, electrical equipment industry and to answer Application in condensation material field.
The invention aims to overcome defect in the prior art, tied due to polymerizeing in aromatic polyamide class high polymer Shu Hou, there are still amidos for the terminal groups of macromolecular chain, and amidine functional group exposure easily aoxidizes in air, by high temperature After reason, the degree of meeting accelerated oxidation, so that the yellowish of aromatic polyamide class high polymer product deepens, in polymerization system Monofunctional chlorobenzoyl chloride monomer is added to block polymerization system, avoid terminal groups be amido when, polymer product The problem of exposing oxidation stain in air.And after chlorobenzoyl chloride sealing end is added, the molecular weight of polymer still can be steady It is scheduled on a higher level, fiber made from spinning is able to maintain original excellent high temperature resistance and mechanical property, and makes The dyeing effect of product improves.
Beneficial effect
(1) the aromatic polyamide class high polymer of chlorobenzoyl chloride of the invention sealing end anti-oxidation can change colour, polymer solution Fibre color after dyeing improved, and can be for a long time in air using not oxidized, in high-temperature process Afterwards, the degree of oxidation can be alleviated, fibre whiteness value is up to 87% or more.
(2) improved method that the present invention prepares the aromatic polyamide class high polymer of chlorobenzoyl chloride sealing end, step is simple, effect Rate is high, at low cost.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
By 10.655*10-3It is 8.196*10 that mol/L chlorobenzoyl chloride, which is added dropwise to terminal amido content,-3The poly- isophthalic of mol/L In two formyl m-phenylene diamine (MPD) polymeric solutions, stirring carries out end capping reaction in polymeric kettle, obtains the poly- isophthalic of chlorobenzoyl chloride sealing end Two formyl m-phenylene diamine (MPD)s.
The poly of the sealing end of chlorobenzoyl chloride made from the present embodiment is through spinning, washing, drying, hot-drawn It stretches, the Fanglun 1313 of anti-oxidation discoloration is made.
The poly of the sealing end of chlorobenzoyl chloride made from the present embodiment is precipitated through deionized water, is repeatedly anti- After backwashing is washed, is dried, and the poly resin of anti-oxidation discoloration is made.
Embodiment 2
By 9.150*10-3It is 6.535*10 that mol/L chlorobenzoyl chloride, which is added dropwise to terminal amido content,-3The poly- isophthalic two of mol/L In formyl m-phenylene diamine (MPD) polymeric solution, stirring carries out end capping reaction in polymeric kettle, the poly- isophthalic of obtained chlorobenzoyl chloride sealing end Two formyl m-phenylene diamine (MPD)s.
The poly of the sealing end of chlorobenzoyl chloride made from the present embodiment is through spinning, washing, drying, hot-drawn It stretches, the Fanglun 1313 of anti-oxidation discoloration is made.
The poly of the sealing end of chlorobenzoyl chloride made from the present embodiment is precipitated through deionized water, is repeatedly anti- After backwashing is washed, is dried, and the poly resin of anti-oxidation discoloration is made.
Embodiment 3
By 7.927*10-3It is 6.098*10 that mol/L chlorobenzoyl chloride, which is added dropwise to terminal amido content,-3The poly- isophthalic two of mol/L In formyl m-phenylene diamine (MPD) polymeric solution, stirring carries out end capping reaction in polymeric kettle, the poly- isophthalic of obtained chlorobenzoyl chloride sealing end Two formyl m-phenylene diamine (MPD)s.
The poly of the sealing end of chlorobenzoyl chloride made from the present embodiment is through spinning, washing, drying, hot-drawn It stretches, the Fanglun 1313 of anti-oxidation discoloration is made.
The poly of the sealing end of chlorobenzoyl chloride made from the present embodiment is precipitated through deionized water, is repeatedly anti- After backwashing is washed, is dried, and the poly resin of anti-oxidation discoloration is made.
Embodiment 4
By 5.652*10-3It is 4.348*10 that mol/L chlorobenzoyl chloride, which is added dropwise to terminal amido content,-3The polyarylsulfone (PAS) acyl of mol/L In amine polymeric solution, stirring carries out end capping reaction in polymeric kettle, the aromatic polysulfonamide of obtained chlorobenzoyl chloride sealing end.
The aromatic polysulfonamide of the sealing end of chlorobenzoyl chloride made from the present embodiment is made anti-through spinning, washing, drying, hot-stretch The aromatic polysulfonamide fiber of oxidation stain.
The aromatic polysulfonamide of the sealing end of chlorobenzoyl chloride made from the present embodiment is precipitated through deionized water, repeatedly washs repeatedly, is dry It is dry, the aromatic polysulfonamide resin of anti-oxidation discoloration is made.
Embodiment 5
By 1.119*10-2It is 6.999*10 that mol/L chlorobenzoyl chloride, which is added dropwise to terminal amido content,-3The piperazine aromatic ring of mol/L In nylon polymerization solution, stirring carries out end capping reaction in polymeric kettle, the piperazine aromatic ring nylon of obtained chlorobenzoyl chloride sealing end.
The piperazine aromatic ring nylon of the sealing end of chlorobenzoyl chloride made from the present embodiment is made through spinning, washing, drying, hot-stretch The piperazine aromatic ring nylon fiber of anti-oxidation discoloration.
Chlorobenzoyl chloride made from the present embodiment sealing end piperazine aromatic ring nylon through deionized water be precipitated, repeatedly repeatedly washing, It is dry, the piperazine aromatic ring nylon resin of anti-oxidation discoloration is made.
Comparative example 1
Terminal amido content is 6.098*10-3After the poly polymeric solution polymerization of mol/L, Obtained poly.
Using Fanglun 1313 obtained after spinning, washing, drying, hot-stretch.
It is precipitated using deionized water, repeatedly washed repeatedly, dry obtained poly resin.
Comparative example 2
Terminal amido content is 4.348*10-3After the aromatic polysulfonamide polymeric solution polymerization of mol/L, obtained poly- virtue Sulfonamide.
Using aromatic polysulfonamide fiber obtained after spinning, washing, drying, hot-stretch.
It is precipitated using deionized water, repeatedly washed repeatedly, dry obtained aromatic polysulfonamide resin.
Comparative example 3
Terminal amido content is 6.999*10-3After the piperazine aromatic ring nylon polymerization polymerisation in solution of mol/L, piperazine is obtained Aromatic ring nylon.
Using piperazine aromatic ring nylon fiber obtained after spinning, washing, drying, hot-stretch.
It is precipitated using deionized water, repeatedly washed repeatedly, dry obtained piperazine aromatic ring nylon resin.
The fiber that comparative example 1-3 and embodiment 1-5 are measured according to national standard GB/T1764-2008, is obtained by calculation test The whiteness of fiber, effect are shown in Table 1.
The whiteness test result of 1 fiber of table
In conjunction with the whiteness test value of 1 each sample of table, it is known that the aromatic polyamide class high polymer by chlorobenzoyl chloride sealing end is fine Dimension is more not plus the aromatic polyamide class high polymer fibre of chlorobenzoyl chloride sealing end, the whiteness value of fiber are above 87%, fiber Whiteness value significantly improves.
After dyeing using two kinds of different dyes of positive ion to the fiber of comparative example 1-3 and embodiment 1-5, fiber is carried out Color test.Through detecting the color of fiber, effect is shown in Table 2.
The color test result of 2 fiber of table
In conjunction with the fiber colour degree test value of 2 each sample of table, it is known that the aromatic polyamide class by chlorobenzoyl chloride sealing end is high Polymer fibre is more not plus the aromatic polyamide class high polymer fibre of chlorobenzoyl chloride sealing end, the color angle value of fiber obtain greatly Amplitude is promoted, and the glossiness of fiber is improved.

Claims (8)

1. a kind of aromatic polyamide class high polymer, chemical structural formula are as follows:
Wherein Ar1、Ar2For aromatic rings or aromatic heterocycle, 120 < n < 230。
2. aromatic polyamide class high polymer according to claim 1, it is characterised in that: the aromatic polyamide class is high Polymers is aromatic polyamide or heterocyclic polyamide.
3. aromatic polyamide class high polymer according to claim 2, it is characterised in that: the aromatic polyamide is poly- Mpd-i or polysulfonamides.
4. aromatic polyamide class high polymer according to claim 2, it is characterised in that: the heterocyclic polyamide is selected from Polyamide, piperazine aromatic polyamide or the poly- quinoline of the heterocycle structure containing triazineTwo keto-amide of quinoline.
5. a kind of preparation method of aromatic polyamide class high polymer as described in claim 1, comprising: terminad contains amido Chlorobenzoyl chloride is added in aromatic polyamide class high polymer system, is carried out blocking modification and is made；Wherein, aromatic polyamide class is high The terminal amido molar content of polymers is 4.348*10-3~8.196*10-3mol/L；The additive amount of chlorobenzoyl chloride is fragrant adoption The 130~200% of amides high polymer terminal amido molar content.
6. one kind is using aromatic polyamide class high polymer described in claim 1 as raw material, through spinning, washing, drying, hot-stretch Aromatic polyamide class high polymer fibre obtained afterwards.
7. one kind is using aromatic polyamide class high polymer described in claim 1 as raw material, through deionized water precipitation, repeatedly water It washes, dry aromatic polyamide class polymeric resin obtained.
8. aromatic polyamide class high polymer described in claim 1 is in protective garment, high-temperature filter material, electrical equipment industry and composite material Application in field.
CN201811456317.0A 2018-11-30 2018-11-30 A kind of aromatic polyamide class high polymer and its preparation method and application Pending CN109575279A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03292327A (en) * 1990-04-11 1991-12-24 Mitsui Toatsu Chem Inc Aromatic polyamide
JP2002179910A (en) * 2000-12-11 2002-06-26 Mitsui Chemicals Inc Polyamide resin composition and molded product thereof
JP2007154356A (en) * 2005-12-05 2007-06-21 Teijin Techno Products Ltd Method for producing meta-aromatic polyamide polymer suitable for wet spinning
CN101476173A (en) * 2009-01-20 2009-07-08 赵海鹏 Direct spinning process for preparing PPTA fibre by end capping resin method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03292327A (en) * 1990-04-11 1991-12-24 Mitsui Toatsu Chem Inc Aromatic polyamide
JP2002179910A (en) * 2000-12-11 2002-06-26 Mitsui Chemicals Inc Polyamide resin composition and molded product thereof
JP2007154356A (en) * 2005-12-05 2007-06-21 Teijin Techno Products Ltd Method for producing meta-aromatic polyamide polymer suitable for wet spinning
CN101476173A (en) * 2009-01-20 2009-07-08 赵海鹏 Direct spinning process for preparing PPTA fibre by end capping resin method

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Application publication date: 20190405