CN103789864A - Preparation method of high-strength, high-modulus and high-temperature-resistant polyurethane elastic fiber - Google Patents
Preparation method of high-strength, high-modulus and high-temperature-resistant polyurethane elastic fiber Download PDFInfo
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Abstract
The invention relates to a preparation method of high-strength, high-modulus and high-temperature-resistant polyurethane elastic fiber. The preparation method comprises the steps of blending polyurethane polymer stock solution with radical initiator (particularly, the initiators which decompose dialkyl peroxide at high temperature) to form spinning stock solution, decomposing the radical initiator in the spinning stock solution to release free radical when high-temperature dry spinning is carried out, and triggering polyurethane polymer to form polyurethane elastic fiber with micro-crosslink among molecules. The polyurethane elastic fiber prepared by the method has the characteristics of being high in strength, high in modulus and good in high temperature resistance, and the characteristics can prevent the silks from being broken when the polyurethane elastic fiber is unwound at high speed, can prevent the silks from being internally broken when being dyed under high temperature, so that the fiber is specifically used as the raw materials of the high-temperature dyeing fabrics and the elastic fiber of the durable and wearproof clothes for military use.
Description
Technical field
The present invention relates to the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus.
Background technology
Polyurethane elastomeric fiber is a kind of synthetic fiber with the excellent properties such as high extension at break, high elasticity response rate, is widely used in the field such as knitted apparel, household articles.Polyurethane elastomeric fiber is when after carrying out, road is weaved, if silk TENSILE STRENGTH is low, stretch modulus is little, when high-speed unwinding, the faults such as fracture of wire easily occur and affects weaving efficiency; When rear road high-temp dyeing, if silk mechanical property is poor with resistance to elevated temperatures, the silk phenomenon that easily occurs to break in dyeing in fabric; When follow-up use, particularly, in the time that it takes elastomer silk as high-elastic jeans etc., need especially fiber to possess excellent warp tensile strength and modulus, just can make clothing there is good property strong to stand up to hard wear.Visible, polyurethane elastomeric fiber need possess that excellent mechanical property and resistance to elevated temperatures could ensure that it carries out that high-speed unwinding is weaved, high-temp dyeing, the instructions for use such as endurable.
Traditional polyurethane elastomeric fiber mechanical property and heat resistance method of modifying mainly concentrate on polymerization molecule inner structure modification in early stage and the intermolecular cross-linking modification of polymerization later stage.Molecule inner structure modification in polymerization early stage is mainly to carry out in-situ polymerization by the design of molecule segment to regulate the contamination etc. of soft or hard section component in polyurethane molecular to carry out chemical modification, also can be undertaken micro-cross-linking modified by introduce the means such as polyfunctional group alcohols and amine in molecule; The intermolecular cross-linking modification of polymerization later stage is mainly to be undertaken processing modifiedly by add the auxiliary agents such as crosslinking agent in polyether polyols with reduced unsaturation, comprises that isocyanate group and imino group cross-linking reaction, isocyanate group or hydroxy-end capped base polyurethane prepolymer for use as are crosslinked, alkoxysilane-terminated base polyurethane prepolymer for use as hydrolytic crosslinking, ethenyl blocking base polyurethane prepolymer for use as are crosslinked, crosslinked with functional side group base polyurethane prepolymer for use as, sulfur cross-linking, formaldehyde crosslinking etc.
Radical initiator refers to the reagent that can produce free radical in radical reaction, and conventional have metal peroxides type free base initator, halogen radical initiator, organic peroxide type free base initator, an azo radical initiator etc.Wherein purposes is organic peroxide type free base initator the most widely, this compounds is the compound that contains peroxide bridge O-O, peroxide bridge is a kind of very special chemical functional group, its be heated after homolysis, produce free radical, this free radical has very high reactivity, can be cross-linked by initiated polymerization thing.Radical initiator is except causing vinyl monomer polymerization as free radical donor, also be widely used in the sulfuration and crosslinked modulus and heat-resisting weatherability with lifting plastics and rubber of plastics and rubber, as dicumyl peroxide is widely used in the crosslinked of electric wire, cable jacket and insulating barrier PE as crosslinking agent, cumyl peroxide is cross-linking modified etc. for EPDM/PP thermoplastic elastomer (TPE) as crosslinking agent.
In theory, radical initiator can cause polyether polyols with reduced unsaturation and be cross-linked, and its main mechanism of crosslinking is (take cumyl peroxide DCP as example):
1) initator pyrolysis is free radical:
2) form free polymer readical:
3) free polymer readical coupling forms crosslinked:
In addition, free radical also can cause Ruan Duan district segment slight being cross-linked occurs, and the crosslinked covalent bond that hard section, Ruan Duan district form, will strengthen the heat resistance of polyether polyols with reduced unsaturation greatly.
Free radical is less as the report of crosslinking agent modified polyurethane goods, and substantially concentrates on fusion method modified polyurethane plastic master batch and plastic products, uses free radical to spin polyurethane elastomeric fiber as crosslinking agent modification dry method and rarely has especially report.This patent creatively adopts radical initiator, particularly pyrolytic organic peroxide type free base initator is as crosslinking agent, dry method is spun to polyurethane elastomeric fiber and carry out radical crosslinking modification, stretch modulus and the TENSILE STRENGTH of polyurethane elastomeric fiber are successfully promoted, and the heat resistance of fiber is also significantly enhanced, made a kind of high-strength and high-modulus fire resistant special type polyurethane elastomeric fiber, fiber has higher economic worth.
Summary of the invention
Technical problem: the preparation method who the object of this invention is to provide the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus, the polyurethane elastomeric fiber that adopts the method to prepare has high strength, high-modulus and high-temperature stability, these performances are disconnected etc. helpful in silk when fracture of wire, high-temp dyeing when preventing polyurethane elastomeric fiber high-speed unwinding, and fiber spy is suitable as high-temp dyeing fabric raw material and clothing strong to stand up to hard wear elastomer uses.
Technical scheme: the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus of the present invention, the method is to make polyurethane spinning solution by polyether polyols with reduced unsaturation stoste and radical initiator blend, in polyurethane spinning solution, radical initiator is in the time of high-temperature dry spinning, decompose and discharge free radical, initiation polyether polyols with reduced unsaturation forms finally has micro-crosslinked polyurethane elastomeric fiber, wherein:
Polyurethane spinning solution is to form performed polymer by PTMEG or polyester-diol and vulcabond through condensation addition polymerization, performed polymer forms polyether polyols with reduced unsaturation by diamine, the common chain extension of chain terminating agent, then by polyether polyols with reduced unsaturation and radical initiator and other additive blend and make; Above-mentioned polyurethane spinning solution adopts dry spinning technology to be spun into final fiber.
Described PTMEG is polytetrahydrofuran diol, polyoxygenated alkene glycol or copolyether glycol, and PTMEG has the molecular weight of 1000-5000.
Described vulcabond is methyl diphenylene diisocyanate MDI, toluene di-isocyanate(TDI) TDI, naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI, poly methylene poly phenyl poly isocyanate PAPI or 4,4, one dicyclohexyl methyl hydride diisocyanate HMDI.
In described performed polymer, vulcabond isocyanate groups and PTMEG oh group mol ratio are 1.65-2.50.
Described diamine is 1,2-ethylenediamine EDA, 1,2-propane diamine PDA, 1-methyl isophthalic acid, 5-pentanediamine or hexamethylene diamine or p-phenylenediamine (PPD); Described chain terminating agent comprises diethylamine DEA or n-butanol.
In described polyether polyols with reduced unsaturation, the amino molal quantity+phosphonium flame retardant terminal hydroxy group of dihydroxylic alcohols terminal hydroxy group molal quantity+diamine end, the final agent molal quantity=isocyanate groups of carboxyl molal quantity+1/2 chain molal quantity; In described chain extension solution, the amino molal quantity/chain terminating agent end group of diamine number=14.5-21.0.
Described polyether polyols with reduced unsaturation has the number-average molecular weight of 80000-500000.
Described radical initiator is organic peroxide type free base initator, particularly pyrolytic organic peroxide type free base initator, and radical initiator consumption is the 0.05-1.5% of PTMEG or polyester-diol+isocyanates+chain extension amine gross weight.
Described organic peroxide type free base initator comprises carboxylic acid peroxide, alkyl peroxide, ketone peroxide, ester class peroxide or acyl class peroxide, wherein:
1), alkyl peroxide comprises di-tert-butyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-, cumyl t-butyl peroxide, cumyl peroxide, 1,4-bis-(2-tert-butyl peroxy base isopropyl) benzene or 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane;
2), ketone peroxide comprises t-butyl peroxy ketal or tertiary pentyl peroxy ketal;
3), ester class peroxide comprises the peroxidating tert-butyl ester, tert-butyl hydroperoxide trimethylacetic acid ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, the peroxidating laurate tert-butyl ester, peroxidized t-butyl perbenzoate or the peroxidating isooctyl acid tert-butyl ester;
4), acyl class peroxide comprises benzoyl peroxide, lauroyl peroxide, stearoyl or peroxidating chlorination benzoyl.
Described other additive comprises resistance to xanthochromia agent, lubricant, ultra-violet absorber and ester class antioxidant; Described polyurethane spinning solution mass concentration is 30-45%; Described polyurethane elastomeric fiber dawn number is 20D, 30D, 40D, 140D, 840D or 1120D.
Beneficial effect: the present invention relates to the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus, adopt the method can effectively prepare the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus.The innovative point of this method is, creatively by radical initiator and polyether polyols with reduced unsaturation blend, be prepared into spinning solution, in the time of high-temperature dry spinning, radical initiator decomposes in spinning solution, discharge free radical, cause the intermolecular formation of polyether polyols with reduced unsaturation micro-crosslinked, and then promote intensity, modulus and the heat resistance of fiber.The polyurethane elastomeric fiber of preparing by the method, while being difficult for fracture of wire, high-temp dyeing when high-speed unwinding, silk is disconnected in being difficult for, and spy is suitable as high-temp dyeing fabric raw material and clothing strong to stand up to hard wear elastomer uses.
The specific embodiment
The present invention is by making spinning solution by polyether polyols with reduced unsaturation stoste and radical initiator (particularly pyrolytic alkyl peroxide class initator) blend, in spinning solution, radical initiator is in the time of high-temperature dry spinning, decompose and discharge free radical, cause polyether polyols with reduced unsaturation and form intermolecular micro-crosslinked polyurethane elastomeric fiber that has, it is characterized in that:
Polyurethane spinning solution is to form performed polymer by PTMEG (or polyester-diol), vulcabond through condensation addition polymerization, performed polymer forms polyether polyols with reduced unsaturation by diamine, the common chain extension of chain terminating agent, then by polyether polyols with reduced unsaturation and radical initiator and other additive blend and make; Above-mentioned polyurethane spinning solution adopts dry spinning technology to be spun into final fiber.
1, described PTMEG is polytetrahydrofuran diol, polyoxygenated alkene glycol or copolyether glycol, and PTMEG has the molecular weight of 1000-5000, preferably has the polytetrahydrofuran diol of 1810 ± 25 molecular weight.
2, described vulcabond is methyl diphenylene diisocyanate MDI, toluene di-isocyanate(TDI) TDI, naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI, poly methylene poly phenyl poly isocyanate PAPI or 4,4, one dicyclohexyl methyl hydride diisocyanate HMDI, preferably methyl diphenylene diisocyanate (MDI).
3, in described performed polymer, vulcabond isocyanate groups and PTMEG oh group mol ratio are 1.65-2.50, preferably 1.7-2.0.
4, described diamine is, 2-ethylenediamine EDA, 1,2-propane diamine PDA, 1-methyl isophthalic acid, 5-pentanediamine, hexamethylene diamine or p-phenylenediamine (PPD); Described chain terminating agent comprises diethylamine DEA, n-butanol.
5, the amino molal quantity+phosphonium flame retardant terminal hydroxy group of described dihydroxylic alcohols terminal hydroxy group molal quantity+diamine end, the final agent molal quantity=isocyanate groups of carboxyl molal quantity+1/2 chain molal quantity; In chain extension solution, the amino molal quantity/chain terminating agent end group of diamine number=14.5-21.0.
6, described polyether polyols with reduced unsaturation has the number-average molecular weight of 80000-500000, preferably has the polyether polyols with reduced unsaturation of 90000-250000 number-average molecular weight.
7, described radical initiator is organic peroxide type free base initator and azo radical initiator, and radical initiator consumption is the 0.05-1.5% of polyethers (polyester) glycol+isocyanates+chain extension amine gross weight, preferably 0.2-0.5%.
8, described organic peroxide type free base initator comprises carboxylic acid peroxide, alkyl peroxide, ketone peroxide, ester class peroxide, acyl class peroxide.Wherein:
1), alkyl peroxide comprises di-tert-butyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-, cumyl t-butyl peroxide, cumyl peroxide, 1,4-bis-(2-tert-butyl peroxy base isopropyl) benzene, 2,5-dimethyl-2, the peroxide such as 5-bis-(tert-butyl hydroperoxide) hexane;
2), ketone peroxide comprises the peroxide such as t-butyl peroxy ketal, tertiary pentyl peroxy ketal;
3), the peroxide such as the ester class peroxide peroxidating tert-butyl ester, tert-butyl hydroperoxide trimethylacetic acid ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, the peroxidating laurate tert-butyl ester, peroxidized t-butyl perbenzoate, peroxidating isooctyl acid tert-butyl ester;
4), acyl class peroxide comprises the peroxide such as benzoyl peroxide, lauroyl peroxide, stearoyl, peroxidating chlorination benzoyl.
In above-mentioned organic peroxide, preferably there is the alkyl organic peroxide compared with high decomposition temperature, as cumyl peroxide, Isosorbide-5-Nitrae-bis-(2-tert-butyl peroxy base isopropyl) benzene, 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane etc.
9, described other additive comprises antioxidant, resistance to xanthochromia agent, lubricant, ultra-violet absorber and ester class antioxidant; Described polyurethane spinning solution concentration is 30-45%; Described polyurethane elastomeric fiber dawn number is 20D, 30D, 40D, 140D, 840D, 1120D.
Instantiation:
Following case study on implementation is only exemplary case study on implementation, and the scope of request protection of the present invention is not limited in this.
Contrast sample: the preparation of contrast sample
5.27Kg solvent dimethylacetylamide (DMAC) is metered into pre-reactor, open and stir, in pre-reactor, add 9.50Kg PTMG (PTMEG, number-average molecular weight 1810), the cooling reactor to 23 ℃ of water-bath, in the backward pre-reactor of constant temperature 15min, add 2.495Kg methyl diphenylene diisocyanate (MDI), after reaction 20min, heating water bath pre-reactor to 55 ℃ isothermal reaction 3.5h obtain performed polymer PPS.PPS is transferred and entered in chain extending reaction still, in pre-reactor, add 16.775Kg solvent DMAC, clean pre-reactor, solvent is transferred and entered chain extending reaction still, open and stir, the cooling chain extending reaction of refrigerant still to 15 ℃ constant temperature 30min.In chain extending reaction still, drip chain extension amine aqueous solution, adding rate is 90g/min, and wherein chain extension amine aqueous solution mass concentration is 4.5%, consists of 197.1EDA+130.9gPDA+45.6gDEA+7927.0gDMAC.
After being added dropwise to complete, in chain extending reaction still, add slightly excessive rear polymerization chain extension amine, stir after 10min, resulting polymers is transferred and entered slaking still.Open and stir, in slaking still, add 12.4g anti-yellowing agent, 24.8g anti ultraviolet agent, the lubricated agent solution 97.7g(mass concentration 38% of relaxing of separating, solvent is DMAC), ester class antioxidant solution 167.3g(mass concentration 37%, solvent is DMAC).35 ℃ of water bath heat preservations, reaction slaking 5h, obtains polymer dope.Transfer polymer dope to spinning box, vacuum defoamation, obtains spinning solution.Spinning solution is carried out to dry spinning, and upper river in Zhejiang Province Temperature Setting is 242 ℃, and lower river in Zhejiang Province Temperature Setting is 180 ℃, spinning speed 600m/min, silk 40 dawn of number oil-containing dawn, filum terminale product.Each material proportion relation is as shown in table 1 data:
The each material proportioning of table 1 tables of data
Wherein: 1) molal quantity: nEDA+nPDA=nMDI-nPTMEG-nDEA/2
2) A is chain extending reaction still institute polymer, polymer solid content, the quality summation that A is following material: A=mPTMEG+mMDI+mEDA+mPDA+mDEA
The preparation of embodiment 1-3 laboratory sample
When Preparation Example 1-3 sample, Examination on experimental operation is identical with preparation contrast sample method of operating, and difference is before slaking, must in slaking still, add a certain proportion of organic peroxide cumyl peroxide (DCP), and institute adds ratio as shown in table 2 data:
Table 2 laboratory sample 1-3DCP adding proportion
Wherein: 1) molal quantity: nEDA+nPDA=nMDI-nPTMEG-nDEA/2
2) A is chain extending reaction still institute polymer, polymer solid content, the quality summation that A is following material: A=mPTMEG+mMDI+mEDA+mPDA+mDEA
Each embodiment polyurethane elastomeric fiber physical index is listed in table 3:
The each embodiment polyurethane elastomeric fiber of table 3 physical index
Wherein: brute force when SS300 is tensile fiber 300%, brute force when DS is tensile fiber fracture, DE is that fibrous fracture is extended.
Claims (10)
1. the preparation method of the high temperature resistant polyurethane elastomeric fiber of high-strength and high-modulus, it is characterized in that the method is to make polyurethane spinning solution by polyether polyols with reduced unsaturation stoste and radical initiator blend, in polyurethane spinning solution, radical initiator is in the time of high-temperature dry spinning, decompose and discharge free radical, initiation polyether polyols with reduced unsaturation forms finally has micro-crosslinked polyurethane elastomeric fiber, wherein:
Polyurethane spinning solution is to form performed polymer by PTMEG or polyester-diol and vulcabond through condensation addition polymerization, performed polymer forms polyether polyols with reduced unsaturation by diamine, the common chain extension of chain terminating agent, then by polyether polyols with reduced unsaturation and radical initiator and other additive blend and make; Above-mentioned polyurethane spinning solution adopts dry spinning technology to be spun into final fiber.
2. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, it is characterized in that described PTMEG is polytetrahydrofuran diol, polyoxygenated alkene glycol or copolyether glycol, PTMEG has the molecular weight of 1000-5000.
3. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, it is characterized in that described vulcabond is methyl diphenylene diisocyanate MDI, toluene di-isocyanate(TDI) TDI, naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI, poly methylene poly phenyl poly isocyanate PAPI or 4,4, one dicyclohexyl methyl hydride diisocyanate HMDI.
4. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, is characterized in that in described performed polymer, and vulcabond isocyanate groups and PTMEG oh group mol ratio are 1.65-2.50.
5. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, is characterized in that described diamine is 1,2-ethylenediamine EDA, 1,2-propane diamine PDA, 1-methyl isophthalic acid, 5-pentanediamine or hexamethylene diamine or p-phenylenediamine (PPD); Described chain terminating agent comprises diethylamine DEA or n-butanol.
6. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, it is characterized in that in described polyether polyols with reduced unsaturation the amino molal quantity+phosphonium flame retardant terminal hydroxy group of dihydroxylic alcohols terminal hydroxy group molal quantity+diamine end, the final agent molal quantity=isocyanate groups of carboxyl molal quantity+1/2 chain molal quantity; In described chain extension solution, the amino molal quantity/chain terminating agent end group of diamine number=14.5-21.0.
7. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, is characterized in that described polyether polyols with reduced unsaturation has the number-average molecular weight of 80000-500000.
8. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, it is characterized in that described radical initiator is organic peroxide type free base initator, particularly pyrolytic organic peroxide type free base initator, radical initiator consumption is the 0.05-1.5% of PTMEG or polyester-diol+isocyanates+chain extension amine gross weight.
9. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 8, it is characterized in that described organic peroxide type free base initator comprises carboxylic acid peroxide, alkyl peroxide, ketone peroxide, ester class peroxide or acyl class peroxide, wherein:
1), alkyl peroxide comprises di-tert-butyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-, cumyl t-butyl peroxide, cumyl peroxide, 1,4-bis-(2-tert-butyl peroxy base isopropyl) benzene or 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane;
2), ketone peroxide comprises t-butyl peroxy ketal or tertiary pentyl peroxy ketal;
3), ester class peroxide comprises the peroxidating tert-butyl ester, tert-butyl hydroperoxide trimethylacetic acid ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, the peroxidating laurate tert-butyl ester, peroxidized t-butyl perbenzoate or the peroxidating isooctyl acid tert-butyl ester;
4), acyl class peroxide comprises benzoyl peroxide, lauroyl peroxide, stearoyl or peroxidating chlorination benzoyl.
10. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 1, is characterized in that described other additive comprises resistance to xanthochromia agent, lubricant, ultra-violet absorber and ester class antioxidant; Described polyurethane spinning solution mass concentration is 30-45%; Described polyurethane elastomeric fiber dawn number is 20D, 30D, 40D, 140D, 840D or 1120D.
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| CN105019052A (en) * | 2015-06-29 | 2015-11-04 | 浙江华峰氨纶股份有限公司 | Preparation method of high performance polyurethane elastic fiber |
| CN106213593A (en) * | 2016-09-30 | 2016-12-14 | 深圳市六月玫瑰内衣科技有限公司 | A kind of comfortable cool underwear |
| CN107216438A (en) * | 2017-07-07 | 2017-09-29 | 宋文通 | A kind of high-strength composite high-molecular material of light weight |
| CN110563909A (en) * | 2019-09-03 | 2019-12-13 | 四川睿铁科技有限责任公司 | restrictive pouring modified polyurethane resin for guide rail of guide rail electric car and preparation method thereof |
| US11806912B2 (en) | 2020-08-12 | 2023-11-07 | Kimberly-Clark Worldwide, Inc. | Modified thermoplastic polyurethanes and methods of extruding same |
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| US11806912B2 (en) | 2020-08-12 | 2023-11-07 | Kimberly-Clark Worldwide, Inc. | Modified thermoplastic polyurethanes and methods of extruding same |
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| CN103789864B (en) | 2016-01-13 |
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