CN1272479C - Inorganic granular soliquoid for modified Nitrilon, preparing method and use thereof - Google Patents
Inorganic granular soliquoid for modified Nitrilon, preparing method and use thereof Download PDFInfo
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- CN1272479C CN1272479C CN 03141473 CN03141473A CN1272479C CN 1272479 C CN1272479 C CN 1272479C CN 03141473 CN03141473 CN 03141473 CN 03141473 A CN03141473 A CN 03141473A CN 1272479 C CN1272479 C CN 1272479C
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Abstract
The present invention relates to spinning suspension liquid. The suspension liquid is composed of 0.5 to 8% weight of nanometer metal oxide, 0 to 2% weight of polyethyleneglycol, dispersing agents with the weight of 2 to 10% of that of the nanometer metal oxide and deionized water or water solution containing 9 to 15% of NaSCN or 40 to 60% of N, N-dimethylformamide or water solution of N-dimethylformamide, wherein polyethylenimine is used as the dispersing agents. The suspension liquid is prepared by stirring and mixing the substances, the suspension liquid is relatively stable, the volume fraction of sedimentation is smaller than 6%, and the particle diameter can reach about 130 nm. The suspension liquid is used as a coagulating bath, a prestretching bath, a preheating bath and a thermal stretching bath in the spinning forming of polyacrylonitrile or is used for spinning antistatic polyacrylonitrile fibers in a bath groove before fiber drying. The large-scale production of antistatic polyacrylonitrile fibers can be carried out under the condition of no change of original polyacrylonitrile production devices. The fiber has the advantages of good antistatic performance and high mechanical performance, and can be widely used for antistatic working clothes, dustproof working clothes, aseptic working clothes and explosion-proof special working clothes of the departments of oil refining and petroleum and carpets, sheets, copying belts, etc.
Description
Technical field
The invention belongs to Polymer Synthesizing fibre technology field, be specifically related in polyacrylonitrile fibre spinning moulding process, contain the preparation method and the purposes of the nanometer metal oxide powder suspension that improves the polyacrylonitrile fibre antistatic behaviour.
Background technology
Polyacrylonitrile fibre is soft, mildew-resistant, mothproof, and very superior light resistance, radiation resistance and corrosion resistance are arranged, bulkiness and warmth retention property are better than other synthetic fiber, therefore be widely used in dress ornament, decoration and industrial circle, its output is positioned at the 4th in synthetic fiber at present.But because intrinsic hydrophobicity and the insulating properties of polyacrylonitrile fibre, electrostatic phenomenon is serious: fiber after add man-hour because of friction produces static, make the boundling difficulty and be wrapped on the parts, product is subject to stain and dust suction; Make human body that uncomfortable sensation is arranged when wearing, the part can cause that scytitis and blood pH raise; Under the low humidity condition, static can also cause fire, and these have seriously limited the application of polyacrylonitrile in a lot of fields.Therefore, people have carried out extensive studies to giving the anti-static polyacrylonitrile aspect.
When improving the polyacrylonitrile fibre antistatic property, mainly contain following problem: 1. how when improving the fiber antistatic behaviour, also keep original excellent mechanical property of fiber and serviceability; 2. how to improve problems such as when adopting the inorganic antistatic material, easily mixing inhomogeneous, obstruction spinning head with the polyacrylonitrile fibre blend.
For reducing the antistatic effect of gathering of polyacrylonitrile, make the antistatic polypropylene nitrile, often adopt following measure: 1 utilizes chemical method to carry out antistatic modified to polyacrylonitrile.1. with the function comonomer of possess hydrophilic property, antistatic behaviour, as the vinyl monomer that contains functional groups such as hydroxyl, ether, carboxyl, amide groups, substituted amido is direct and acrylonitrile carries out copolymerization, thereby on the polymer macromolecule chain, introduce ionogenic group, to reach anlistatig purpose, for example clock spins high moisture absorption polyacrylonitrile Aqualon, the Donava that Bayer A.G produces; 2. handle polyacrylonitrile fibre with the DMF that contains 2% NaOH, cyano group and alkali effect are hydrolyzed into carboxyl and amide groups, the hygroscopicity of raising fiber, thus make Process of Antistatic PAN Fiber.But the shortcoming of this Process of Antistatic PAN Fiber is bigger to the dependence of ambient humidity, and is undesirable at the weather conditions antistatic property of drying.Apply antistatic material at fiber surface during 2 fiber finishings.Mainly contain the PAN that Celanese Corp. crosses heat stabilisation process and be dipped in the cuprous ion source, then handle, utilize on the big molecule of PAN-CN and monovalence copper (Cu with vulcanizing agent
+) complexing, and with active sulfur (S
2-) reaction, form fine and close conductive layer Cu at fiber surface
2S can make the resistivity of fiber reduce to 10
2Below the Ω cm, and has the incombustible performance of match flame; In addition, also have methods such as fiber usefulness antistatic agent solution post processings.But the shortcoming of post treatment method is that the feel of fiber is poor, and washability is bad.
3 sneak into materials such as small amounts of carbon black, metal oxide in spinning solution.Mitsubishi rayon, clock spin etc. and to add in the polyacrylonitrile spinning solution after company is dispersed in carbon black in the organic solvent, have improved the antistatic behaviour of polyacrylonitrile fibre greatly, major defect be the antistatic fibre that makes the color is too dark, can only be used to dye dark cloth.And the electric conductivity of other ordinary white metal oxides is lower, therefore have in preparation and need add a large amount of white metal oxides when excellent antistatic capability has polyacrylonitrile fibre, adopt general spinning technique, easily stop up spinning head during spinning, the fibrous mechanical property that makes is very poor, have only and adopt complicated composite spinning technology to prepare Process of Antistatic PAN Fiber with skin-core structure, just has mechanical property preferably, but this method use cost height has seriously limited the extensive use of this kind method.
Develop new suspension, in spinning process, add,, caused people's very big interest so that can produce the multifunction polyacrylonitrile fibre that not only has antistatic behaviour but also keep original mechanical property of fiber and stainability.
Summary of the invention:
The purpose of this invention is to provide a kind of nanoparticle suspension that is used for spinning process.
Purpose of the present invention also provides a kind of preparation method of above-mentioned spinning suspension.
Another object of the present invention provides a kind of purposes of above-mentioned spinning suspension.Be used for the preparation of the polypropylene arm antistatic fibre of modification.
In order to improve the antistatic behaviour of polyacrylonitrile fibre, solve and easily stop up spinning head, degradation problem under fibrous mechanical property, the dyeability when adopting co-blended spinning.In the spinning technique flow process of common polyacrylonitrile fibre, the present invention is with the mixture (nano ATO) of nano-stannic oxide and antimony oxide, cupric oxide, white nano-metal-oxide such as titanium dioxide is as antistatic material, by adding suitable dispersant, with its relatively stable water that is scattered in, perhaps contain thiocyanic acid and receive (NASCN), dimethyl sulfoxide (DMSO) (DMSO) or N, in the aqueous solution of the polyacrylonitrile solvent of dinethylformamide (DMF) etc., again with this suspension as the coagulating bath in the polyacrylonitrile spinning moulding process, predraft is bathed, pre-heating bath, in the preceding a certain suitable bath of heat stretching bath or fiber drying, with the concentration difference of nano metal vapour in polyacrylonitrile fibre and suspension is driving force, nano-metal-oxide can be spread, migration enters fibrous inside, thereby gives the fiber antistatic behaviour and keep its original mechanical property and dyeability.
The composition of suspension provided by the invention has following several types:
1, by percetage by weight be 0.5-15% nano-metal-oxide, with respect to the percetage by weight of nano-metal-oxide weight be 2-10% dispersant, all the other form for deionization;
2, be the polyethylene glycol of nano-metal-oxide, the 1-2% of 0.5-15%, be the 2-10% dispersant that by percetage by weight all the other are that deionized water is formed with respect to the percetage by weight of nano-metal-oxide weight;
3 is the nano-metal-oxide of 0.5-15% by percetage by weight, percetage by weight with respect to nano-metal-oxide weight is the dispersant of 2-10%, and percetage by weight is that the aqueous solution of the NaSCN aqueous solution of 9-15% or DMF that percetage by weight is 40-60% or DMSO is formed.
Suspension of the present invention is the metastable suspension of particle diameter in the 20-150 nanometer.
The preparation method of suspension of the present invention is: with percetage by weight is that the nano-metal-oxide of 0.5-15% adds deionized water or percetage by weight is in the NaSCN aqueous solution of 9-15%, or percetage by weight is in the DMF aqueous solution of 40-60%, homogenizer stirred 30-60 minute, adding is the dispersant of 2-10% with respect to the percetage by weight of nano-metal-oxide weight, high-speed stirred 30-60 minute again, or add the polyethylene glycol of the 0-2% of suspension weight again, make the metastable suspension of particle diameter about 130 nanometers.Technological process as shown in Figure 1.
Suspension of the present invention can be used for the spinning technique flow process of Process of Antistatic PAN Fiber: at the spinning technique of general polyacrylonitrile fibre, above-mentioned suspension is bathed, added the bath that contains above-mentioned suspension before pre-heating bath, heat stretching bath or the fiber drying and realize as the coagulating bath in the polyacrylonitrile spinning moulding process, predraft.
Also can in suspension, add polyethylene glycol (PEG) back as washing before the spinning technique flow process of pre-heating bath: spinning solution → coagulating bath shapings → predraft (be dispersed in above-mentioned nano-metal-oxide in the deionized water and add PEG) → washing → pre-heating bath → hot-stretch → oil → compacting by drying → curling → HEAT SETTING → cut-out → Process of Antistatic PAN Fiber.
In the method for the invention, the addition of described nano-metal-oxide is the 0.5-15% of suspension weight, and optimum amount is at 4-8%, and dispersant is 4-8% with respect to the optimum weight percent of the weight of nano-metal-oxide.
Add the spinning that also can be used as pre-heating bath before the washing behind the PEG in suspension, the consumption of described polyethylene glycol (PEG) is the 1-2% of the weight of suspension, and its molecular weight is 1000-4000 for well.
Suspension of the present invention is fit to the spinning process of the Process of Antistatic PAN Fiber of the one-step method of NaSCN, DMF or DMSO or two step method etc.
Suspension of the present invention also is fit to use the spinning technique of the Process of Antistatic PAN Fiber that comprises methods such as dry method, wet method, frozen glue method.
Description of drawings
Fig. 1 is preparation technology's flow chart of suspension of the present invention;
Fig. 2 is the laser particle analyzer figure as a result of a kind of suspension of the present invention;
Fig. 3 is the transmission electron microscope results figure of a kind of suspension of the present invention.
Use the Process of Antistatic PAN Fiber of suspension preparation of the present invention to have excellent antistatic energy, higher mechanical property, can under the situation that does not change original polyacrylonitrile production equipment, carry out large-scale production.This Process of Antistatic PAN Fiber can be widely used in particular job clothes of the explosion-proof type of antistatic Work Clothes, dustless Work Clothes, aseptic Work Clothes, oil refining and oil sector, and carpet, coverlet, copying band etc.
The specific embodiment:
Embodiment 1
In being 10% the NaSCN aqueous solution, weight fraction adds nano ATO, the percetage by weight of ATO is 12%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, make suspension, sample number into spectrum is No. 1.
Add nano ATO in deionized water, the percetage by weight of ATO was 2%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, makes suspension, and sample number into spectrum is No. 2.
Embodiment 3
Add nano ATO in deionized water, the percetage by weight of ATO was 4%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, makes suspension, and sample number into spectrum is No. 3.
Add nano ATO in deionized water, the percetage by weight of ATO was 8%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, makes suspension, and sample number into spectrum is No. 4.
Add nano ATO in deionized water, the percetage by weight of ATO was 4%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 2% (with respect to ATO), high-speed stirred is 30 minutes again, makes suspension, and sample number into spectrum is No. 5.
Add nano ATO in deionized water, the percetage by weight of ATO was 4%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 8% (with respect to ATO), high-speed stirred is 30 minutes again, makes suspension, and sample number into spectrum is No. 6.
Embodiment 7
In being 10% the NaSCN aqueous solution, weight fraction adds nano ATO (about 130 nanometers), the percetage by weight of ATO is 12%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be cooled to about 5 ℃, obtain coagulating bath (the ATO particle diameter is about 140 nanometers in the bath), carry out spinning by following spinning technique then, sample number into spectrum is 8: spinning solution → coagulating bath shaping (above-mentioned interpolation suspension in the coagulating tank) → predraft → washing → pre-heating bath → hot-stretch → oil → compacting by drying → curl → HEAT SETTING → cut-out → Process of Antistatic PAN Fiber.
Embodiment 8
In deionized water, add nano ATO (about 130 nanometers), the percetage by weight of ATO is 0.5%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be heated to about 60 ℃, obtain pre-heating bath (the ATO particle diameter is about 130 nanometers in the bath), PAN is dissolved in the NaSCN solution, and as spinning solution, carry out spinning by following spinning technique, sample number into spectrum is 9: spinning solution → coagulating bath is shaped → pre-heating bath (adding above-mentioned suspension in the bath) → hot-stretch → washing → compacting by drying → Process of Antistatic PAN Fiber.
Embodiment 9
In deionized water, add nano ATO (about 130 nanometers), the percetage by weight of ATO is 5%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be heated to about 60 ℃, obtain pre-heating bath (the ATO particle diameter is about 130 nanometers in the bath), PAN is dissolved in the NaSCN solution, and as spinning solution, carry out spinning by following spinning technique, sample number into spectrum is 10: spinning solution → coagulating bath is shaped → pre-heating bath (adding above-mentioned suspension in the bath) → hot-stretch → washing → compacting by drying → Process of Antistatic PAN Fiber.
In deionized water, add nano ATO (about 130 nanometers), the percetage by weight of ATO is 8%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be heated to about 60 ℃, obtain pre-heating bath (the ATO particle diameter is about 130 nanometers in the bath), PAN is dissolved in the NaSCN solution, and as spinning solution, carry out spinning by following spinning technique, sample number into spectrum is 11: spinning solution → coagulating bath is shaped → pre-heating bath (adding above-mentioned suspension in the bath) → hot-stretch → washing → compacting by drying → Process of Antistatic PAN Fiber.
Embodiment 11
In deionized water, add nano ATO (about 130 nanometers), the percetage by weight of ATO is 8%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, add weight fraction then and be 1% polyethylene glycol, after being stirred to dissolving, this suspension is heated to about 60 ℃, obtain pre-heating bath (the ATO particle diameter is about 130 nanometers in the bath), PAN is dissolved in the NaSCN solution, and as spinning solution, 7. carry out spinning by spinning technique, sample number into spectrum is 12.
Embodiment 12
In deionized water, add nano ATO (about 130 nanometers), the percetage by weight of ATO is 4%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be heated to about 60 ℃, obtain pre-heating bath (the ATO particle diameter is about 130 nanometers in the bath), PAN is dissolved in the NaSCN solution, and as spinning solution, carry out spinning by following spinning technique, sample number into spectrum is 13: spinning solution → coagulating bath shaping → predraft → washing → pre-heating bath (adding above-mentioned suspension in the bath) → hot-stretch → oil → compacting by drying → curl → HEAT SETTING → cut-out → Process of Antistatic PAN Fiber.
Embodiment 13
In deionized water, add nano ATO (about 130 nanometers), the percetage by weight of ATO is 4%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be heated to about 60 ℃, obtain pre-heating bath (the ATO particle diameter is about 130 nanometers in the bath), PAN is dissolved in the DMF solution, and as spinning solution, carry out spinning by following two kinds of spinning techniques, sample number into spectrum is 14: spinning solution → coagulating bath is shaped → pre-heating bath (adding above-mentioned suspension in the bath) → hot-stretch → washing → compacting by drying → antistatic polypropylene nitrile fibre; Perhaps spinning solution → coagulating bath shaping → predraft → washing → pre-heating bath (adding above-mentioned suspension in the bath) → hot-stretch → oil → compacting by drying → curl → HEAT SETTING → cut-out → Process of Antistatic PAN Fiber.
Embodiment 14
In being 55% the DMF aqueous solution, weight fraction adds nano ATO, the percetage by weight of ATO is 12%, with homogenizer making beating 30 minutes, adding weight fraction in suspension is the polyethylene of dispersing agent imines of 4% (with respect to ATO), high-speed stirred is 30 minutes again, be cooled to about 5 ℃, obtain coagulating bath, following then carries out spinning by spinning technique, and sample number into spectrum is 15: spinning solution → coagulating bath shaping (above-mentioned interpolation suspension in the coagulating tank) → predraft → washing → pre-heating bath → hot-stretch → oil → compacting by drying → curl → HEAT SETTING → cut-out → Process of Antistatic PAN Fiber.
Suspension embodiment stability of sample, dispersiveness and viscosity test result are as shown in the table:
| Sample number into spectrum | Settling volume mark (%) | Average grain diameter (nm) | Viscosity (mps) |
| 1 | 32％ | 148 | 1.45 |
| 2 | 14％ | 140 | 1.1 |
| 3 | 9.6％ | 137 | 1.12 |
| 4 | 5.6％ | 129 | 1.15 |
| 5 | 10.0％ | 145 | 1.04 |
| 6 | 9.6％ | 133 | 1.2 |
The laser particle analyzer of No. 4 embodiment samples, transmission electron microscope results are shown in accompanying drawing 2 and 3.
As a comparison, numbering 7 samples is conventional polyacrylonitrile fibre sample, and the test result of the relevant performance of all the other each embodiment samples is listed in the following table.
| Sample number into spectrum | Resistivity Ω cm (20 ℃ of RH65%) | Intensity cN/dtex | Spinnability |
| 7 | ～10 14 | 2.65～3.53 | Good |
| 8 | 1.8×10 7 | 1.97 | Better |
| 9 | 8.9×10 9 | 2.92 | Good |
| 10 | 7.6×10 8 | 2.82 | Good |
| 11 | 5.5×10 8 | 2.70 | Good |
| 12 | 1.2×10 9 | 2.57 | Good |
| 13 | 1.3×10 8 | 2.4 | Good |
| 14 | 2.7×10 8 | 2.54 | Better |
Claims (7)
1, a kind of spinning suspension, it is made up of following substances respectively:
1) by percetage by weight be 0.5-15% nano-metal-oxide, with respect to the percetage by weight of nano-metal-oxide weight be 2-10% dispersant, all the other form for deionized water;
Or 2) be the polyethylene glycol of nano-metal-oxide, the 1-2% of 0.5-15%, be the dispersant of 2-10% that by percetage by weight all the other are that deionized water is formed with respect to the percetage by weight of nano-metal-oxide weight;
Or 3) by percetage by weight be the nano-metal-oxide of 0.5-15%, percetage by weight with respect to nano-metal-oxide weight is the dispersant of 2-10%, and the NASCN aqueous solution of percetage by weight 9-15% or percetage by weight are that the DMF of 40-60% or the aqueous solution of DMSO are formed;
Described nano-metal-oxide is the mixture of nano-stannic oxide and antimony oxide.
2, a kind of spinning suspension as claimed in claim 1, the particle diameter that it is characterized in that particulate in the described suspension is the 20-150 nanometer.
3, a kind of spinning suspension as claimed in claim 1, the content that it is characterized in that described nano-metal-oxide is the 4-8% of suspension weight.
4, a kind of spinning suspension as claimed in claim 1 is characterized in that the 2-10% of described dispersant with respect to the weight of nano-metal-oxide.
5, spinning suspension as claimed in claim 1 is characterized in that described molecular weight polyethylene glycol is 1000-4000.
6, the preparation method that receives of a kind of spinning suspension as claimed in claim 1, it is characterized in that percetage by weight with respect to the weight of nano-metal-oxide is the polyethyleneimine: of 2-10% and is scattered in water or is scattered in the N that the thiocyanic acid that contains 9-15% weight is received or is scattered in 40-60% weight by the nano-metal-oxide of the 0.5-15% of the polyethylene glycol of the 0-2% of dispersant, suspension weight, suspension weight is relatively stable, in the aqueous solution of the dimethyl sulfoxide (DMSO) of dinethylformamide or 40-60% weight, mix.
7, as the purposes of claim 1 or 7 described a kind of spinning suspension, the coagulating bath, predraft that it is characterized in that being used for Process of Antistatic PAN Fiber spinning moulding process bathed, carry out the spinning of Process of Antistatic PAN Fiber before pre-heating bath, heat stretching bath or the fiber drying in the bath.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141473 CN1272479C (en) | 2003-07-08 | 2003-07-08 | Inorganic granular soliquoid for modified Nitrilon, preparing method and use thereof |
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|---|---|---|---|
| CN 03141473 CN1272479C (en) | 2003-07-08 | 2003-07-08 | Inorganic granular soliquoid for modified Nitrilon, preparing method and use thereof |
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| CN1272479C true CN1272479C (en) | 2006-08-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103726113A (en) * | 2013-12-25 | 2014-04-16 | 中国科学院化学研究所 | Novel fiber-drawing hot bath medium and application thereof |
| CN106480529A (en) * | 2015-08-24 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of organic inorganic hybridization Process of Antistatic PAN Fiber |
| CN105951212A (en) * | 2016-05-23 | 2016-09-21 | 太和县蓝翎养殖有限公司 | Airy artificial wig fiber containing peacock feather |
| CN106868621A (en) * | 2017-02-15 | 2017-06-20 | 叶长青 | Anti-electric building safety net |
| CN106902638B (en) * | 2017-04-13 | 2019-07-19 | 淮阴师范学院 | A kind of attapulgite-class graphite phase carbon nitride-polyvinylidene fluoride nanometer composite hyperfiltration membrane and its preparation method and application |
| CN106902650B (en) * | 2017-04-13 | 2018-09-14 | 淮阴师范学院 | A kind of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane and its preparation method and application |
| CN112725911B (en) * | 2020-12-22 | 2022-06-28 | 南通新帝克单丝科技股份有限公司 | High-dpf polyamide industrial yarn for electronic components and production method thereof |
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