CN106498535A - Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent and preparation method thereof and product - Google Patents

Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent and preparation method thereof and product Download PDF

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Publication number
CN106498535A
CN106498535A CN201611014772.6A CN201611014772A CN106498535A CN 106498535 A CN106498535 A CN 106498535A CN 201611014772 A CN201611014772 A CN 201611014772A CN 106498535 A CN106498535 A CN 106498535A
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mpd
fiber
phenylene diamine
modified poly
paraphenylene terephthalamide
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Inventor
赵炯心
汪晓峰
王林
陈晟晖
胡祖明
谢灵娇
张幼维
李文刚
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Shanghai Tanlon Fiber Co Ltd
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Shanghai Tanlon Fiber Co Ltd
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Priority to CN201611014772.6A priority Critical patent/CN106498535A/en
Publication of CN106498535A publication Critical patent/CN106498535A/en
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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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • 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
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36—Cored or coated yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides

Abstract

The present invention relates to modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of a kind of hydrogen bond inert diluent and preparation method thereof and product, first by m-phenylene diamine (MPD), hydrogen bond inert diluent and paraphthaloyl chloride carry out copolycondensation in organic non-protonic polar solvent and obtain spinning solution, then spinning solution is carried out spinning and obtains the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, obtained fiber is used separately as core yarn fiber and cladding yarn fiber composition heat-proof combustion-resistant yarn finally, or obtained fiber is used separately as fiber web layer and skeleton reinforcing fiber, combined by needle point method and adhesive-bonded fabric is obtained.The inventive method is easy, obtained fibrous mechanical property and hot property are excellent, obtained flame-retardant yarn excellent flame retardancy, obtained adhesive-bonded fabric durability and good impact resistance, can be applicable to make the particular products such as the grade textiles of heat-proof combustion-resistant protective garment and indoor decoration.

Description

The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent and its preparation side Method and product
Technical field
The invention belongs to modified fibre field, is related to a kind of modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent Fiber and preparation method thereof and product.
Background technology
In oil, chemical industry, the industries such as gold, fire-fighting are controlled, often in occasions such as high temperature naked lights, this is just to work for production operation environment Making personnel's labour protection fire retardant protective clothing for dressing in operation has particular/special requirement.Additionally, building interior decoration and public place make The raising of the technical textile anti-flammability such as textile, important to ensureing that people's security of the lives and property and fire prevention and control have Meaning.Flame retardant textiles have formed wide and stable market, develop fire resistance higher and more Comfortable attractive fire-retardant Protective garment and fabrics for industrial use also become the needs of the development of economic society.
In existing organic high temperature-resistant fire resistance fibre kind, aromatic polysulfonamide fiber, poly aromatic nylon all have resistance The function of combustion protection, and obtain preferably research application progress.Meta-aramid condensate poly is polymerized Thing vitrification point is 270 DEG C, the polymer fiber can under the conditions of 200 DEG C Long-Time Service, fibrous mechanical property is excellent, is to work as The best high-temperature fibre kind of front development.Aromatic polysulfonamide fiber has than poly polymer fiber More excellent heat resistance, can at 250 DEG C Long-Time Service, still keep preferable dimensional stability and durability at high temperature. But more or less there is various, such as poly polymer fiber use in above-mentioned kind There is temperature certain limitation, aromatic polysulfonamide fiber then to enbrittle, while its spinning processing poor-performing also limit Its application extension.
However, poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) polymer kind of poly aromatic acid amides fails the weight for obtaining people always Depending on.The U.S. of United States Patent (USP) US3006899, S.L.Kwolek and the P.W.Morgan of H.W.Hill et al. et al. is authorized in one's early years The interface including a series of fully aromatic polyamides including poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) is disclosed in patent US3063966 Polymerization, poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of preparation authorize Takashi compared with conventional organic aprotic solvents are insoluble in Et al. Japan Patent JP51053598 in, disclose with the hydrotropy salt DMAc containing 6%LiCl as solvent, continuous in agitator Prepare poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) that inherent viscosity is stable, molecular weight is homogeneous.But the polymer solution of LiCl salt has Highly corrosive, it is difficult to meet preparation of industrialization high strength fibre requirement.Authorize Korean Patent KR2013078585A of Lee et al. In, disclose with the CaCl of salt containing hydrotropy2NMP be the spinning new method of solvent, be prepared into the poly- to benzene of high heat-resisting and high intensity Two formyl m-phenylene diamine (MPD) fibers.In fact, as NMP is easy to water suction, therefore eliminating water before polymerization works and polymer spun Difficult solvent recovery in silk liquid.
Content of the invention
The purpose of the present invention is the shortcoming for overcoming prior art, prepares one kind and dissolves in organic aprotic solvents, molecule Chain has certain rigidity and the modified poly- paraphenylene terephthalamide's isophthalic two of the hydrogen bond inert diluent with excellent heat-resistant stability Amine fiber.
For reaching above-mentioned purpose, the technical solution used in the present invention is：
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, step are as follows：
(1) m-phenylene diamine (MPD), hydrogen bond inert diluent and paraphthaloyl chloride are entered in organic non-protonic polar solvent Row copolycondensation, obtains the spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent；
(2) by the spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent through solution-polymerized SBR system Obtain the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent.
As preferred technical scheme：
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, has as above Body step is as follows：
(1) m-phenylene diamine (MPD) and hydrogen bond inert diluent are dissolved in organic non-protonic polar solvent, are obtained and contain two The solution of first amine monomers；
(2) adding paraphthaloyl chloride in the solution containing diamine monomer carries out copolycondensation；
(3) add calcium oxide to terminate the copolycondensation, obtain through the modified poly- terephthaldehyde of hydrogen bond inert diluent The spinning solution of acyl m-phenylene diamine (MPD)；
(4) spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent is extruded through spinning head Enter in coagulating bath afterwards, obtain nascent strand；
(5) to obtain hydrogen bond inert diluent through plasticization drawing, washing and hot-stretch modified poly- to benzene two for the nascent strand Formyl m-phenylene diamine (MPD) fiber.
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, walks as above Suddenly in (1), the hydrogen bond inert diluent be DDS or 3,3 '-DADPS, the m-phenylene diamine (MPD) Mol ratio with hydrogen bond inert diluent is 1～4:1, when hydrogen bond inert diluents in modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) molecule When the ratio of agent exceedes diamine monomer total amount 50% in polymer, the fiber of preparation is not good in fragility mechanical property, works as hydrogen bond When the ratio of inert diluent is less than diamine monomer total amount 20% in polymer, polymer-modified in organic non-protonic polar In solvent, dissolubility is poor, and organic non-protonic polar solvent is DMAc, DMF or DMSO, described contains diamine monomer Solution in m-phenylene diamine (MPD) concentration be 12.5～17.5wt%；
In step (2), the paraphthaloyl chloride with the mol ratio of m-phenylene diamine (MPD) and hydrogen bond inert diluents agent composition is 1:1, the temperature of the copolycondensation is 0～20 DEG C, and the time is 15min；
In step (3), the calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, described through hydrogen bond inert diluent The solid content of the spinning solution of modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) is 10%～17.5%；
In step (4), the coagulating bath is the mixed solution of organic non-protonic polar solvent and water, organic non-matter Subtype polar solvent is 40%～60% with the volumetric concentration of the mixed solution of the aqueous solution；
In step (5), the multiple of the plasticization drawing is 1.5～3, and temperature is 25～45 DEG C, the multiple of the hot-stretch For 1～2.5, temperature is 285～370 DEG C.
Present invention also offers a kind of modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the hydrogen bond The hook strength of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of inert diluent is 2.0～3.5cN/dtex, and fracture strength is 3.0～5.0cN/dtex；
The vitrification point of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of the hydrogen bond inert diluent is 270～350 ℃；Limited oxygen index >=29 of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of the hydrogen bond inert diluent.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of as above hydrogen bond inert diluent, the hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of agent is that the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS is fine The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of dimension, 4,4 '-DADPS or 3,3 '-DADPS are modified poly- to benzene The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of two formyl m-phenylene diamine (MPD)/4,4 '-DADPS.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of as above hydrogen bond inert diluent, described 3,3 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of diphenyl sulphone (DPS) is combined Fiber is modified by the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) spinning solution of 3,3 '-DADPS and 4,4 '-DADPS Spinning after poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) spinning solution mixing is obtained, and 3 in mixed spinning solution, 3 '-DADPS changes The mass ratio of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) and 4,4 '-DADPS of property For 1:99～99:1.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent obtained in of the invention have solubility property and The advantage of fine heat-resisting performance is as follows the reason for solubility property is improved：
On the one hand, poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) before modified be by m-phenylene diamine (MPD), paraphthaloyl chloride copolycondensation and Into its molecular structure symmetry is good, the donor (- NH-) of hydrogen bond and acceptor (=O) quantity equal proportion in molecule, is formed stronger Hydrogen bond action, therefore poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) is more difficult is dissolved in organic aprotic solvents such as DMAc, DMF, DMSO etc., The present invention is by introducing 4,4 '-DADPS of Third monomer or 3,3 '-diaminourea two as hydrogen bond inert diluent Benzene sulfone, changes in the molecular structure of poly- paraphenylene terephthalamide's m-phenylene diamine (MPD), the donor (- NH-) of hydrogen bond and acceptor (=O) ratio, By original mol ratio 1:1 is adjusted to 1:1.2～2, weaken HYDROGEN BOND INTENSITY in molecule and cause poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) Dissolubility improved；
On the other hand, the DDS as hydrogen bond inert diluent or 3,3 '-DADPS draw Enter the regularity for suitably destroying poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) main chain, reduce the position of rotation in singly-bound in molecular structure Build, become easier to molecule singly-bound inward turning, improve poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) molecular flexibility, further improve molten Solution performance.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber fine heat-resisting performance of hydrogen bond inert diluent obtained in of the invention Reason is due to strong electron withdraw group sulfuryl (- SO in hydrogen bond inert diluent2-) common with the double bond of sulfuryl formation by phenyl ring Yoke system, significantly reduces the cloud density of nitrogen-atoms on amido link, i.e., steady with the resonance of acid amides bond formed by electron delocalization It is set for using, improves the heat resistance of modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fibrous mechanical property of hydrogen bond inert diluent obtained in of the invention is preferable Reason be due in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber diamines molecular backbone of hydrogen bond inert diluent containing contraposition or The benzene ring building blocks of meta connection, strand has larger rigidity, which is simultaneous also have while consolidated heat resistance very excellent Good mechanical property.
Present invention also offers one kind is obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent Heat-proof combustion-resistant yarn, the flame-retardant yarn are a kind of higher than poly polymer heat-resistant flame retardant rating gathering Compound yarn, while being more easy to spinning processing than aromatic polysulfonamide fiber, the heat-proof combustion-resistant yarn by core yarn fiber and is coated on The cladding yarn fiber composition on core yarn fiber surface；
The core yarn fiber is the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS, described Cladding yarn fiber is that the hydrogen bond inert diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the mixed of fiber Condensating fiber；
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of the hydrogen bond inert diluent changes for 3,3 '-DADPS Property poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber, the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 4,4 '-DADPS Or the modified poly- paraphenylene terephthalamide of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of 3,3 '-DADPS M-phenylene diamine (MPD) composite short fiber；
Modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of the 3,3 '-DADPS is modified poly- Paraphenylene terephthalamide's m-phenylene diamine (MPD) composite short fiber is by the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 3,3 '-DADPS It is mixed to get with the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of DDS, or is 3,3 '-diaminourea two The compound fibre of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of benzene sulfone The chopped fiber of dimension.
Heat-proof combustion-resistant yarn as above, in the heat-proof combustion-resistant yarn, the content of each component is：
Core yarn fiber：5～40wt%；
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of hydrogen bond inert diluent：58～93wt%；
Antistatic charcoal leads fiber：2wt%；
Using GB/T5455-1997《Textile combustion performance test normal beam technique》Measure the afterflame of the heat-proof combustion-resistant yarn Time≤2 second, smoldering time≤8 second.
The present invention also provides a kind of nothing obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent Yarn fabric, the adhesive-bonded fabric are made up of fiber web layer and skeleton reinforcing fiber, and the fiber web layer is led to skeleton reinforcing fiber Cross needle point method and be combined into a complete adhesive-bonded fabric entirety；
Fiber in the fiber web layer is the short fibre of the poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS modification The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of dimension, 4,4 '-DADPS or 3,3 '-DADPS are modified poly- right The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite short fiber of phenyl-diformyl m-phenylene diamine (MPD)/4,4 '-DADPS；3,3 '-two The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber bending excellent strength of ADP sulfone, can give composite heat resistance filter material enough Toughness, up to 345 DEG C of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament softening temperature of DDS, is better than The PPS fibers and PMIA fibers of adhesive-bonded fabric chopped fiber is commonly used for, i.e., while heat-resisting, overcomes PSA fiber (aromatic polysulfonamide again Fiber) etc. fiber weakness shortcoming；
Modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of the 3,3 '-DADPS is modified poly- Paraphenylene terephthalamide's m-phenylene diamine (MPD) composite short fiber is by the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 3,3 '-DADPS It is mixed to get with the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of DDS, or is 3,3 '-diaminourea two The compound fibre of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of benzene sulfone The chopped fiber of dimension；
The skeleton reinforcing fiber is the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS, The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS as adhesive-bonded fabric supporting material, its glass Change up to 345 DEG C of temperature and there is very high Young's modulus, with excellent dimensional stability.
Adhesive-bonded fabric as above, in the adhesive-bonded fabric, the content of fiber web layer is 70～95wt%, skeleton reinforcement The content of fiber is 5～30wt%；The adhesive-bonded fabric is less than 3% in 200 DEG C of shrinkage factor, and the tension of weight per unit area is strong Degree is more than 0.2 (N/cm)/(g/m2).
Beneficial effect
1) present invention, is prepared for a kind of heat resistance fiber with excellent mechanical property, and its fracture strength exists More than 3.0cN/dtex, hook strength in more than 2.0cN/dtex, its vitrification point more than 270 DEG C, limited oxygen index 29 More than；
2) modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) obtained in the present invention is soluble in conventional organic aprotic solvents, gram The difficult problem of traditional poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) dissolving has been taken, application has been widened；
3) obtained in the present invention, heat-proof combustion-resistant yarn thermal stability is higher, and easy spinning processing can prepare oil, chemical industry The heat-proof combustion-resistant protective garment that the industries such as iron and steel, cement, electric power and fire-fighting are used, it is also possible to make the rooms such as public place curtain, tablecloth The grade textiles of interior trim, application are extensive；
4) adhesive-bonded fabric obtained in the present invention has excellent heat resistance, chemical proofing while having good thermal environment Lower use mechanical strength, under the conditions of 200 DEG C, shrinkage factor is less than 3%, the tensile strength of weight per unit area more than 0.2 (N/cm)/ (g/m2), can be used as durable filtering material under thermal shock environments.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this Bright rather than restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, art technology Personnel can be made various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
Embodiment 1
A kind of 3, the preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3 '-DADPS, step are as follows：
(1) by mol ratio be 1:1 m-phenylene diamine (MPD) and 3,3 '-DADPS are dissolved in DMAc, and prepared concentration is The solution containing diamine monomer of 12.5wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 3,3 '-DADPS mixture:1, the temperature of copolycondensation is 0 DEG C, Time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 12% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMAc that volumetric concentration is 40%；
(5) strand of coming into being obtains 3,3 '-diaminourea two again through 1.5 times of 25 DEG C of plasticization drawings, washing and 285 DEG C of hot-stretch 1 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of benzene sulfone.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3,3 '-DADPS obtained in final is 3,3 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after obtain 3,3 '-DADPS is modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, 3, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of 3 '-DADPS Function admirable is learned, hook strength is 3.5cN/dtex, fracture strength is 5cN/dtex, hot property is excellent, and vitrification point is 270 DEG C, limited oxygen index is 29.
Embodiment 2
A kind of 3, the preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3 '-DADPS, step are as follows：
(1) by mol ratio be 1.5:1 m-phenylene diamine (MPD) and 3,3 '-DADPS are dissolved in DMF, and prepared concentration is The solution containing diamine monomer of 13.2wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 3,3 '-DADPS mixture:1, the temperature of copolycondensation is 2 DEG C, Time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 13.2% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMF that volumetric concentration is 45%；
(5) strand of coming into being obtains 3,3 '-diaminourea again through 1.6 times of 28 DEG C of plasticization drawings, washing and 290 DEG C of hot-stretch 1.2 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of diphenyl sulphone (DPS).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3,3 '-DADPS obtained in final is 3,3 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after obtain 3,3 '-DADPS is modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, 3, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of 3 '-DADPS Function admirable is learned, hook strength is 3.2cN/dtex, fracture strength is 4.6cN/dtex, hot property is excellent, and vitrification point is 276 DEG C, limited oxygen index is 29.5.
Embodiment 3
A kind of 3, the preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3 '-DADPS, step are as follows：
(1) by mol ratio be 2.2:1 m-phenylene diamine (MPD) and 3,3 '-DADPS are dissolved in DMSO, and concentration is obtained The solution containing diamine monomer for 13.6wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 3,3 '-DADPS mixture:1, the temperature of copolycondensation is 4 DEG C, Time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 14.5% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMSO that volumetric concentration is 50%；
(5) strand of coming into being obtains 3,3 '-diaminourea again through 1.8 times of 30 DEG C of plasticization drawings, washing and 295 DEG C of hot-stretch 1.5 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of diphenyl sulphone (DPS).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3,3 '-DADPS obtained in final is 3,3 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after obtain 3,3 '-DADPS is modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, 3, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of 3 '-DADPS Function admirable is learned, hook strength is 2.8cN/dtex, fracture strength is 4.0cN/dtex, hot property is excellent, and vitrification point is 283 DEG C, limited oxygen index is 30.1.
Embodiment 4
A kind of 3, the preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3 '-DADPS, step are as follows：
(1) by mol ratio be 3.2:1 m-phenylene diamine (MPD) and 3,3 '-DADPS are dissolved in DMAc, and concentration is obtained The solution containing diamine monomer for 14.1wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 3,3 '-DADPS mixture:1, the temperature of copolycondensation is 6 DEG C, Time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 15.3% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMAc that volumetric concentration is 52%；
(5) strand of coming into being obtains 3,3 '-diaminourea again through 1.9 times of 32 DEG C of plasticization drawings, washing and 305 DEG C of hot-stretch 1.8 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of diphenyl sulphone (DPS).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 3,3 '-DADPS obtained in final is 3,3 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after obtain 3,3 '-DADPS is modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, 3, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of 3 '-DADPS Function admirable is learned, hook strength is 2.5cN/dtex, fracture strength is 3.6cN/dtex, hot property is excellent, and vitrification point is 289 DEG C, limited oxygen index is 30.8.
Embodiment 5
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of DDS, step are as follows：
(1) by mol ratio be 1:1 m-phenylene diamine (MPD) and DDS are dissolved in DMF, and prepared concentration is The solution containing diamine monomer of 14.5wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 4,4 '-DADPS mixture:1, the temperature of copolycondensation is 8 DEG C, Time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 10% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMF that volumetric concentration is 56%；
(5) strand of coming into being obtains 4,4 '-diaminourea hexichol again through 2 times of 35 DEG C of plasticization drawings, washing and 315 DEG C of hot-stretch 2 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of sulfone.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 4,4 '-DADPS obtained in final is 4,4 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after to obtain DDS modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of DDS Function admirable is learned, hook strength is 3.1cN/dtex, fracture strength is 4.8cN/dtex, hot property is excellent, and vitrification point is 295 DEG C, limited oxygen index is 31.5.
Embodiment 6
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of DDS, step are as follows：
(1) by mol ratio be 1.5:1 m-phenylene diamine (MPD) and DDS are dissolved in DMSO, and concentration is obtained The solution containing diamine monomer for 15.0wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 4,4 '-DADPS mixture:1, the temperature of copolycondensation is 10 DEG C, the time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 11.1% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMSO that volumetric concentration is 48%；
(5) strand of coming into being obtains 4,4 '-diaminourea again through 2.2 times of 38 DEG C of plasticization drawings, washing and 332 DEG C of hot-stretch 2.1 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of diphenyl sulphone (DPS).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 4,4 '-DADPS obtained in final is 4,4 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after to obtain DDS modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of DDS Function admirable is learned, hook strength is 2.8cN/dtex, fracture strength is 4.3cN/dtex, hot property is excellent, and vitrification point is 312 DEG C, limited oxygen index is 32.1.
Embodiment 7
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of DDS, step are as follows：
(1) by mol ratio be 2.1:1 m-phenylene diamine (MPD) and DDS are dissolved in DMAc, and concentration is obtained The solution containing diamine monomer for 15.4wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 4,4 '-DADPS mixture:1, the temperature of copolycondensation is 12 DEG C, the time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 12% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMAc that volumetric concentration is 55%；
(5) strand of coming into being obtains 4,4 '-diaminourea again through 2.5 times of 40 DEG C of plasticization drawings, washing and 340 DEG C of hot-stretch 2.2 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of diphenyl sulphone (DPS).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 4,4 '-DADPS obtained in final is 4,4 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after to obtain DDS modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of DDS Function admirable is learned, hook strength is 2.5cN/dtex, fracture strength is 3.8cN/dtex, hot property is excellent, and vitrification point is 320 DEG C, limited oxygen index is 32.8.
Embodiment 8
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of DDS, step are as follows：
(1) by mol ratio be 2.5:1 m-phenylene diamine (MPD) and DDS are dissolved in DMF, and prepared concentration is The solution containing diamine monomer of 15.8wt%；
(2) paraphthaloyl chloride is added and carry out in the above-mentioned solution containing diamine monomer copolycondensation, to benzene two Formyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and 4,4 '-DADPS mixture:1, the temperature of copolycondensation is 14 DEG C, the time is 15min；
(3) calcium oxide is added to terminate copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, consolidate Content is 12.8% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS；
(4) will be through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS through spinning head Enter in coagulating bath after extrusion, obtain nascent strand, the aqueous solution of the coagulating bath for DMF that volumetric concentration is 58%；
(5) strand of coming into being obtains 4,4 '-diaminourea again through 2.6 times of 42 DEG C of plasticization drawings, washing and 355 DEG C of hot-stretch 2.3 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of diphenyl sulphone (DPS).
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of 4,4 '-DADPS obtained in final is 4,4 '-diaminourea The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of diphenyl sulphone (DPS), cleaved after to obtain DDS modified poly- right Phenyl-diformyl m-phenylene diamine (MPD) chopped fiber, the power of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiberoptic fiber of DDS Function admirable is learned, hook strength is 2.2cN/dtex, fracture strength is 3.4cN/dtex, hot property is excellent, and vitrification point is 335 DEG C, limited oxygen index is 33.4.
Embodiment 9
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, step are as follows：
(1) by mol ratio be 3.8:1 m-phenylene diamine (MPD) and 3,3 '-DADPS are dissolved in DMSO, and concentration is obtained The solution containing diamine monomer for 16.5wt%；
(2) by mol ratio be 2.8:1 m-phenylene diamine (MPD) and DDS are dissolved in DMSO, and concentration is obtained The solution containing diamine monomer for 16.5wt%；
(3) carry out in the solution containing diamine monomer that paraphthaloyl chloride is separately added into step (1) and step (2) Copolycondensation, paraphthaloyl chloride and m-phenylene diamine (MPD) and 3,3 '-DADPS (or DDS) mix The mol ratio of thing is 1:1, the temperature of copolycondensation is 18 DEG C, and the time is 15min；
(4) it is separately added into calcium oxide and terminates copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, obtain To the spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS that solid content is 14.5% and admittedly Content is 14.5% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS；
(5) will through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS with through 4,4 '- The spinning solution mixing of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of DADPS, 3,3 '-two in mixed spinning solution The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of ADP sulfone and the modified poly- paraphenylene terephthalamide's isophthalic of 4,4 '-DADPS The mass ratio of diamines is 1:99, mixed spinning solution is entered in coagulating bath after spinning head extrusion, nascent strand is obtained, The aqueous solution of the coagulating bath for DMSO that volumetric concentration is 60%；
(5) strand of coming into being obtains hydrogen bond inert diluents again through 2.8 times of 44 DEG C of plasticization drawings, washing and 370 DEG C of hot-stretch 2.4 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of agent.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent obtained in final is 3,3 '-diaminourea hexichol The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD)/DDS of sulfone, The good mechanical performance of composite fibre, hook strength is 2.0cN/dtex, and fracture strength is 3.0cN/dtex, and hot property is excellent, Vitrification point is 350 DEG C, and limited oxygen index is 33.9.
Embodiment 10
A kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, step are as follows：
(1) by mol ratio be 4:1 m-phenylene diamine (MPD) and 3,3 '-DADPS are dissolved in DMAc, and prepared concentration is The solution containing diamine monomer of 17.5wt%；
(2) by mol ratio be 3:1 m-phenylene diamine (MPD) and DDS are dissolved in DMAc, and prepared concentration is The solution containing diamine monomer of 17.5wt%；
(3) carry out in the solution containing diamine monomer that paraphthaloyl chloride is separately added into step (1) and step (2) Copolycondensation, paraphthaloyl chloride and m-phenylene diamine (MPD) and 3,3 '-DADPS (or DDS) mix The mol ratio of thing is 1:1, the temperature of copolycondensation is 20 DEG C, and the time is 15min；
(4) it is separately added into calcium oxide and terminates copolycondensation, calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, obtain To the spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS that solid content is 17.5% and admittedly Content is 14.5% spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS；
(5) will through the spinning solution of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS with through 4,4 '- The spinning solution mixing of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of DADPS, 3,3 '-two in mixed spinning solution The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of ADP sulfone and the modified poly- paraphenylene terephthalamide's isophthalic of 4,4 '-DADPS The mass ratio of diamines is 99:1, mixed spinning solution is entered in coagulating bath after spinning head extrusion, nascent strand is obtained, The aqueous solution of the coagulating bath for DMAc that volumetric concentration is 60%；
(5) strand of coming into being obtains hydrogen bond inert diluent again through 3 times of 45 DEG C of plasticization drawings, washing and 310 DEG C of hot-stretch 2.5 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber.
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent obtained in final is 3,3 '-diaminourea hexichol The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD)/DDS of sulfone, The good mechanical performance of composite fibre, hook strength is 2.1cN/dtex, and fracture strength is 3.0cN/dtex, and hot property is excellent, Vitrification point is 295 DEG C, and limited oxygen index is 31.9.
Embodiment 11
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 5, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 3,3 '-DADPS obtained in embodiment 1 is modified poly- to benzene two Formyl m-phenylene diamine (MPD) chopped fiber, in heat-proof combustion-resistant yarn, the content of core yarn fiber is 5wt%, and it is right that the modification of hydrogen bond inert diluent gathers The content of phenyl-diformyl m-phenylene diamine (MPD) chopped fiber is 93wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 2 Second, smoldering time is 8 seconds.
Embodiment 12
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 5, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 3,3 '-DADPS obtained in embodiment 2 is modified poly- to benzene two Formyl m-phenylene diamine (MPD) chopped fiber, in heat-proof combustion-resistant yarn, the content of core yarn fiber is 10wt%, and hydrogen bond inert diluent is modified to be gathered The content of paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber is 88t%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.8 Second, smoldering time is 7 seconds.
Embodiment 13
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 6, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 4,4 '-DADPS obtained in embodiment 5 is modified poly- to benzene two Formyl m-phenylene diamine (MPD) chopped fiber, in heat-proof combustion-resistant yarn, the content of core yarn fiber is 15wt%, and hydrogen bond inert diluent is modified to be gathered The content of paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber is 83wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.7 Second, smoldering time is 6 seconds.
Embodiment 14
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 6, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 4,4 '-DADPS obtained in embodiment 6 is modified poly- to benzene two Formyl m-phenylene diamine (MPD) chopped fiber, in heat-proof combustion-resistant yarn, the content of core yarn fiber is 20wt%, and hydrogen bond inert diluent is modified to be gathered The content of paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber is 78wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.6 Second, smoldering time is 5 seconds.
Embodiment 15
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 7, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 3,3 '-DADPS obtained in embodiment 3 is modified poly- to benzene two Formyl m-phenylene diamine (MPD) chopped fiber is short with the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS obtained in embodiment 7 (mass ratio is 1 to the mixture of fiber:1), in heat-proof combustion-resistant yarn core yarn fiber content be 25wt%, hydrogen bond inert diluent The content of modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber is 73wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.5 Second, smoldering time is 4 seconds.
Embodiment 16
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 7, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 3,3 '-DADPS obtained in embodiment 4 is modified poly- to benzene two Formyl m-phenylene diamine (MPD) chopped fiber is short with the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 4,4 '-DADPS obtained in embodiment 8 (mass ratio is 1 to the mixture of fiber:1), in heat-proof combustion-resistant yarn core yarn fiber content be 31wt%, hydrogen bond inert diluent The content of modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber is 67wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.4 Second, smoldering time is 5 seconds.
Embodiment 17
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 8, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 3,3 '-DADPS obtained in embodiment 9 is modified poly- to benzene two The chopped fiber of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of formyl m-phenylene diamine (MPD)/DDS, resistance to thermal resistance In combustion yarn, the content of core yarn fiber is 36wt%, the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of hydrogen bond inert diluent Content is 62wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.3 Second, smoldering time is 4 seconds.
Embodiment 18
A kind of heat-proof combustion-resistant yarn obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, should Heat-proof combustion-resistant yarn is mainly made up of with the cladding yarn fiber for being coated on core yarn fiber surface core yarn fiber, and core yarn fiber is enforcement The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS obtained in example 8, cladding yarn fiber is that hydrogen bond is lazy Property the diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead the composite fibre of fiber, hydrogen bond inert diluents The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of agent is that 3,3 '-DADPS obtained in embodiment 10 is modified poly- to benzene two The chopped fiber of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of formyl m-phenylene diamine (MPD)/DDS, resistance to thermal resistance In combustion yarn, the content of core yarn fiber is 40wt%, the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of hydrogen bond inert diluent Content is 58wt%, and it is 2wt% that antistatic charcoal leads the content of fiber.
The test of vertical burn test method shows that the fire resistance of obtained heat-proof combustion-resistant yarn is good, and after flame time is 1.1 Second, smoldering time is 3 seconds.
Embodiment 19
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 30wt% of 70wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 5 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 3 '-diaminourea 23 obtained in embodiment 1 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of benzene sulfone.
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.9%, the tensile strength of weight per unit area is 0.22 (N/cm)/(g/m2).
Embodiment 20
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 25wt% of 75wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 5 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 3 '-diaminourea 23 obtained in embodiment 2 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of benzene sulfone.
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.8%, the tensile strength of weight per unit area is 0.25 (N/cm)/(g/m2).
Embodiment 21
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 22wt% of 78wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 6 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 4 '-diaminourea 24 obtained in embodiment 5 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of benzene sulfone.
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.7%, the tensile strength of weight per unit area is 0.26 (N/cm)/(g/m2).
Embodiment 22
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 15wt% of 85wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 6 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 4 '-diaminourea 24 obtained in embodiment 6 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of benzene sulfone.
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.6%, the tensile strength of weight per unit area is 0.28 (N/cm)/(g/m2).
Embodiment 23
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 12wt% of 88wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 7 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 3 '-diaminourea 23 obtained in embodiment 3 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of benzene sulfone is modified with 4,4 '-DADPS obtained in embodiment 7 poly- to benzene (mass ratio is 1 to the mixture of two formyl m-phenylene diamine (MPD) chopped fibers:1).
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.5%, the tensile strength of weight per unit area is 0.3 (N/cm)/(g/m2).
Embodiment 24
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 10wt% of 90wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 7 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 3 '-diaminourea 23 obtained in embodiment 4 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of benzene sulfone is modified with 4,4 '-DADPS obtained in embodiment 8 poly- to benzene (mass ratio is 1 to the mixture of two formyl m-phenylene diamine (MPD) chopped fibers:1).
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.5%, the tensile strength of weight per unit area is 0.32 (N/cm)/(g/m2).
Embodiment 25
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 8wt% of 92wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 8 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 3 '-diaminourea 23 obtained in embodiment 9 The compound fibre of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of benzene sulfone The chopped fiber of dimension.
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.2%, the tensile strength of weight per unit area is 0.35 (N/cm)/(g/m2).
Embodiment 26
A kind of adhesive-bonded fabric obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, the nonwoven Fabric is made up of the skeleton reinforcing fiber of the fiber web layer and 5wt% of 95wt%, and fiber web layer passes through pin with skeleton reinforcing fiber Acupuncture manipulation is combined into a complete adhesive-bonded fabric entirety, and skeleton reinforcing fiber is DDS obtained in embodiment 8 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament, the fiber in fiber web layer are 3 '-diaminourea 3 obtained in embodiment 10 The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of diphenyl sulphone (DPS) is combined The chopped fiber of fiber.
Test shows that obtained adhesive-bonded fabric dimensional stability is higher, and good mechanical performance in 200 DEG C of shrinkage factors is 2.0%, the tensile strength of weight per unit area is 0.38 (N/cm)/(g/m2).

Claims (10)

1. a kind of preparation method of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent, is characterized in that, step As follows：
(1) m-phenylene diamine (MPD), hydrogen bond inert diluent and paraphthaloyl chloride are carried out in organic non-protonic polar solvent altogether Polycondensation reaction, obtains the spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent；
(2) spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent is obtained hydrogen through solution-polymerized SBR The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of key inert diluent.
2. the preparation of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of a kind of hydrogen bond inert diluent according to claim 1 Method, it is characterised in that comprise the following steps that：
(1) m-phenylene diamine (MPD) and hydrogen bond inert diluent are dissolved in organic non-protonic polar solvent, are obtained and contain diamine The solution of monomer；
(2) adding paraphthaloyl chloride in the solution containing diamine monomer carries out copolycondensation；
(3) add calcium oxide to terminate the copolycondensation, obtain through between the modified poly- paraphenylene terephthalamide of hydrogen bond inert diluent The spinning solution of phenylenediamine；
(4) spinning solution through the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of hydrogen bond inert diluent is extruded through spinning head laggard Enter in coagulating bath, obtain nascent strand；
(5) the nascent strand obtains the modified poly- paraphenylene terephthalamide of hydrogen bond inert diluent through plasticization drawing, washing and hot-stretch M-phenylene diamine (MPD) fiber.
3. the preparation of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of a kind of hydrogen bond inert diluent according to claim 2 Method, it is characterised in that in step (1), the hydrogen bond inert diluent be DDS or 3,3 '-diaminourea Diphenyl sulphone (DPS), the m-phenylene diamine (MPD) are 1～4 with the mol ratio of hydrogen bond inert diluent:1, organic non-protonic polar solvent For DMAc, DMF or DMSO, the concentration of the m-phenylene diamine (MPD) in the solution containing diamine monomer is 12.5～17.5wt%；
In step (2), the paraphthaloyl chloride is 1 with the mol ratio of m-phenylene diamine (MPD) and hydrogen bond inert diluents agent composition:1, The temperature of the copolycondensation is 0～20 DEG C, and the time is 15min；
In step (3), the calcium oxide is 1 with the mol ratio of paraphthaloyl chloride:1, described modified through hydrogen bond inert diluent Poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) spinning solution solid content be 10%～17.5%；
In step (4), the coagulating bath is the mixed solution of organic non-protonic polar solvent and water, organic aprotic Polar solvent is 40%～60% with the volumetric concentration of the mixed solution of water；
In step (5), the multiple of the plasticization drawing is 1.5～3, and temperature is 25～45 DEG C, the multiple of the hot-stretch is 1～ 2.5, temperature is 285～370 DEG C.
4. modified poly- to benzene two using hydrogen bond inert diluent obtained in the preparation method as described in any one of claims 1 to 3 Formyl m-phenylene diamine (MPD) fiber, is characterized in that：
The hook strength of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of the hydrogen bond inert diluent is 2.0～3.5cN/ Dtex, fracture strength are 3.0～5.0cN/dtex；
The vitrification point of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of the hydrogen bond inert diluent is 270～350 DEG C；Institute State limited oxygen index >=29 of the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent.
5. the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent according to claim 4, its feature exist In the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of the hydrogen bond inert diluent is 3, and 3 '-DADPS is modified poly- right The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of phenyl-diformyl m-phenylene diamine (MPD) fiber, 4,4 '-DADPS or 3,3 '-diamino The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of base diphenyl sulphone (DPS) is multiple Condensating fiber.
6. the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent according to claim 5, its feature exist In, described 3, the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD)/DDS of 3 '-DADPS is modified poly- to benzene Two formyl m-phenylene diamine (MPD) composite fibres by the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) spinning solution of 3,3 '-DADPS and 4, Spinning after the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) spinning solution mixing of 4 '-DADPS is obtained, in mixed spinning solution The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) of 3,3 '-DADPS and 4,4 '-DADPS are modified poly- to benzene two The mass ratio of formyl m-phenylene diamine (MPD) is 1:99～99:1.
7. using resistance to obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent as claimed in claim 6 Hot flame-retardant yarn, is characterized in that：The heat-proof combustion-resistant yarn is fine with the wrap yarn for being coated on core yarn fiber surface by core yarn fiber Dimension composition；
The core yarn fiber is the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of DDS, the cladding Yarn fiber is the mixing fibre that the hydrogen bond inert diluent poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of modification and antistatic charcoal lead fiber Dimension；
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of the hydrogen bond inert diluent is that 3,3 '-DADPS is modified poly- The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber, 4,4 '-DADPS or 3, The modified poly- paraphenylene terephthalamide's isophthalic of modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of 3 '-DADPS Diamines composite short fiber；
Modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of the 3,3 '-DADPS is modified poly- to benzene Two formyl m-phenylene diamine (MPD) composite short fibers by the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 3,3 '-DADPS and 4, The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 4 '-DADPS is mixed to get, or is 3,3 '-DADPS Modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/4,4 '-poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of DADPS modification Chopped fiber.
8. heat-proof combustion-resistant yarn according to claim 7, it is characterised in that each component contains in the heat-proof combustion-resistant yarn Measure and be：
Core yarn fiber：5～40wt%；
The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of hydrogen bond inert diluent：58～93wt%；
Antistatic charcoal leads fiber：2wt%；
Vertical burn test method measures after flame time≤2 second of the heat-proof combustion-resistant yarn, smoldering time≤8 second.
9. using nothing obtained in the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent as claimed in claim 6 Yarn fabric, is characterized in that：The adhesive-bonded fabric is made up of fiber web layer and skeleton reinforcing fiber, and the fiber web layer is mended with skeleton Strong fiber is combined into a complete adhesive-bonded fabric entirety by needle point method；
Fiber in the fiber web layer be the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 3,3 '-DADPS, 4, The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 4 '-DADPS or 3,3 '-DADPS are modified poly- to benzene two The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite short fiber of formyl m-phenylene diamine (MPD)/4,4 '-DADPS；
Modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/the 4,4 '-DADPS of the 3,3 '-DADPS is modified poly- to benzene Two formyl m-phenylene diamine (MPD) composite short fibers by the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 3,3 '-DADPS and 4, The modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) chopped fiber of 4 '-DADPS is mixed to get, or is 3,3 '-DADPS Modified poly- paraphenylene terephthalamide m-phenylene diamine (MPD)/4,4 '-poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) composite fibre of DADPS modification Chopped fiber；
The skeleton reinforcing fiber is the modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber filament of 4,4 '-DADPS.
10. adhesive-bonded fabric according to claim 9, it is characterised in that the content of fiber web layer is in the adhesive-bonded fabric 70～95wt%, the content of skeleton reinforcing fiber is 5～30wt%；The adhesive-bonded fabric is less than 3% in 200 DEG C of shrinkage factor, The tensile strength of weight per unit area is more than 0.2 (N/cm)/(g/m2).
CN201611014772.6A 2016-11-18 2016-11-18 Modified poly- paraphenylene terephthalamide's m-phenylene diamine (MPD) fiber of hydrogen bond inert diluent and preparation method thereof and product Pending CN106498535A (en)

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CN201826079U (en) * 2010-10-26 2011-05-11 保定三源纺织科技有限公司 Core-spun yarn and fiber textile fabric containing same
CN104785017A (en) * 2015-03-10 2015-07-22 江苏菲斯特滤料有限公司 High temperature resistant filter material and manufacturing method thereof
CN104846468A (en) * 2014-02-14 2015-08-19 上海特安纶纤维有限公司 Fiber, yarn, fabric and product prepared from sulfonyl-containing aromatic polymer and preparation method thereof

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CN201826079U (en) * 2010-10-26 2011-05-11 保定三源纺织科技有限公司 Core-spun yarn and fiber textile fabric containing same
CN104846468A (en) * 2014-02-14 2015-08-19 上海特安纶纤维有限公司 Fiber, yarn, fabric and product prepared from sulfonyl-containing aromatic polymer and preparation method thereof
CN104785017A (en) * 2015-03-10 2015-07-22 江苏菲斯特滤料有限公司 High temperature resistant filter material and manufacturing method thereof

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