CN108179491A - A kind of copolymerization flame-retardant acrylic fibre fiber and preparation method thereof - Google Patents
A kind of copolymerization flame-retardant acrylic fibre fiber and preparation method thereof Download PDFInfo
- Publication number
- CN108179491A CN108179491A CN201710877154.2A CN201710877154A CN108179491A CN 108179491 A CN108179491 A CN 108179491A CN 201710877154 A CN201710877154 A CN 201710877154A CN 108179491 A CN108179491 A CN 108179491A
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- Prior art keywords
- ionic liquid
- monomer
- retardant
- acrylic fibre
- fibre fiber
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- 0 CC[C@](*)[C@](C(C)C(C)N)C1(C)CC1 Chemical compound CC[C@](*)[C@](C(C)C(C)N)C1(C)CC1 0.000 description 2
Classifications
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
Abstract
The invention discloses a kind of copolymerization flame-retardant acrylic fibre fiber, prepared by ingredient and preparation.In addition to the first monomers acrylonitrile (AN), second comonomer methyl acrylate (MA), Third monomer isopropanol, also the 4th comonomer：One comonomer based on ionic liquid structure, the monomer introduce flame-retardant composition simultaneously.The acrylic fiber obtained in the present invention can dyeability improve, the antistatic property of acrylic fiber improves.Ionic liquid fire retardant in the present invention will not volatilize, and have preferable water-soluble." designability " of the structure of ionic liquid can provide the fire retardant design of best compatibility for the technique of acrylic fiber blending method.Splendid compatibility and super excellent anti-flammability are all that conventional flame retardant cannot reach.
Description
Technical field
The invention belongs to field of functional materials, more particularly to a kind of copolymerization flame-retardant acrylic fibre fiber and preparation method thereof.
Background technology
Acrylic fibers (PAN fiber), scientific name is also known as polyacrylonitrile fibre, and " artificial wool " is also known as in China, in foreign countries then
Referred to as " Orlon ", " cashmere synthetic fibre ".
The polyacrylonitrile fibre has that fluffy degree is high, comfortable feel, good heat preservation performance, it is easy to dye the advantages that, in clothing
, daily ornament and commercial Application etc. it is widely used.But its disadvantage is to be readily burned, and poison is generated during burning
Property larger hydrogen cyanide etc., therefore its application of fire-retardant occasion is required to be restricted many.
The polyacrylonitrile fibre of countries in the world production is made mostly by terpolymer, and acrylonitrile accounts for 90%~94%, the
Two monomer additions are 5%~8%, and Third monomer is 013%~210%.
The purpose for adding in second comonomer is in order to improve the mechanical strength of fiber, elasticity and feel, to a certain extent
Dyeability can be improved.
Common second comonomer has methyl acrylate, methyl methacrylate, vinyl acetate and acrylamide etc..
The purpose for adding in Third monomer is to introduce a certain number of close dye groups, increases affinity of the fiber to dyestuff,
The fiber that chromatography is complete, bright-colored, dyefastness is good can be made.
Third monomer is divided to two major class：
One kind is that have affinity to the dye of positive ion, the monomer containing carboxyl or sulfonic acid group, such as sodium allylsulfonate, first
Base sodium allylsulfonate, dimethyl succinic acid (also known as itaconic acid), p- vinylbenzenesulfonic acid sodium etc..
Another kind of to have affinity to acid dyes, the monomer containing amido, amide groups, pyridine etc., such as vinylpyridine contain
2 ethylene methacrylic pyridines of α of basic dyeing group etc..
The main production flow of acrylic fibers is as follows：
Polymerization → spinning → preheating → steam drafting → washing → drying → heat setting → curling → cut-out → packing.
Copolymerization method is to prepare the anti-flammabilitys such as acrylonitrile monemer and vinyl chloride, vinylidene chloride monomer copolymerization containing halogen, phosphorus
The fire-resistant copolyesters body then spinning technique of ignition-proof elements is waited, this is the flame resistant method that most of flame-retardant acrylic fibre products use at present,
Its Typical Representative is Vinyon N.
Copolymer is prepared generally using aqueous polymerization, but many anti-flammability water solubility of monomer such as ethylene halide are low, volatility
Height makes polymerisation reactivity and aggregate rate relatively low, while also brings certain difficulty to production operation.
Invention content
Goal of the invention：In order to solve the deficiencies in the prior art, the present invention provides it is a kind of copolymerization flame-retardant acrylic fibre fiber and its
Preparation method.The acrylic fiber obtained in the present invention can dyeability improve, the antistatic property of acrylic fiber improves.This
Ionic liquid fire retardant in invention will not volatilize, and have preferable water-soluble." designability " of the structure of ionic liquid,
The fire retardant design of best compatibility can be provided for the technique of acrylic fiber blending method.Splendid compatibility and super excellent resistance
Combustion property is all that conventional flame retardant cannot reach.
Technical solution：A kind of copolymerization flame-retardant acrylic fibre fiber, the copolymerization flame-retardant acrylic fibre fiber is in the first monomers acrylonitrile
(AN), except second comonomer methyl acrylate (MA), Third monomer isopropanol (IPA), a 4th comonomer group is introduced
Into the 4th comonomer is：One comonomer based on ionic liquid structure, the monomer introduce simultaneously it is fire-retardant into
Point.
Further, the structural formula of the ionic liquid monomer is as follows：A+B-；Under the structure of cation can be
One kind in array structure：
Wherein, R0-5 at least one chosen from following groups：
Other R can choose from following groups respectively：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-
10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base
(Cl-C8) alkyl；
Above-mentioned group does not have substituent group or has substituents group：One or two halogen, nitro, three fluoro first
Base, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC
(1-5))2；
It is chosen in the anion that anion can be listed from having structure：
Wherein, R chooses from following groups：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkanes
Base, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkane
Base；
Above-mentioned group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, three fluoro
Methyl, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O)
(OC(1-5))2。
Further, the ionic liquid fire retardant is that single ionic liquid or several ionic liquids mix
With.
Further, the ionic liquid monomer accounts for the 0.1%-50% of the ratio of entire monomer.
Further, the ionic liquid monomer accounts for the 1%-40% of the ratio of entire monomer.
Further, the ionic liquid monomer accounts for the 3%-30% of the ratio of entire monomer.
Further, the ionic liquid monomer accounts for the 5%-20% of the ratio of entire monomer.
Further, described copolymerization flame-retardant acrylic fibre fiber can by using water as the suspension polymerisation of medium and using solvent as
The polymerisation in solution of medium obtains.
A kind of preparation method of copolymerization flame-retardant acrylic fibre fiber described in basis, includes the following steps：
The ionic liquid fire retardant of (1) 20% parts by weight and acrylonitrile (AN), the second comonomer of 31.2% parts by weight
The sodium thiocyanate solution of methyl acrylate (MA), isopropanol (IPA) and 48.8% parts by weight is put after being measured respectively with batch box
Enter allotment bucket；
(2) by initiator azodiisobutyronitrile (AIBN) and light-colored agent thiourea dioxide (TUD) it is weighed after also add in adjust
With bucket；
(3) Third monomer itaconic acid (ITA) is tuned into certain density aqueous solution and adds in allotment bucket through batch box, through filling
After dividing mixing and temperature adjustment, it is continually fed into polymeric kettle with metering pump and carries out polymerisation；
(4) whole materials gradually form thick slurry, and the slurries after the completion of polymerizeing are discharged by kettle top, transport to demonomerization tower
Monomer is sloughed, then inputs hopper, being sent to the removing of vacuum defoamation tower with gear pump after mixing stays in air in slurries
Bubble；
(5) slurries are sent to heat exchanger and carry out temperature adjustment, while add delustering agent, slurries are filtered to remove impurity, then
Spinning is sent to stable pressure.
Advantageous effect：The specific advantage of the present invention is as follows：
(1) the ionic liquid fire retardant in the present invention will not volatilize, and have preferable water-soluble.
(2) " designability " of the structure of ionic liquid can provide best compatible for the technique of acrylic fiber blending method
Property fire retardant design.Splendid compatibility and super excellent anti-flammability are all that conventional flame retardant cannot reach.
(3) since the special structure of " ion " introduces different molecular force between fire retardant and acrylic fibers macromolecular chain so that
Flame-retardant acrylic fibre durability is good very much.
(4) since ionic liquid has organic matter, inorganic matter, high molecular material good dissolubility, ionic liquid resistance
Combustion agent can be used in compounding, and can improve compatibility and dispersibility of the conventional flame retardant in acrylic fibers with conventional flame retardant, reduction pair
The influence of the physical mechanical property of acrylic fiber.
(5) fire retardant in the present invention can be response type, can also addition type.The acrylic fibers obtained in the present invention
Fiber can dyeability improve, the antistatic property of acrylic fiber improves.
Description of the drawings
Fig. 1 is the common ion liquid cation structure diagram in the present invention；
Fig. 2 is the anion structure schematic diagram of the common ion liquid in the present invention.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, so that the technology of this field
Personnel can be better understood from advantages and features of the invention, so as to make apparent boundary to protection scope of the present invention
It is fixed.Embodiment described in the invention is only part of the embodiment of the present invention, instead of all the embodiments, based on this hair
Embodiment in bright, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment shall fall within the protection scope of the present invention.
As shown in Figs. 1-2, a kind of copolymerization flame-retardant acrylic fibre fiber, the copolymerization flame-retardant acrylic fibre fiber is in the first monomer third
Except alkene nitrile (AN), second comonomer methyl acrylate (MA), Third monomer isopropanol (IPA), the 4th comonomer is introduced
Composition, the 4th comonomer are：One comonomer based on ionic liquid structure, the monomer introduce fire-retardant simultaneously
Ingredient.
The ionic liquid fire retardant includes ionic liquid ingredient, and molecular formula is as follows：A+B-；The structure of cation
It can be one kind in having structure：
Wherein, R0-5 at least one chosen from following groups：
Other R can choose from following groups respectively：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-
10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base
(Cl-C8) alkyl；Above-mentioned group does not have substituent group or has substituents group：One or two halogen, nitro, three fluoro
Methyl, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O)
(OC(1-5))2；
It is chosen in the anion that anion can be listed from Fig. 2, wherein, R chooses from following groups：Hydrogen, C (1-20) alkane
Base, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkane
Base, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkyl；Above-mentioned group can not have substituent group, it is possibility to have substituents
Group：One or two halogen, nitro, trifluoromethy, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-
NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-5)) 2.
The ionic liquid fire retardant is that single ionic liquid or several ionic liquids are used with.
The ionic liquid monomer accounts for the 0.1%-50% of the ratio of entire monomer or is 1%-40%, Huo Zhewei
3%-30% is 5%-20%.
Described copolymerization flame-retardant acrylic fibre fiber can by using water as the suspension polymerisation of medium and using solvent as the solution of medium
Polymerization obtains.
Specific embodiment
1- pi-allyl -3- methyl miaow Cuo bromides
(1) 20%1- pi-allyls -3- methyl miaow Cuo bromides compound and acrylonitrile (AN), second comonomer methyl acrylate
(MA), isopropanol (IPA) and 48.8% sodium thiocyanate solution are put into allotment bucket after being measured respectively with batch box；
(2) by initiator azodiisobutyronitrile (AIBN) and light-colored agent thiourea dioxide (TUD) it is weighed after also add in adjust
With bucket；
(3) Third monomer itaconic acid (ITA) is tuned into certain density aqueous solution and adds in allotment bucket through batch box, through filling
After dividing mixing and temperature adjustment, it is continually fed into polymeric kettle with metering pump and carries out polymerisation；
(4) whole materials gradually form thick slurry, and the slurries after the completion of polymerizeing are discharged by kettle top, transport to demonomerization tower
Monomer is sloughed, then inputs hopper, being sent to the removing of vacuum defoamation tower with gear pump after mixing stays in air in slurries
Bubble；
(5) slurries are sent to heat exchanger and carry out temperature adjustment, while add delustering agent, slurries are filtered to remove impurity, then
Spinning is sent to stable pressure.
Fire retardant in the present invention is based on ion liquid compound.Fire retardant can be response type, can also add
Type.Ionic liquid refers in room temperature or close to liquid, the salt that is made of completely zwitterion is presented at room temperature, also referred to as
For low temperature molten salt.For ionic liquid as ionic compound, lower melting-point main cause is because of substitutions certain in its structure
The asymmetry of base prevents ion from being regularly piled into caused by crystal.
It is made of organic cation and inorganic or organic anion, it is described cation See Figure 1, have quaternary ammonium salt from
Son, quaternary phosphine salt ion, imidazolium ion and pyrroles's salt ion etc..The anion See Figure 2, there is halide ion, tetrafluoro boric acid
Radical ion, hexafluorophosphoricacid acid ions, phosphate anion, sulphonic acid ester anion etc..
Ionic liquid fire retardant in the present invention will not volatilize, and have preferable water-soluble.The structure of ionic liquid
" designability " can provide the fire retardant design of best compatibility for the technique of acrylic fiber blending method.Splendid compatibility
All it is that conventional flame retardant cannot reach with super excellent anti-flammability.
Since the special structure of " ion " introduces different molecular force between fire retardant and acrylic fibers macromolecular chain so that resistance
It is good many to fire acrylic fibers durability.
Since ionic liquid has good dissolubility to organic matter, inorganic matter, high molecular material, ionic liquid is fire-retardant
Agent can be used in compounding with conventional flame retardant, and can improve compatibility and dispersibility of the conventional flame retardant in acrylic fibers, be reduced to nitrile
The influence of the physical mechanical property of synthetic fibre fiber.
Fire retardant in the present invention can be response type, can also addition type.The acrylic fiber obtained in the present invention
Can dyeability improve, the antistatic property of acrylic fiber improves.
Claims (9)
1. a kind of copolymerization flame-retardant acrylic fibre fiber, it is characterised in that：The copolymerization flame-retardant acrylic fibre fiber is in the first monomers acrylonitrile
(AN), except second comonomer methyl acrylate (MA), Third monomer isopropanol (IPA), a 4th comonomer composition is introduced,
4th comonomer is：One comonomer based on ionic liquid structure, the monomer introduce flame-retardant composition simultaneously.
2. copolymerization flame-retardant acrylic fibre fiber according to claim 1, it is characterised in that：The structure of the ionic liquid monomer
Molecular formula is as follows：A+B-；The structure of cation can be one kind in having structure：
Wherein, R0-5 at least one chosen from following groups：
Other R can choose from following groups respectively：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkanes
Base, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkane
Base；
Above-mentioned group does not have substituent group or has substituents group：One or two halogen, nitro, trifluoromethy, trifluoro
For methoxyl group, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-5)) 2；
It is chosen in the anion that anion can be listed from having structure：
Wherein, R chooses from following groups：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-
ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkyl；
Above-mentioned group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, trifluoromethy,
Trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-
5))2。
3. copolymerization flame-retardant acrylic fibre fiber according to claim 2, it is characterised in that：The ionic liquid fire retardant is single
One ionic liquid or several ionic liquids are used with.
4. copolymerization flame-retardant acrylic fibre fiber according to claim 3, it is characterised in that：The ionic liquid monomer accounts for entirely
The 0.1%-50% of the ratio of monomer.
5. copolymerization flame-retardant acrylic fibre fiber according to claim 3, it is characterised in that：The ionic liquid monomer accounts for entirely
The 1%-40% of the ratio of monomer.
6. copolymerization flame-retardant acrylic fibre fiber according to claim 3, it is characterised in that：The ionic liquid monomer accounts for entirely
The 3%-30% of the ratio of monomer.
7. copolymerization flame-retardant acrylic fibre fiber according to claim 3, it is characterised in that：The ionic liquid monomer accounts for entirely
The 5%-20% of the ratio of monomer.
8. copolymerization flame-retardant acrylic fibre fiber according to claim 3, it is characterised in that：The copolymerization flame-retardant acrylic fibre fiber can
By being obtained using polymerisation in solution of the water as the suspension polymerisation of medium and using solvent as medium.
9. a kind of preparation method of copolymerization flame-retardant acrylic fibre fiber according to claim 1, it is characterised in that：Including walking as follows
Suddenly：
The ionic liquid fire retardant of (1) 20% parts by weight and acrylonitrile (AN), the second comonomer propylene of 31.2% parts by weight
The sodium thiocyanate solution of sour methyl esters (MA), isopropanol (IPA) and 48.8% parts by weight is put into tune after being measured respectively with batch box
With bucket；
(2) by initiator azodiisobutyronitrile (AIBN) and light-colored agent thiourea dioxide (TUD) it is weighed after also add in allotment bucket；
(3) Third monomer itaconic acid (ITA) is tuned into certain density aqueous solution and adds in allotment bucket through batch box, be adequately mixed
After temperature adjustment, it is continually fed into polymeric kettle with metering pump and carries out polymerisation；
(4) whole materials gradually form thick slurry, and the slurries after the completion of polymerizeing are discharged by kettle top, are transported to demonomerization tower and are sloughed list
Then body inputs hopper, being sent to the removing of vacuum defoamation tower with gear pump after mixing stays in air bubble in slurries；
(5) slurries are sent to heat exchanger and carry out temperature adjustment, while add delustering agent, slurries are filtered to remove impurity, then with steady
Fixed pressure sends to spinning.
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| CN201710877154.2A CN108179491A (en) | 2017-09-25 | 2017-09-25 | A kind of copolymerization flame-retardant acrylic fibre fiber and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710877154.2A CN108179491A (en) | 2017-09-25 | 2017-09-25 | A kind of copolymerization flame-retardant acrylic fibre fiber and preparation method thereof |
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ID=62545110
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109295523A (en) * | 2018-09-30 | 2019-02-01 | 天津工业大学 | A kind of permanent anti-static acrylonitrile copolymer and its fiber producing processes |
| CN111088544A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Flame retardant, flame-retardant acrylic fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536107A (en) * | 2003-04-04 | 2004-10-13 | 中国石油天然气集团公司 | Preparation method of polyacrylonitrile carbon raw yarn |
| CN100999604A (en) * | 2007-01-12 | 2007-07-18 | 东华大学 | Soluble polyacrylic cyanide composite and preparation process thereof |
| CN103980419A (en) * | 2014-05-05 | 2014-08-13 | 东华大学 | Halogen-free phosphorus-free flame retardant polyacrylonitrile compound and preparation method |
-
2017
- 2017-09-25 CN CN201710877154.2A patent/CN108179491A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536107A (en) * | 2003-04-04 | 2004-10-13 | 中国石油天然气集团公司 | Preparation method of polyacrylonitrile carbon raw yarn |
| CN100999604A (en) * | 2007-01-12 | 2007-07-18 | 东华大学 | Soluble polyacrylic cyanide composite and preparation process thereof |
| CN103980419A (en) * | 2014-05-05 | 2014-08-13 | 东华大学 | Halogen-free phosphorus-free flame retardant polyacrylonitrile compound and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109295523A (en) * | 2018-09-30 | 2019-02-01 | 天津工业大学 | A kind of permanent anti-static acrylonitrile copolymer and its fiber producing processes |
| CN109295523B (en) * | 2018-09-30 | 2021-01-26 | 天津工业大学 | Permanent antistatic acrylonitrile-based copolymer and preparation method of fiber thereof |
| CN111088544A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Flame retardant, flame-retardant acrylic fiber and preparation method thereof |
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Application publication date: 20180619 |