CN100545181C - A kind of hydrophilicity spinning fluid of PAN-based carbon fiber and preparation method - Google Patents
A kind of hydrophilicity spinning fluid of PAN-based carbon fiber and preparation method Download PDFInfo
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- CN100545181C CN100545181C CNB2007100560821A CN200710056082A CN100545181C CN 100545181 C CN100545181 C CN 100545181C CN B2007100560821 A CNB2007100560821 A CN B2007100560821A CN 200710056082 A CN200710056082 A CN 200710056082A CN 100545181 C CN100545181 C CN 100545181C
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 34
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000009987 spinning Methods 0.000 title claims abstract description 34
- 239000012530 fluid Substances 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 148
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 54
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical class C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000009736 wetting Methods 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims description 42
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Chemical group 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- -1 isobutyl- Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 229920002239 polyacrylonitrile Polymers 0.000 description 12
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OQTRPSFMBXCQIY-UHFFFAOYSA-N azane;2-methylidenebutanedioic acid Chemical compound N.OC(=O)CC(=C)C(O)=O OQTRPSFMBXCQIY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- UNYNVICDCJHOPO-UHFFFAOYSA-N quabalactone III Natural products CC1OC(=O)C(O)=C1C UNYNVICDCJHOPO-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Abstract
A kind of hydrophilicity spinning fluid of PAN-based carbon fiber constitutes the dimethyl sulphoxide solution of main monomer vinyl cyanide and comonomer multipolymer; Comonomer 1 is a vinyl imidazole salt, and comonomer 2 is methylene-succinic acid, vinylformic acid, methacrylic acid or their mixture; Main monomer is 90～99.5% of a total monomer weight, and the comonomer gross weight is 0.5～10% of a total monomer weight; Wherein comonomer 1 accounts for 10～90% of comonomer gross weight, and comonomer 2 accounts for 90～10% of comonomer gross weight, and the total monomer weight percent is 15～25%.Press proportioning with the solvent dimethyl sulfoxide (DMSO); the main monomer vinyl cyanide; comonomer 1 and comonomer 2, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device; at room temperature mix; behind the nitrogen bubble 20 minutes, under nitrogen protection, in 50-70 ℃ of isothermal reaction 6～36 hours; remove residual monomer and bubble then, get a kind of wetting ability carbon fiber spinning solution.
Description
Technical field
The present invention relates to a kind of wetting ability alkene itrile group carbon fiber spinning solution that contains vinyl imidazole salt structural unit and preparation method thereof.
Background technology
Carbon fiber has characteristics such as high specific strength, high ratio modulus, heat-resisting, corrosion-resistant, antifatigue, creep resistance, is a kind of high performance fibre material, has been widely used in industries such as aerospace, national defense construction, Leisure Sport articles for use, medicine equipment and building.PAN-based carbon fiber has outstanding mechanical property, is the focus of carbon fiber research in recent years.Someone thinks, the high-quality polyacrylonitrile fibril is one of key of preparation high-performance polyacrylonitrile-based carbon fiber, must set about from synthetic high-quality acrylonitrile copolymer and optimization spinning technique two aspects and will obtain the high-quality polyacrylonitrile fibril, have only the acrylonitrile copolymer of excellent performance just can spin out the high-quality polyacrylonitrile fibril, thereby prepare high performance PAN-based carbon fiber.
United States Patent (USP) 4336022,4603041 and 6221492 B1 show, improve the wetting ability of polyacrylonitrile resin, help controlling the process of setting of nascent strand, suppress to be separated fast, thereby obtain the high-quality precursor of fine and close, few defective.After wetting ability increases, precursor can combine infiltration better with water vapor in the water vapor drafting process, water can play plastification to polyacrylonitrile, like this under the hot steam condition, precursor is easier to be drafted, and the precursor subsurface defect is also easier makes up, and this helps improving the hole in orientation degree and the minimizing precursor, avoid the introducing of other impurity element to cause the carbon fiber downgrade simultaneously, thereby obtained the high quality precursor of the low linear density of high strength.Yet up to the present, people never find suitable method to improve the wetting ability of polyacrylonitrile resin.Document (polymer material science and engineering, 2005,21 (2): 132～134 were arranged in recent years; Synthetic technology and application, 2003,18 (1): 4～7) report can adopt acrylamide to improve the wetting ability of polyacrylonitrile resin as comonomer.Also can improve the wetting ability of spinning solution with the methylene-succinic acid ammonium as comonomer, and then improve properties of carbon (Journal of Polymer Research, 2007,14:91～97).But the reactivity ratio difference of these two kinds of monomers and vinyl cyanide is all very big, is difficult to obtain the uniform acrylonitrile copolymer of chain structure.
Chinese patent 02130021.6,02130023.2 and 02130024.0 shows, can first synthesis of acrylonitrile homopolymer, in reaction solution, feed ammonia then, reacted 2 hours down at 80-100 ℃, make part functional group be converted into carboxyl and amide group, synthesis of ternary multipolymer indirectly, this method can be improved the spinning property and the wetting ability of polyacrylonitrile effectively.Yet the reaction of ammonia and polyacrylonitrile viscous fluid is the heterogeneous reaction of a complexity, and the mass transfer difficulty reacts wayward, and circulation ratio is relatively poor.(chemistry circular such as Li Junjie; 2006; (10): 781～784) utilize unshielded sugar lactone and methacrylic acid-2-aminoethyl ester hydrochloride reaction to synthesize a kind of straight chain sugar of novelty; and itself and vinyl cyanide have been carried out copolymerization with the method for water precipitation polymerization, can improve the wetting ability of polyacrylonitrile resin.Prepare the wetting ability polyacrylonitrile-based carbon fiber spinning solution with polymerisable ionic liquid as comonomer, have not yet to see bibliographical information.
Summary of the invention
The purpose of this invention is to provide a kind of wetting ability carbon fiber spinning solution and preparation method thereof.
The composition of a kind of wetting ability carbon fiber spinning solution provided by the invention constitutes and proportioning is: it is the dimethyl sulphoxide solution of main monomer and comonomer multipolymer;
Described that main monomer is a vinyl cyanide; Comonomer has comonomer 1 and comonomer 2, and comonomer 1 is a vinyl imidazole salt, and comonomer 2 is methylene-succinic acid, vinylformic acid, methacrylic acid or their mixture; Main monomer is 90～99.5% of a total monomer weight, and the comonomer gross weight is 0.5～10% of a total monomer weight; Wherein comonomer 1 accounts for 10～90% of comonomer gross weight, and comonomer 2 accounts for 90～10% of comonomer gross weight, and the total monomer weight percent is 15～25%.
The structure of the vinyl imidazole salt of described comonomer 1 is as follows:
Wherein, X is a chlorine or bromine; R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl or isobutyl-.
14 kinds of vinyl imidazole salt that are preferably as follows:
The R=ethyl, the X=bromine
-ViEtIm
+Br; The R=normal-butyl, the VinBuIm of X=chlorine
+Cl
-The R=methyl, the ViMeIm of X=chlorine
+Cl
-The R=ethyl, the ViEtIm of X=chlorine
+Cl
-The R=n-propyl, the VinPrIm of X=chlorine
+Cl
-The R=sec.-propyl, the ViiPrIm of X=chlorine
+Cl
-The R=sec-butyl, the VisBuIm of X=chlorine
+Cl
-The R=isobutyl-, the ViiBuIm of X=chlorine
+Cl
-The R=methyl, the ViMeIm of X=bromine
+Br
-The R=n-propyl, the VinPrIm of X=bromine
+Br
-The R=sec.-propyl, the ViiPrIm of X=bromine
+Br
-The R=normal-butyl, the VinBuIm of X=bromine
+Br
-The R=sec-butyl, the VisBuIm of X=bromine
+Br
-The R=isobutyl-, the ViiBuIm of X=bromine
+Br
-
Preparation method's step and the condition that the invention provides a kind of wetting ability carbon fiber spinning solution is as follows:
The comonomer 1 that the present invention uses is vinyl imidazole salt, and structure is as follows:
Wherein, X is a chlorine or bromine; R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl or isobutyl-.
Preferred ViMeIm
+Cl
-,, ViEtIm
+Cl
-,, VinPrIm
+Cl
-,, ViiPrIm
+Cl
-, VisBuIm
+Cl
-, ViiBuIm
+Cl
-, ViMeIm
+Br
-, VinPrIm
+Br
-, ViiPrIm
+Br
-, VinBuIm
+Br
-, VisBuIm
+Br
-, ViiBuIm
+Br
-The preparation method of these 12 kinds of vinyl imidazole salt and ViEtIm described below
+Br
-And VinBuIm
+Cl
-Identical.
1) R=ethyl, the X=bromine
-(ViEtIm
+Br); The R=normal-butyl, X=chlorine (VinBuIm
+Cl
-) the preparation method as follows:
ViEtIm
+Br
-(being the R=ethyl, the X=bromine) and VinBuIm
+Cl
-The detailed preparation method of (being the R=normal-butyl, X=chlorine) these two kinds of vinyl imidazole salt can be referring to document (Journal of PolymerScience:Part A:Polymer Chemistry, Vol.42,208-212 (2004).
2) with the solvent dimethyl sulfoxide (DMSO), the main monomer vinyl cyanide, comonomer 1 and comonomer 2, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device, at room temperature mix, behind the nitrogen bubble 20 minutes, under nitrogen protection, in 50-70 ℃ of isothermal reaction 6～36 hours, remove residual monomer and bubble then, get a kind of high-hydrophilic carbon fiber spinning solution;
The weight percent proportioning of described material is: main monomer is 90～99.5% of a total monomer weight, and the comonomer gross weight is 0.5～10% of a total monomer weight; Wherein comonomer 1 accounts for 10～90% of comonomer gross weight, and comonomer 2 accounts for 90～10% of comonomer gross weight; The consumption of Diisopropyl azodicarboxylate is 0.25～0.75% of a total monomer weight, and the total monomer weight percent is 15～25%.
Advantage of the present invention:
1, because vinyl imidazole salt is not only water-soluble fabulous, and volume is bigger, in the hydrophilic while of improving spinning solution greatly, the raising of spinning property and the diffusion of cyclisation heat release all there is great promoter action, therefore can reduce the consumption of introducing the comonomer in the vinyl cyanide greatly, finally cause the raising of carbon fiber performance.The imidazole ring that wherein has rigid structure can weaken (strong interaction CN) of itrile group in the macromole, thereby the macromole that improves in its solution tangles, the fracture of wire of minimizing when carrying out dry-jet wet-spinning, and the speed that oxygen enters fibrous inside can improve preoxidation the time, make the external and internal compositions of the fiber after the preoxidation more even, thereby improve properties of carbon.
2, because vinyl imidazole salt has concurrently and improves wetting ability and spinning property dual function, we are incorporated into traditional vinyl cyanide/methylene-succinic acid (or acrylic or methacrylic acid)/acrylic ester ternary polymerization system with vinyl imidazole salt.We find through kinetic determination: the reactivity ratio of vinyl imidazole salt and vinyl cyanide is very approaching, and when the molar content of vinyl imidazole salt is higher, can obtain a kind of water miscible multipolymer.Behind vinyl imidazole salt replacement acrylate, adopt vinyl cyanide/methylene-succinic acid (or acrylic or methacrylic acid or their mixture)/free-radical polymerized method of vinyl imidazole salt, obtained the uniform narrow distribution high-hydrophilic spinning solution of chain structure.The weight-average molecular weight of multipolymer is 10～600,000 adjustable, and molecular weight distributing index can be controlled between 2.0～2.5, and monomer conversion is between 92.6%～99.5%.Compare with not adding vinyl imidazole salt, the contact angle that adds vinyl imidazole salt post polymerization thing and water can be reduced to 34.5 ° by 69.5 °, shows that the introducing of vinyl imidazole salt improves the wetting ability of acrylonitrile copolymer greatly.
Embodiment
Embodiment 1
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer VinBuIm
+Br
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 98% of a total monomer weight, comonomer VinBuIm
+Br
-Be 1% of total monomer weight, the comonomer methylene-succinic acid is 1% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.5% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 23.1 ten thousand, and molecular weight distributing index is 2.13, and the contact angle of polymkeric substance and water is to 40.0 °.
Embodiment 2
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViEtIm
+Br
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 90% of a total monomer weight, comonomer ViEtIm
+Br
-Be 5% of total monomer weight, the comonomer methylene-succinic acid is 5% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.5% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 10.4 ten thousand, and molecular weight distributing index is 2.20, and the contact angle of polymkeric substance and water is to 34.5 °.
Embodiment 3
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViMeIm
+Cl
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer ViMeIm
+Cl
-Be 1% of total monomer weight, the comonomer methylene-succinic acid is 2% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.5% of a total monomer weight, and total monomer is 25%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 27.6 ten thousand, and molecular weight distributing index is 2.23, and the contact angle of polymkeric substance and water is to 41.0 °.
Embodiment 4
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViEtIm
+Cl
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 98% of a total monomer weight, comonomer ViEtIm
+Cl
-Be 1% of total monomer weight, the comonomer methylene-succinic acid is 1% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 25%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 24.2 ten thousand, and molecular weight distributing index is 2.18, and the contact angle of polymkeric substance and water is to 38.0 °.
Embodiment 5
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer VinPrIm
+Cl
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 99% of a total monomer weight, comonomer VinPrIm
+Cl
-Be 0.75% of total monomer weight, the comonomer methylene-succinic acid is 0.25% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.25% of a total monomer weight, and total monomer is 23.5%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 50 ℃ of isothermal reactions 36 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 56.2 ten thousand, and molecular weight distributing index is 2.26, and the contact angle of polymkeric substance and water is to 46.0 °.
Embodiment 6
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer VinBuIm
+Cl
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 99.5% of a total monomer weight, comonomer VinBuIm
+Cl
-Be 0.25% of total monomer weight, the comonomer methylene-succinic acid is 0.25% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.25% of a total monomer weight, and total monomer is 23.5%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 70 ℃ of isothermal reactions 6 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 28.5 ten thousand, and molecular weight distributing index is 2.50, and the contact angle of polymkeric substance and water is to 52.0 °.
Embodiment 7
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViMeIm
+Br
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 96% of a total monomer weight, comonomer ViMeIm
+Br
-Be 2.0% of total monomer weight, the comonomer methylene-succinic acid is 2.0% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.35% of a total monomer weight, and total monomer is 15%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 70 ℃ of isothermal reactions 6 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 15.3 ten thousand, and molecular weight distributing index is 2.15, and the contact angle of polymkeric substance and water is to 35.0 °.
Embodiment 8
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViiPrIm
+Br
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer ViiPrIm
+Br
-Be 2.0% of total monomer weight, the comonomer methylene-succinic acid is 1.0% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 25.2 ten thousand, and molecular weight distributing index is 2.28, and the contact angle of polymkeric substance and water is to 49.0 °
Embodiment 9
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViiBuIm
+Br
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer ViiBuIm
+Br
-Be 2.0% of total monomer weight, the comonomer methylene-succinic acid is 1.0% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 27.2 ten thousand, and molecular weight distributing index is 2.48, and the contact angle of polymkeric substance and water is to 46.5 °.
Embodiment 10
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer VisBuIm
+Br
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer VisBuIm
+Br
-Be 1.5% of total monomer weight, the comonomer methylene-succinic acid is 1.5% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 27.6 ten thousand, and molecular weight distributing index is 2.48, and the contact angle of polymkeric substance and water is to 46.5 °.
Embodiment 11
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer VinPrIm
+Br
-, vinylformic acid and methacrylic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer VinPrIm
+Br
-Be 1.0% of total monomer weight, comonomer vinylformic acid is 1.0% of total monomer weight, and the comonomer methacrylic acid is 1.0% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 29.8 ten thousand, and molecular weight distributing index is 2.48, and the contact angle of polymkeric substance and water is to 45.5 °.
Embodiment 12
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer VisBuIm
+Cl
-And methylene-succinic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer VisBuIm
+Cl
-Be 1.5% of total monomer weight, the comonomer methylene-succinic acid is 1.5% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 21.2 ten thousand, and molecular weight distributing index is 2.25, and the contact angle of polymkeric substance and water is to 45.5 °.
Embodiment 13
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViiPrIm
+Cl
-And vinylformic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer ViiPrIm
+Cl
-Be 1.5% of total monomer weight, comonomer vinylformic acid is 1.5% of total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 24.3 ten thousand, and molecular weight distributing index is 2.42, and the contact angle of polymkeric substance and water is to 47.5 °.
Embodiment 14
With the solvent dimethyl sulfoxide (DMSO), main monomer vinyl cyanide, comonomer ViiBuIm
+Cl
-And methacrylic acid, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device.Add raw-material weight percent proportioning and be: the main monomer vinyl cyanide is 97% of a total monomer weight, comonomer ViiBuIm
+Cl
-Be 1.5% of total monomer weight, the comonomer methacrylic acid is 1.5% of a total monomer weight, and the consumption of Diisopropyl azodicarboxylate is 0.75% of a total monomer weight, and total monomer is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, gets a kind of high-hydrophilic carbon fiber spinning solution.The multipolymer weight-average molecular weight is 23.4 ten thousand, and molecular weight distributing index is 2.30, and the contact angle of polymkeric substance and water is to 47 °.
Claims (2)
1, a kind of hydrophilicity spinning fluid of PAN-based carbon fiber is characterized in that composition constitutes and proportioning is:
The dimethyl sulphoxide solution of main monomer and comonomer multipolymer;
Wherein main monomer is a vinyl cyanide; Comonomer has comonomer 1 and comonomer 2, and comonomer 1 is a vinyl imidazole salt, and comonomer 2 is methylene-succinic acid, vinylformic acid, methacrylic acid or their mixture; Main monomer is 90～99.5% of a total monomer weight, and the comonomer gross weight is 0.5～10% of a total monomer weight; Wherein comonomer 1 accounts for 10～90% of comonomer gross weight, and comonomer 2 accounts for 90～10% of comonomer gross weight, and the total monomer weight percent is 15～25%;
The structure of the vinyl imidazole salt of described comonomer 1 is as follows:
Wherein, X is a chlorine or bromine; R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl or isobutyl-.
2, the preparation method of the hydrophilicity spinning fluid of a kind of PAN-based carbon fiber as claimed in claim 1 is characterized in that step and condition are as follows:
Press proportioning with the solvent dimethyl sulfoxide (DMSO), the main monomer vinyl cyanide, comonomer 1 and comonomer 2, the radical initiator Diisopropyl azodicarboxylate joins in the reactor that has prolong and mechanical stirring device, at room temperature mix, behind the nitrogen bubble 20 minutes, under nitrogen protection, in 50-70 ℃ of isothermal reaction 6～36 hours, remove residual monomer and bubble then, get a kind of wetting ability carbon fiber spinning solution;
The weight percent proportioning of described material is: main monomer is 90～99.5% of a total monomer weight, and the comonomer gross weight is 0.5～10% of a total monomer weight; Wherein comonomer 1 accounts for 10～90% of comonomer gross weight, and comonomer 2 accounts for 90～10% of comonomer gross weight, and the consumption of Diisopropyl azodicarboxylate is 0.25～0.75% of a total monomer weight, and the total monomer weight percent is 15～25%.
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| CN105624819A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method of hydrophilic polyacrylonitrile-based carbon fiber precursor |
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| CN101805936A (en) * | 2010-03-09 | 2010-08-18 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with high molecular weight and narrow distribution and preparation method thereof |
| CN101781809B (en) * | 2010-03-09 | 2012-01-11 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with uniform chain structure and narrow molecular-weight distribution and preparation method thereof |
| CN102102234B (en) * | 2010-12-22 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Ternary copolymerization highly hydrophilic polyacrylonitrile-based carbon fiber spinning solution and preparation method thereof |
| CN103173883B (en) * | 2013-04-18 | 2015-04-15 | 中国科学院长春应用化学研究所 | Acrylonitrile copolymer spinning solution and preparation method thereof |
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