CN105734712B - A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material - Google Patents
A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material Download PDFInfo
- Publication number
- CN105734712B CN105734712B CN201510632542.5A CN201510632542A CN105734712B CN 105734712 B CN105734712 B CN 105734712B CN 201510632542 A CN201510632542 A CN 201510632542A CN 105734712 B CN105734712 B CN 105734712B
- Authority
- CN
- China
- Prior art keywords
- polyquaternium
- poly
- pyrrole throat
- preparation
- electrospinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 229920000289 Polyquaternium Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 24
- 238000001523 electrospinning Methods 0.000 title claims description 14
- 238000009987 spinning Methods 0.000 claims abstract description 53
- 239000002121 nanofiber Substances 0.000 claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 21
- -1 ammonium carboxylate salts Chemical class 0.000 claims abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 150000001412 amines Chemical group 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229940125904 compound 1 Drugs 0.000 claims description 15
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- XLXVRIOQCHHBTC-UHFFFAOYSA-N 2,2-bis(phenoxycarbonyl)propanedioic acid Chemical compound C=1C=CC=CC=1OC(=O)C(C(O)=O)(C(=O)O)C(=O)OC1=CC=CC=C1 XLXVRIOQCHHBTC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 71
- 238000006243 chemical reaction Methods 0.000 description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- 238000013019 agitation Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 15
- 150000003863 ammonium salts Chemical class 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000003115 biocidal effect Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 239000003242 anti bacterial agent Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 229940088710 antibiotic agent Drugs 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- 0 CCC=C[C@](CCC(C*(C)(C)C)C=C)CC(*)(*)Cl Chemical compound CCC=C[C@](CCC(C*(C)(C)C)C=C)CC(*)(*)Cl 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- DNERPWQVMYIKPA-UHFFFAOYSA-N 1,7-bis(chloromethyl)naphthalene Chemical class ClCC1=CC2=C(C=CC=C2C=C1)CCl DNERPWQVMYIKPA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CQKOHEPVNHWULI-UHFFFAOYSA-N C(=O)O.C(=O)O.C(=O)O.C(=O)O.C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1 Chemical compound C(=O)O.C(=O)O.C(=O)O.C(=O)O.C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1 CQKOHEPVNHWULI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- PENXUAAQSIVXBE-UHFFFAOYSA-N 1-(dichloromethyl)naphthalene Chemical compound C1=CC=C2C(C(Cl)Cl)=CC=CC2=C1 PENXUAAQSIVXBE-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QBYJBZPUGVGKQQ-SJJAEHHWSA-N aldrin Chemical group C1[C@H]2C=C[C@@H]1[C@H]1[C@@](C3(Cl)Cl)(Cl)C(Cl)=C(Cl)[C@@]3(Cl)[C@H]12 QBYJBZPUGVGKQQ-SJJAEHHWSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- AIUDWMLXCFRVDR-UHFFFAOYSA-N dimethyl 2-(3-ethyl-3-methylpentyl)propanedioate Chemical class CCC(C)(CC)CCC(C(=O)OC)C(=O)OC AIUDWMLXCFRVDR-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229940066779 peptones Drugs 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention discloses a kind of preparation methods of poly- pyrrole throat/polyquaternium composite antibacterial material.The composite material is obtained according to the following steps：(1) ammonium carboxylate salts of tetra-atomic acid and quaternary amine mixed dissolution are provided；(2) synthesis modification polyquaternium；(3) it is mixed into modified polyquaternium in ammonium carboxylate salts, spinning solution is made；(4) to spinning solution high-voltage electrostatic spinning, high-temperature heat treatment.There is the method for invention spinning solution to mix evenly, not only improve the problem of poly- pyrrole throat is difficult to Electrospun, and improve the not high problem of polyquaternium intensity, poly- pyrrole throat/polyquaternium composite antibacterial material nanofiber degree of orientation higher obtained final simultaneously, uniform diameter, also good antibacterial effect.
Description
Technical field
The present invention relates to the preparation sides that a kind of molecule based on electrospinning assembles poly- pyrrole throat/polyquaternium composite antibacterial material
Method.
Technical background
Poly- pyrrole throat is the trapezoidal or half trapezoidal aromatic heterocyclic polymer of a kind of rigidity, is contained simultaneously in strand more than two total
There is yoke ring layer structure, strand to have very big rigidity.This rigid molecule chain arrangement canon are whole, and therefore, poly- pyrrole throat has very high
Glass transition temperature and heat decomposition temperature.Still there is good mechanical performance at high temperature, can be used as the necks such as space flight, microelectronics
The high-temperature material in domain.Poly- pyrrole throat can also do separation membrane material, have higher selective penetrated property, resistance to ablation than common separation film
Property.Therefore poly- pyrrole throat polymer is widely studied, but is mostly the research of film.This kind of polymer is usually in polyphosphoric acids etc.
High boiling solvent high temperature synthesizes.Since the polymer such as poly- pyrrole throat neither melt, ordinary organic solvents are also insoluble in, poly- pyrrole throat
Machinability is extremely restricted.It does not melt insoluble characteristic and makes it difficult to be prepared with melting electrostatic spinning or solution electrostatic spinning
The nanofiber of the polymer.
Polyquaternium is a kind of good polymer antibacterial agent, not volatile, stability is good, easy processing, production process
Safely and skin will not be penetrated into, while also there is bactericidal property more better than small molecule fungicide, and polyquaternium is solidifying
Poly- power is strong, is not easy plastic.But polyquaternium intensity is not high, chemical stability is bad, 200 DEG C or so will decompose.
Hence it is highly desirable to by the improvement of formula and production technology, it is compound anti-to develop a kind of poly- pyrrole throat/polyquaternium
The preparation method of bacterium material.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of molecules to assemble poly- pyrrole throat/polyquaternium composite antibacterial material
Preparation method.Poly- pyrrole throat/polyquaternium composite material of the present invention is by the way that tetra-atomic acid and quaternary amine are dissolved in solvent
In, polyquaternium is added, adjusts the viscosity and concentration of solution, spinning solution is made, is made through electrostatic spinning and heat treatment.Specific packet
It includes including step：
Ammonium carboxylate salts including at least tetra-atomic acid and quaternary amine are provided, poly- pyrrole throat precursor solution is made；
Polyquaternium is added in poly- pyrrole throat precursor solution, spinning solution is made, electrostatic spinning forms composite nano fiber
Presoma；
To being heat-treated under above-mentioned composite nano fiber presoma vacuum, poly- pyrrole throat/polyquaternium composite antibacterial material is made.
In one embodiment, the polyquaternium is made by 2,8- dichloromethyls naphthalene, tetramethyl butane diamine and compound 1
, the structural formula of compound is as follows：
In one embodiment, compound 1 and the molar ratio of two tertiary amines are 0.1~0.5 in the polyquaternium：0.5.
In one embodiment, the tetra-atomic acid includes at least bibenzene tetracarboxylic, benzophenone tetracarboxylic, diphenyl ether tetramethyl
Acid, diphenyl methane tetracarboxylic acid, bis trifluoromethyl diphenyl tetracarboxylic acid, naphthalenetetracarbacidic acidic, hexamethylene tetracid, tetracarboxylic acid benzimidazole
With one kind in diphenyl sulfone tetraformic acid.
In one embodiment, the quaternary amine includes at least biphenyl tetramine, equal benzene tetramine, pyridine tetramine, ring penta 4
One kind in amine and carbazole tetramine.
In one embodiment, the molar ratio of the tetra-atomic acid and tetra-atomic acid is 0.8：1~1：0.8.
In one embodiment, the quality of the polyquaternium account for poly- pyrrole throat/polyquaternium composite material 50%~
70%.
In one embodiment, ammonium carboxylate salt mass fraction is 5%~20% in the precursor solution.
In one embodiment, polyquaternium mass fraction is 5%~25% in the spinning solution.
In one embodiment, the condition of the heat treatment includes, first in 100~150 DEG C of 2~5h of constant temperature, then existing
150~200 DEG C of 2~5h of constant temperature, 250~350 DEG C of 10~60min of annealing under last vacuum.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific implementation mode
With reference to preferred implementation method of the invention below detailed description and including embodiment this public affairs can be more easily understood
Open content.A large amount of terms can be referred in following description and claims, and these terms are defined as following contain
Justice.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise.
" optionally " or refer to " optionally " that the item described thereafter or event may or may not occur, and this is retouched
State the situation that the situation occurred including event and event do not occur.
Approximate language in specification and claims is for modifying quantity, indicating that the present invention is not limited to the specific numbers
Amount, further includes the modified part of the acceptable change without lead to related basic function close to the quantity.At certain
In a little examples, approximate term likely corresponds to the precision of the instrument of measured value.In present specification and claims,
Range restriction can be combined and/or be exchanged, these ranges if not stated otherwise include all subranges contained by period.
In preparing precursor solution, " tetra-atomic acid " refers in monomer containing there are four the substances of carboxyl；" the quaternary
Amine " refers in monomer containing there are four the substances of amino.
The present invention relates to the preparation sides that a kind of molecule based on electrospinning assembles poly- pyrrole throat/polyquaternium composite antibacterial material
Method, including：
Ammonium carboxylate salts including at least tetra-atomic acid and quaternary amine are provided, poly- pyrrole throat precursor solution is made；
Polyquaternium is added in poly- pyrrole throat precursor solution, spinning solution is made, electrostatic spinning forms composite nano fiber
Presoma；
To being heat-treated under above-mentioned composite nano fiber presoma vacuum, poly- pyrrole throat/polyquaternium composite antibacterial material is made.
In one embodiment, in the precursor solution, the molar ratio of tetra-atomic acid and tetra-atomic acid is 0.8：1~1：
0.8；Preferably, the molar ratio of tetra-atomic acid and quaternary amine is 1：1.
In one embodiment, following synthetic method can be used in the polyquaternium：
(1) preparation of compound 1
3 mole of urea and 25ml concentrated hydrochloric acids are added in the three-necked flask of 200ml distilled water, stirs, waits for that urea is completely dissolved,
Slowly it is added dropwise 1 mole 1 in whipping process, 1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- diacetyl react 5h, have precipitation to generate, and decompression is taken out
Filter, after distillation washing three times, acetone is washed 2 times, and compound 2 is dried to obtain.2 structural formula of the compound is as follows：
Be added in three-necked flask 1 mole of above compound 2 and 30ml formaldehyde (mass fraction 37%) ultrasonic dissolution in
In the concentrated sulfuric acid of 30ml, under agitation, heating reaction 2 hours, then vacuum distillation removes the water in reaction mixture, rises
Temperature is to 160~170 DEG C, and the reaction was continued 6~7 hours；After reaction, it is down to room temperature, reactant is poured into 300ml water, is analysed
Go out precipitation, is filtered after placing 15min；Then precipitation is washed with 1000ml aqueous acetone solutions (mass fraction 25%) twice, sink again
Starch washs filtering with (mass fraction 80%) aqueous acetone solution again, then with after 100ml water washings 3 times, in vacuum drying oven about
60 DEG C of drying are for 24 hours to get to compound 1.1 structural formula of the compound：
Reaction process is represented by：
(2) preparation of polyquaternium
It is 1.2 that molar ratio is added in the three-necked flask equipped with electromagnetic agitation, reflux condensing tube and thermometer：The 2,8- of 1
Dichloromethyl naphthalene and dry tetramethyl butane diamine and 20ml acetonitriles, make it be completely dissolved in acetonitrile, are warming up to reflux, make poly- season
Ammonium salt autohemagglutination, reaction for 24 hours, go out product with acetone precipitation, are purified twice with ethyl alcohol/ether, be dried in vacuo to obtain white product 3.In vain
The structural formula of color product 3 is：
Reaction process is represented by：
100ml ethyl alcohol is added in three-necked flask, 320 parts of above-mentioned white product, 15~20 parts of rooms of compound are then added
For 24 hours, 6 parts of benzene and 10 points of anhydrous Aluminum chlorides are then added in the lower magnetic stirring of temperature, in ice salt bath, stirring, and end capping reaction 10h, reaction
After, it is crossed after standing and filters out precipitation, adjust PH to 8, washing is dried in vacuo to obtain the modified polyquaternium of compound 1.Reaction
Process is represented by：
In one embodiment, the compound 1 and the molar ratio of tetramethyl butane diamine are 0.1~0.5：0.5；It is preferred that
The molar ratio of ground, compound 1 and tetramethyl butane diamine is 0.5：0.5.
In one embodiment, the tetra-atomic acid includes at least bibenzene tetracarboxylic, benzophenone tetracarboxylic, diphenyl ether tetramethyl
Acid, diphenyl methane tetracarboxylic acid, bis trifluoromethyl diphenyl tetracarboxylic acid, naphthalenetetracarbacidic acidic, hexamethylene tetracid, tetracarboxylic acid benzimidazole
With one kind in diphenyl sulfone tetraformic acid.
In one embodiment, the quaternary amine includes at least biphenyl tetramine, equal benzene tetramine, pyridine tetramine, ring penta 4
One kind in amine and carbazole tetramine.
In one embodiment, ammonium carboxylate salts are made in tetra-atomic acid and quaternary amine mixed dissolution, this process is usual
Solvent can be used.The solvent can include but is not limited to dimethylacetylamide (DMAC), dimethylformamide (DMF), dimethyl
Sulfoxide (DMSO) and repefral (DMP) etc. have the solvent of good solubility.
In one embodiment, polyquaternium is added in above-mentioned ammonium carboxylate salts, it is molten that poly- pyrrole throat presoma is made
Liquid, the polyquaternium can form poly ammonium salt complex compound, increase spinning fluid viscosity.
In one embodiment, the quality of the polyquaternium account for poly- pyrrole throat/polyquaternium composite material 50%~
70%；Preferably, the quality of polyquaternium accounts for the 60% of poly- pyrrole throat/polyquaternium composite material.
In one embodiment, ammonium carboxylate salt mass fraction is 5%~20% in the poly- pyrrole throat precursor solution；It is excellent
Selection of land, acid ammonium salt mass fraction are 12%~16%.
In one embodiment, polyquaternium mass fraction is 5%~25% in the spinning solution；Preferably, gather
Quaternary ammonium salt mass fraction is 20%~25%.
In one embodiment, during the poly- pyrrole throat precursor solution electrostatic spinning, spinning voltage is specifically 10
Between~30KV；Preferably, spinning voltage is 20~30KV；Needle point is to the distance of reception device, i.e. spinning reception is away from optionally
Control is in the range of 10~40cm；Preferably, spinning is received away from for 25cm.
Condition used by the electrostatic spinning：Spinning temperature is less than 30 DEG C；Preferably, spinning temperature is 5~20 DEG C.
The nanofiber diameter of electrostatic spinning is between 200~1500nm；Preferably, ranging from the 500 of nanometer diameter~
900nm；It is highly preferred that nanofiber diameter gives 600~800nm.
In one embodiment, the condition of the heat treatment includes, first in 100~150 DEG C of 2~5h of constant temperature, then existing
150~200 DEG C of 2~5h of constant temperature, 250~350 DEG C of 10~60min of annealing under last vacuum.The heating rate of whole process controls
In 3 DEG C/min, and carried out under the protection of high pure nitrogen.
Raw material：
A1：Bibenzene tetracarboxylic
A2：Benzophenone tetracarboxylic
A3：Diphenyl ether tetraformic
A4：Diphenyl methane tetracarboxylic acid
A5：Naphthalene tetracid
A6：Bis trifluoromethyl diphenyl tetracarboxylic acid
A7：Hexamethylene tetracid
A8：Diphenyl sulfone tetraformic acid
A9：Tetracarboxylic acid benzimidazole
B1：Biphenyl tetramine
B2：Equal benzene tetramine
B3：Pyridine tetramine
B4：Penta tetramine of ring
B5：Carbazole tetramine
D1：Polyquaternium, preparation method are：
(1) preparation of compound 1
3 mole of urea and 25ml concentrated hydrochloric acids are added in the three-necked flask of 200ml distilled water, stirs, waits for that urea is completely dissolved,
Slowly it is added dropwise 1 mole 1 in whipping process, 1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- diacetyl react 5h, have precipitation to generate, and decompression is taken out
Filter, after distillation washing three times, acetone is washed 2 times, and compound 2 is dried to obtain.2 structural formula of the compound is as follows：
Above compound 2 and 30ml formaldehyde (mass fraction 37%) ultrasonic dissolution are added in three-necked flask in the dense of 30ml
In sulfuric acid, under agitation, heating reaction 2 hours, then vacuum distillation removes the water in reaction mixture, is warming up to 160
~170 DEG C, the reaction was continued 6~7 hours；After reaction, it is down to room temperature, reactant is poured into 300ml water, precipitation is precipitated,
It is filtered after placing 15min；Then precipitation is washed with 1000ml aqueous acetone solutions (mass fraction 25%) twice, sediment is used again again
The washing filtering of (mass fraction 80%) aqueous acetone solution, then with after 100ml water washings 3 times, dried with about 60 DEG C in vacuum drying oven
For 24 hours to get to compound 1.1 structural formula of the compound is：
Reaction process is represented by：
(2) preparation of polyquaternium
It is 1.2 that molar ratio is separately added into the three-necked flask equipped with electromagnetic agitation, reflux condensing tube and thermometer：1
2,8- dichloromethyl naphthalenes and dry tetramethyl butane diamine and 20ml acetonitriles, make it be completely dissolved in acetonitrile, are warming up to reflux, make
Polyquaternium autohemagglutination, reaction 20~for 24 hours, go out product with acetone precipitation, purified twice with ethyl alcohol/ether, is dried in vacuo white
Product 3.The structural formula of white product 3 is：
Reaction process is represented by：
100ml ethyl alcohol is added in three-necked flask, 20 parts of above-mentioned product is then added, magnetic stirs 16 parts of compound at room temperature
22~for 24 hours, and 6 parts of benzene and 5 parts of anhydrous Aluminum chlorides are then added, in ice salt bath, stirring, end capping reaction 10h, after reaction,
It is crossed after standing and filters out precipitation, adjust PH to 8, washing is dried in vacuo to obtain the modified polyquaternium D1 of compound 1, and number is divided equally
Son amount is 8720.Wherein compound 1 and tetramethyl butane diamine molar ratio are about 0.1：0.5.Reaction process is represented by：
D2：Polyquaternium, preparation method are：
(1) preparation of compound 1
3 mole of urea and 25ml concentrated hydrochloric acids are added in the three-necked flask of 200ml distilled water, stirs, waits for that urea is completely dissolved,
Slowly it is added dropwise 1 mole 1 in whipping process, 1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- diacetyl react 5h, have precipitation to generate, and decompression is taken out
Filter, after distillation washing three times, acetone is washed 2 times, and compound 2 is dried to obtain.2 structural formula of the compound is as follows：
Above compound 2 and 30ml formaldehyde (mass fraction 37%) ultrasonic dissolution are added in three-necked flask in the dense of 30ml
In sulfuric acid, under agitation, heating reaction 2 hours, then vacuum distillation removes the water in reaction mixture, is warming up to 160
~170 DEG C, the reaction was continued 6~7 hours；After reaction, it is down to room temperature, reactant is poured into 300ml water, precipitation is precipitated,
It is filtered after placing 15min；Then precipitation is washed with 1000ml aqueous acetone solutions (mass fraction 25%) twice, sediment is used again again
The washing filtering of (mass fraction 80%) aqueous acetone solution, then with after 100ml water washings 3 times, dried with about 60 DEG C in vacuum drying oven
For 24 hours to get to compound 1.1 structural formula of the compound is：
Reaction process is represented by：
(2) preparation of polyquaternium
It is 1.2 that molar ratio is separately added into the three-necked flask equipped with electromagnetic agitation, reflux condensing tube and thermometer：1
2,8- dichloromethyl naphthalenes and dry tetramethyl butane diamine and 20ml acetonitriles, make it be completely dissolved in acetonitrile, are warming up to reflux, make
Polyquaternium autohemagglutination, reaction 20~for 24 hours, go out product with acetone precipitation, purified twice with ethyl alcohol/ether, is dried in vacuo white
Product 3.The structural formula of white product 3 is：
Reaction process is represented by：
100ml ethyl alcohol is added in three-necked flask, 320 parts of above-mentioned white product is then added, compound 118 part is at room temperature
Magnetic stirring 22~for 24 hours, 6 parts of benzene and 5 parts of anhydrous Aluminum chlorides are then added, in ice salt bath, stirring, end capping reaction 10h, reaction knot
Shu Hou is crossed after standing and is filtered out precipitation, adjusts PH to 8, and washing is dried in vacuo and obtains the modified polyquaternium D2 of compound 1,
Number-average molecular weight is 9343.Wherein compound 1 and tetramethyl butane diamine molar ratio are about 0.3：0.5.Reaction process can indicate
For：
D3：Polyquaternium, preparation method are：
(1) preparation of compound 1
3 mole of urea and 25ml concentrated hydrochloric acids are added in the three-necked flask of 200ml distilled water, stirs, waits for that urea is completely dissolved,
Slowly it is added dropwise 1 mole 1 in whipping process, 1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2,3- diacetyl react 5h, have precipitation to generate, and decompression is taken out
Filter, after distillation washing three times, acetone is washed 2 times, and compound 2 is dried to obtain.2 structural formula of the compound is as follows：
Above compound 2 and 30ml formaldehyde (mass fraction 37%) ultrasonic dissolution are added in three-necked flask in the dense of 30ml
In sulfuric acid, under agitation, heating reaction 2 hours, then vacuum distillation removes the water in reaction mixture, is warming up to 160
~170 DEG C, the reaction was continued 6~7 hours；After reaction, it is down to room temperature, reactant is poured into 300ml water, precipitation is precipitated,
It is filtered after placing 15min；Then precipitation is washed with 1000ml aqueous acetone solutions (mass fraction 25%) twice, sediment is used again again
The washing filtering of (mass fraction 80%) aqueous acetone solution, then with after 100ml water washings 3 times, dried with about 60 DEG C in vacuum drying oven
For 24 hours to get to compound 1.1 structural formula of the compound is：
Reaction process is represented by：
(2) preparation of polyquaternium
It is 1.2 that molar ratio is separately added into the three-necked flask equipped with electromagnetic agitation, reflux condensing tube and thermometer：1
2,8- dichloromethyl naphthalenes and dry tetramethyl butane diamine and 20ml acetonitriles, make it be completely dissolved in acetonitrile, are warming up to reflux, make
Polyquaternium autohemagglutination, reaction 20~for 24 hours, go out product with acetone precipitation, purified twice with ethyl alcohol/ether, is dried in vacuo white
Product 3.The structural formula of white product 3 is：
Reaction process is represented by：
100ml ethyl alcohol is added in three-necked flask, 320 parts of above-mentioned white product is then added, 120 parts of compound is at room temperature
Magnetic stirring 22~for 24 hours, 6 parts of benzene and 5 parts of anhydrous Aluminum chlorides are then added, in ice salt bath, stirring, end capping reaction 10h, reaction knot
Shu Hou is crossed after standing and is filtered out precipitation, adjusts PH to 8, and washing is dried in vacuo to obtain the modified polyquaternium D3 of compound 1, number
Average molecular weight is 9880.Wherein compound 1 and tetramethyl butane diamine molar ratio are about 1：1.Reaction process is represented by：
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment 1：
By A1 and B2 in molar ratio 1:1 is dissolved in DMAC, and control mass fraction is between 5%~8%, magnetic agitation 2h,
Acid ammonium salt solution is made.D1 is added in poly- pyrrole throat precursor solution, spinning solution is made, making D1, concentration is about in spinning solution
It is 8%~12%, stirring 4h makes it uniformly mix, and adjusting A1, B2 and D1, total concentration is 10%~15% in the solution.
Spinning solution obtained above is subjected to electrostatic spinning, spinning voltage control is just extremely 15KV, and cathode is -2KV,
The distance of needle point to reception device is 25cm.It collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation, high speed
The flywheel of rotation is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.By obtained composite nano fiber presoma 60
DEG C vacuum drying 6h.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 100 DEG C of constant temperature 4h, 150 DEG C of constant temperature 5h, 250 DEG C under vacuum
Anneal 60min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 2：
By A2 and B1 in molar ratio 1:1 is dissolved in DMAC, and control mass fraction is between 8%~12%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D2 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D2 quality in spinning solution
Score about 12%~16%, stirring 4h so that it is uniformly mixed, adjust A2, B1 and D2 in the solution total mass fraction be 20%~
25%.
Spinning solution obtained above is subjected to electrostatic spinning, spinning voltage control is just extremely 15KV, and cathode is -8KV,
The distance of needle point to reception device is 25cm.It collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation, high speed
The flywheel of rotation is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.Obtained preceding composite nano fiber presoma is existed
60 DEG C of vacuum drying 6h.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 120 DEG C of constant temperature 4h, 150 DEG C of constant temperature 5h, 280 DEG C under vacuum
Anneal 50min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 3：
By A3 and B3 in molar ratio 1:1 is dissolved in DMF, and control mass fraction is between 12%~16%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D2 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D2 quality in spinning solution
Score about 16%~20%, stirring 4h so that it is uniformly mixed, adjust A3, B3 and D2 in the solution total mass fraction be 20%~
25%.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 10KV, needle point to reception device are 25cm.It collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 130 DEG C of constant temperature 3h, 180 DEG C of constant temperature 4h, 280 DEG C under vacuum
Anneal 40min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 4：
By A4 and B3 in molar ratio 1:1 is dissolved in DMP, and control mass fraction is between 16%~20%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D3 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D3 quality in spinning solution
Score about 20%~25%, stirring 4h so that it is uniformly mixed, adjust A4, B3 and D3 in the solution total mass fraction be 20%~
25%.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 12KV, needle point to reception device are that 25cm. collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 120 DEG C of constant temperature 4h, 200 DEG C of constant temperature 3h, is annealed at 300 DEG C
40min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 5：
By A5 and B4 in molar ratio 1:1 is dissolved in DMAC, and controlled concentration is between 12%~16%, magnetic agitation 2h, system
Obtain acid ammonium salt solution.Spinning solution is made in the D1 being added in poly- pyrrole throat precursor solution, and making D1, concentration is about in spinning solution
16%~20%, stirring 4h makes it uniformly mix, and adjusting A5, B4 and D1, total concentration is 25%~30% in the solution.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 12KV, needle point to reception device are 25cm.It collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 150 DEG C of constant temperature 2h, 200 DEG C of constant temperature 3h, 350 DEG C under vacuum
Anneal 30min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 6：
By A6 and B5 in molar ratio 1:1 is dissolved in DMF, and control mass fraction is between 12%~16%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D3 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D3 quality in spinning solution
Score about 20%~25%, stirring 4h so that it is uniformly mixed, adjust A6, B5 and D3 in the solution total mass fraction be 30%~
35%.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 15KV, needle point to reception device are that 25cm. collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 150 DEG C of constant temperature 2h, 200 DEG C of constant temperature 3h, is annealed at 350 DEG C
30min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 7：
By A7 and B3 in molar ratio 1:1 is dissolved in DMAC, and control mass fraction is between 8%~12%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D1 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D1 quality in spinning solution
Score is about 16%~20%, stirring 4h so that it is uniformly mixed, adjust A7, B3 and D1 in the solution total mass fraction be 25%~
30%.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 15KV, needle point to reception device are that 25cm. collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 120 DEG C of constant temperature 3h, 180 DEG C of constant temperature 4h, is annealed at 350 DEG C
30min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 8：
By A8 and B3 in molar ratio 1:1 is dissolved in DMP, and control mass fraction is between 8%~12%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D2 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D2 concentration in spinning solution
It is 8%~12%, stirring 4h makes it uniformly mix, and adjusting A8, B3 and D2, total concentration is 25%~30% in the solution.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 10KV, needle point to reception device are that 25cm. collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 150 DEG C of constant temperature 2h, 200 DEG C of constant temperature 3h, is annealed at 320 DEG C
30min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Embodiment 9：
By A9 and B5 in molar ratio 1:1 is dissolved in DMAC, and control mass fraction is between 8%~12%, magnetic agitation 2h,
Acid ammonium salt solution is made.The D3 being added in poly- pyrrole throat precursor solution is made spinning solution, makes D3 quality in spinning solution
Score be 20%~25%, stirring 4h so that it is uniformly mixed, adjust A9, B5 and D3 in the solution total mass fraction be 25%~
30%.
By spinning solution obtained above carry out electrostatic spinning, spinning voltage control be just extremely 15KV, cathode be-
The distance of 10KV, needle point to reception device are that 25cm. collects to obtain composite material nanometer tunica fibrosa using the roller of slow rotation,
High-speed rotating flywheel is collected to obtain the composite material nanometer fiber band of fiber-wall-element model.The composite nano fiber presoma that will be obtained
6h is dried in vacuo at 60 DEG C.
Composite nano fiber presoma obtained above is heat-treated, the quaternary in composite nano fiber presoma is made
Acid, quaternary amine molecule are from ordered arrangement is formed, and dehydrating polycondensation is at poly- pyrrole throat structure.Finally obtained is poly- pyrrole throat/polyquaternium
Composite nano fiber anti-biotic material.The program of heat treatment is preferably 120 DEG C of constant temperature 4h, 160 DEG C of constant temperature 3h, is annealed at 300 DEG C
40min.The heating rate of entire processing procedure is 3 DEG C/min, and is carried out under the protection of high pure nitrogen.
Comparative example 1：
The poly- pyrrole throat nanofiber that non-electrostatic methods obtains.
Comparative example 2：
The polyquaternium made from 2,8-, bis- chloropropyl naphthalenes and two tertiary amines.
Test method：
(1) pattern and diameter characterization：
It carries out observing poly- pyrrole throat/poly- season with scanning electron microscope (VEGA3LMU, Tescan companies of Czech)
The pattern and diameter of ammonium salt composite antibacterial material；
(2) heat decomposition temperature measures：
Using WRT-3P types thermogravimetric analyzer (the permanent Science and Technology Ltd. in Beijing), heating rate is 15 DEG C/min, test
Atmosphere is air.
(3) tensile property measures：
(newly thinking carefully material tests in Shenzhen with the miniature control electronic universal testers of CMT8102 by GB/T 1042-1992
Co., Ltd) it measures.
(4) fiber strength：
The diameter of single fiber is accurately measured using atomic force microscope (Shanghai Zhuo Lun Co., Ltds), and intensity uses
JQ03new type Miniature tensions instrument (upper marine morning Digital Equipment Co., Ltd) measures, and the result of each sample is by 10 this group of samples
The average value of product obtains.
(5) antibiotic property is tested：
Using the initial bacteria suspensions of 1ml as reference liquid, the initial number of wherein bacterium is measured.Initial bacterium solution：10g peptones,
Beef extract, 5g sodium oxide molybdenas, 500ml distilled water.
It takes in 10 conical flasks equipped with 100ml sterile waters and 1ml initial mixing bacterium solutions, is separately added into same molar
Embodiment, comparative example, then by conical flask be placed on oscillation case on, in 30 DEG C of constant incubator cultivate 48h after measure it is remaining
Alive bacteria amount, with the anti-microbial property of quantitative assessment material.The calculation formula of antibacterial is as follows：
Antibiotic rate=(reference liquid clump count-antimicrobial sample bacterium colony)/reference liquid clump count × 100%
Testing result is shown in Table 1.
As can be seen from the above data, compared with the poly- pyrrole throat material that non-electrostatic spinning obtains, using being based in the present invention
Poly- pyrrole throat/polyquaternium composite material of molecule assembling, not only solves the problem of poly- pyrrole throat is difficult to electrostatic spinning, and again gram
Polyquaternium insufficient strength, the bad problem of thermal stability are taken.The poly- pyrrole throat that the molecule construction from part based on electrospinning obtains/
Polyquaternium composite material not only has higher mechanical property and thermal stability, also good bactericidal effect, and obtain
Nanofiber is more uniform, filament strength higher, thus provides the advantageous effects of the present invention.
Example above-mentioned is merely illustrative, some features for explaining the method for the invention.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (9)
1. a kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material, including step：
Ammonium carboxylate salts including at least tetra-atomic acid and quaternary amine are provided, poly- pyrrole throat precursor solution is made；Before poly- pyrrole throat
It drives and the obtained spinning solution of polyquaternium is added in liquid solution, electrostatic spinning forms composite nano fiber presoma；
To being heat-treated under above-mentioned composite nano fiber presoma vacuum, poly- pyrrole throat/polyquaternium composite antibacterial material is made；
The polyquaternium is made by 2,8- dichloromethyls naphthalene, tetramethyl butane diamine and compound 1,1 structural formula of the compound
It is as follows：
2. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that the molar ratio of the compound 1 and tetramethyl butane diamine is 0.1~0.5: 0.5.
3. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that the tetra-atomic acid includes at least bibenzene tetracarboxylic, benzophenone tetracarboxylic, diphenyl ether tetraformic, diphenyl
Methane tetracarboxylic acid, bis trifluoromethyl diphenyl tetracarboxylic acid, naphthalenetetracarbacidic acidic, hexamethylene tetracid, tetracarboxylic acid benzimidazole and diphenyl sulphone (DPS)
One kind in tetracarboxylic acid.
4. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that the quaternary amine includes at least biphenyl tetramine, equal benzene tetramine, pyridine tetramine, penta tetramine of ring and carbazole four
One kind in amine.
5. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that the molar ratio of tetra-atomic acid and tetra-atomic acid is 0.8: 1~1: 0.8.
6. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that the quality of the polyquaternium accounts for the 50%~70% of poly- pyrrole throat/polyquaternium composite material.
7. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that ammonium carboxylate salt mass fraction is 5%~20% in the poly- pyrrole throat precursor solution.
8. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that polyquaternium mass fraction is 5%~25% in the spinning solution.
9. the molecule according to claim 1 based on electrospinning assembles the preparation of poly- pyrrole throat/polyquaternium composite antibacterial material
Method, which is characterized in that the condition of the heat treatment includes, first in 100~150 DEG C of 2~5h of constant temperature, then at 150~200 DEG C
2~5h of constant temperature, 250~350 DEG C of 10~60min of annealing under last vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510632542.5A CN105734712B (en) | 2015-09-29 | 2015-09-29 | A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510632542.5A CN105734712B (en) | 2015-09-29 | 2015-09-29 | A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105734712A CN105734712A (en) | 2016-07-06 |
| CN105734712B true CN105734712B (en) | 2018-07-17 |
Family
ID=56296189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510632542.5A Active CN105734712B (en) | 2015-09-29 | 2015-09-29 | A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105734712B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832596A (en) * | 2017-03-21 | 2017-06-13 | 安媛 | Environment protection type high-strength antibacterial polypropylene bio-based plastics master batch high and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059300A (en) * | 2013-01-23 | 2013-04-24 | 中国科学技术大学 | Polypyrron with sulfated side chain and preparation method of polypyrron |
| CN103087337A (en) * | 2011-11-01 | 2013-05-08 | 清华大学 | Polypyrrolone/sulfonated polymer composite proton exchange membrane material, and preparation method and application thereof |
-
2015
- 2015-09-29 CN CN201510632542.5A patent/CN105734712B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087337A (en) * | 2011-11-01 | 2013-05-08 | 清华大学 | Polypyrrolone/sulfonated polymer composite proton exchange membrane material, and preparation method and application thereof |
| CN103059300A (en) * | 2013-01-23 | 2013-04-24 | 中国科学技术大学 | Polypyrron with sulfated side chain and preparation method of polypyrron |
Non-Patent Citations (1)
| Title |
|---|
| 静电纺丝法制备聚吡咙纳米纤维;王晓琳等;《科技创新导报》;20091231;第5-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105734712A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9011739B2 (en) | Methods of continuously manufacturing polymide fibers | |
| DK2710173T3 (en) | PROCEDURE FOR THE PREPARATION OF LIGNIN-CONTAINING OUTLET FIBERS AND ALSO CARBON FIBERS | |
| CN101967279B (en) | Method for preparing reversible discolouring membrane made from polyaniline composite nanofiber | |
| JP4647680B2 (en) | Easy-dyeing meta-type wholly aromatic polyamide fiber | |
| CN105709611B (en) | A kind of poly- pyrrole throat/compound porous catalytic membrane of polyimides and preparation method thereof | |
| CN107268109A (en) | The manufacture method of polyimide fiber and polyimide fiber | |
| CN109666979B (en) | Preparation method of polyimide nanofiber | |
| CN105709612B (en) | A kind of preparation method of poly- pyrrole throat/aromatic polyamides composite membrane based on molecule assembling | |
| CN105734712B (en) | A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyquaternium composite antibacterial material | |
| CN105732984B (en) | A kind of preparation method of poly- pyrrole throat/Sulfonated Polyethersulfone Proton Exchange Membrane | |
| CN107012532B (en) | A kind of preparation method of mosquito repellent spandex | |
| Wang et al. | Preparation and characterization of electrospun poly (phthalazinone ether nitrile ketone) membrane with novel thermally stable properties | |
| CN107675281A (en) | The preparation method of PVP/PAN nano-composite fibers | |
| CN105714472B (en) | A kind of poly- pyrrole throat/sulfonated poly (phenylene oxide) composite membrane and preparation method | |
| EP0668942B2 (en) | Fibers and films of improved flame resistance | |
| CN105714411B (en) | A kind of preparation method of poly- pyrrole throat/polyether sulfone/carbon nanometer pipe ternary composite material | |
| CN105714400B (en) | A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat nanofiber | |
| CN105821662B (en) | A kind of preparation method of poly- pyrrole throat/TPE composite materials based on molecule assembling | |
| CN105714410B (en) | A kind of preparation method and its product of poly- pyrrole throat/polyimide composite fiber based on molecule assembling | |
| CN106637472B (en) | The method that Electrospinning Method prepares polyimides micrometer fibers | |
| CN105714409B (en) | A kind of molecule based on electrospinning assembles the preparation method of poly- pyrrole throat/polyimides composite nano fiber | |
| CN107151833B (en) | A kind of polyimide fine denier fiber and preparation method thereof | |
| CN102560894A (en) | Production method of polybenzoxazole nanofiber nonwoven fabric and its application | |
| Duan et al. | Heat and Solvent Resistant Electrospun Polybenzoxazole Nanofibers from Methoxy‐Containing Polyaramide | |
| CN110396730A (en) | A kind of electrically conductive polyaniline blended fiber and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240327 Address after: 330000, No. 1001, West Seventh Road, Yaohu, Nanchang hi tech Industrial Development Zone, Nanchang City, Jiangxi Province Patentee after: JIANGXI ADVANCED NANOFIBER S&T Co.,Ltd. Country or region after: China Address before: 330095 No.99 Ziyang Avenue, Nanchang City, Jiangxi Province Patentee before: Jiangxi Normal University Country or region before: China |