CN103789864B - The preparation method of a kind of high-strength and high-modulus is high temperature resistant polyurethane elastomeric fiber - Google Patents
The preparation method of a kind of high-strength and high-modulus is high temperature resistant polyurethane elastomeric fiber Download PDFInfo
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Abstract
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, its preparation method is: polyether polyols with reduced unsaturation stoste and radical initiator (particularly pyrolytic alkyl peroxide class initator) is blended makes spinning solution, in spinning solution, radical initiator is when high-temperature dry spinning, decompose and discharge free radical, cause polyether polyols with reduced unsaturation and formed and intermolecular there is micro-crosslinked polyurethane elastomeric fiber.The polyurethane elastomeric fiber adopting the method to prepare has high strength, high-modulus and high-temperature stability, these performances are to 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 vegetable raw materials and military clothing elastomer strong to stand up to hard wear uses.
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, elastic recovery rate, is widely used in the field such as knitted apparel, household articles.When road is weaved after carrying out, if silk TENSILE STRENGTH is low, stretch modulus is little, during high-speed unwinding, easily there is the faults such as fracture of wire and affect weaving efficiency in polyurethane elastomeric fiber; During rear road high-temp dyeing, if silk mechanical property and resistance to elevated temperatures poor, in fabric, easily there is to break in dyeing phenomenon in silk; During follow-up use, particularly when it takes elastomer silk as high-elastic jeans etc., need fiber to possess excellent warp tensile strength and modulus especially, clothing just can be made to have 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 to wear well.
Traditional polyurethane elastomeric fiber mechanical property and heat resistance method of modifying mainly concentrate on polymerization intra-molecular structure modification in early stage and polymerization later stage intermolecular cross-linking modification.Polymerization intra-molecular structure modification in early stage is mainly carried out in-situ polymerization by the design of molecule segment and is regulated 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 introducing the means such as polyfunctional group alcohols and amine in the molecule; Polymerization later stage intermolecular cross-linking modification is mainly undertaken processing modified by adding the auxiliary agents such as crosslinking agent in polyether polyols with reduced unsaturation, comprises isocyanate group and imino group cross-linking reaction, isocyanate group or hydroxyl terminated polyurethane performed polymer are crosslinked, alkoxysilane-terminated base polyurethane prepolymer for use as hydrolytic crosslinking, ethenyl blocking base polyurethane prepolymer for use as are crosslinked, sulfur cross-linking, formaldehyde crosslinking etc. crosslinked with functional side group base polyurethane prepolymer for use as.
Radical initiator refers to the reagent that can produce free radical in radical reaction, and conventional has metal peroxides type free base initator, halogen radical initiator, organic peroxide type free base initator, azo type free radical initator etc.Wherein purposes is organic peroxide type free base initator the most widely, this compounds is the compound containing 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 except vinyl monomer polymerization as free radical donor, also be widely used in the sulfuration of plastics and rubber and be cross-linked to promote the modulus of plastics and rubber and heat-resisting weatherability, as dicumyl peroxide is widely used in the crosslinked of electric wire, cable jacket and insulating barrier PE as crosslinking agent, cumyl peroxide is used for the cross-linking modified etc. of 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 (for cumyl peroxide DCP):
1) initator pyrolysis is free radical:
2) free polymer readical is formed:
3) free polymer readical coupling is formed crosslinked:
In addition, free radical also can cause Ruan Duan district segment and occur slight crosslinked, and the crosslinking covalent bonds that hard section, Ruan Duan district are formed, 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 report especially.This patent creatively adopts radical initiator, particularly pyrolytic organic peroxide type free base initator is as crosslinking agent, polyurethane elastomeric fiber is spun to dry method and carries out radical crosslinking modification, successfully improve stretch modulus and the TENSILE STRENGTH of polyurethane elastomeric fiber, and the heat resistance of fiber have also been obtained and significantly promotes, 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 that 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 adopting the method to prepare has high strength, high-modulus and high-temperature stability, these performances are to 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 vegetable raw materials and clothing elastomer strong to stand up to hard wear 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 by polyether polyols with reduced unsaturation stoste and radical initiator is blended makes polyurethane spinning solution, in polyurethane spinning solution, radical initiator is when high-temperature dry spinning, decompose and discharge free radical, initiation polyether polyols with reduced unsaturation is formed finally has micro-crosslinked polyurethane elastomeric fiber, wherein:
Polyurethane spinning solution forms 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 blended and obtained; Above-mentioned polyurethane spinning solution adopts dry spinning technology to be spun into final fiber.
Described PTMEG is polytetrahydrofuran diol, polyoxygenated olefin diols 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 final agent molal quantity=isocyanate groups molal quantity of dihydroxylic alcohols terminal hydroxy group molal quantity+diamine Amino End Group molal quantity+phosphonium flame retardant terminal hydroxy group, carboxyl molal quantity+1/2 chain; In described chain extension solution, the amino molal quantity/chain terminating agent end group number=14.5-21.0 of diamine.
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-2,5-two (tert-butyl peroxy base) hexane, 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 t-amyl peroxy ketal;
3), ester class peroxide comprises t-butylperbenzoate, tert-butyl hydroperoxide trimethylacetic acid ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, the peroxylauric acid 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 benzoyl chloride.
Other additive described comprises color inhibition 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 preparation method that the present invention relates to the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus, adopts the method effectively can 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 blended, be prepared into spinning solution, when 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 the intensity of lifting fiber, modulus and heat resistance.By polyurethane elastomeric fiber prepared by the method, during high-speed unwinding not easily fracture of wire, high-temp dyeing time silk not easily in disconnected, spy is suitable as high-temp dyeing vegetable raw materials and clothing elastomer strong to stand up to hard wear uses.
Detailed description of the invention
The present invention is by by polyether polyols with reduced unsaturation stoste and radical initiator (particularly pyrolytic alkyl peroxide class initator) is blended makes spinning solution, in spinning solution, radical initiator is when high-temperature dry spinning, decompose and discharge free radical, cause polyether polyols with reduced unsaturation to be formed and intermolecular there is micro-crosslinked polyurethane elastomeric fiber, it is characterized in that:
Polyurethane spinning solution forms 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 blended and obtained; Above-mentioned polyurethane spinning solution adopts dry spinning technology to be spun into final fiber.
1, described PTMEG is polytetrahydrofuran diol, polyoxygenated olefin diols 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, preferred methyl diphenylene diisocyanate (MDI).
3, in described performed polymer, vulcabond isocyanate groups and PTMEG oh group mol ratio are 1.65-2.50, preferred 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, described dihydroxylic alcohols terminal hydroxy group molal quantity+diamine Amino End Group molal quantity+phosphonium flame retardant terminal hydroxy group, the final agent molal quantity=isocyanate groups molal quantity of carboxyl molal quantity+1/2 chain; In chain extension solution, the amino molal quantity/chain terminating agent end group number=14.5-21.0 of diamine.
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 type free radical initator, and radical initiator consumption is the 0.05-1.5% of polyethers (polyester) glycol+isocyanates+chain extension amine gross weight, preferred 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-2,5-two (tert-butyl peroxy base) hexane, cumyl t-butyl peroxide, cumyl peroxide, 1,4-bis-(2-tert-butyl peroxy base isopropyl) benzene, 2, the peroxide such as 5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane;
2), ketone peroxide comprises the peroxide such as t-butyl peroxy ketal, t-amyl peroxy ketal;
3), the peroxide such as ester class peroxide t-butylperbenzoate, tert-butyl hydroperoxide trimethylacetic acid ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, the peroxylauric acid 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 benzoyl chloride.
In above-mentioned organic peroxide, preferably there is the alkyl organic peroxide compared with high decomposition temperature, as cumyl peroxide, Isosorbide-5-Nitrae-two (2-tert-butyl peroxy base isopropyl) benzene, 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexanes etc.
9, other additive described comprises antioxidant, color inhibition 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, 9.50Kg PTMG (PTMEG, number-average molecular weight 1810), water-bath cooling reactor to 23 DEG C is added in pre-reactor, in pre-reactor, 2.495Kg methyl diphenylene diisocyanate (MDI) is added after constant temperature 15min, after reaction 20min, heating water bath pre-reactor to 55 DEG C isothermal reaction 3.5h obtains performed polymer PPS.PPS transfer is entered in chain extending reaction still, in pre-reactor, adds 16.775Kg solvent DMAC, cleaning pre-reactor, solvent transfer is entered chain extending reaction still, opens and stir, refrigerant cooling chain extending reaction still to 15 DEG C 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, adding in chain extending reaction still and be polymerized chain extension amine little over after amount, after stirring 10min, resulting polymers transfer is entered slaking still.Open and stir, add 12.4g anti-yellowing agent, 24.8g anti ultraviolet agent in slaking still, lubrication reeling agent solution 97.7g(mass concentration 38%, solvent is DMAC), ester class antioxidant solution 167.3g(mass concentration 37%, solvent is DMAC).35 DEG C of water bath heat preservations, reaction slaking 5h, obtains polymer dope.Transfer polymer dope is to spinning box, and vacuum defoamation, obtains spinning solution.Carry out dry spinning to spinning solution, upper river in Zhejiang Province temperature is set as 242 DEG C, and lower river in Zhejiang Province temperature is set as 180 DEG C, spinning speed 600m/min, silk oil-containing dawn number 40 dawn, most filum terminale product.Each material proportion relation is as shown in table 1 data:
Table 1 each material proportioning 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, and namely A is the quality summation of following material: A=mPTMEG+mMDI+mEDA+mPDA+mDEA
The preparation of embodiment 1-3 laboratory sample
During preparation embodiment 1-3 sample, it is identical that Examination on experimental operation and preparation contrast sample method of operating, and before difference is slaking, must add a certain proportion of organic peroxide cumyl peroxide (DCP) in slaking still, added ratio is 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, and namely A is the quality summation of following material: A=mPTMEG+mMDI+mEDA+mPDA+mDEA
Each embodiment polyurethane elastomeric fiber physical index is listed in table 3:
Table 3 each embodiment polyurethane elastomeric fiber physical index
Wherein: powerful when SS300 is tensile fiber 300%, powerful when DS is tensile fiber fracture, DE is that fibrous fracture is extended.
Claims (7)
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 by polyether polyols with reduced unsaturation stoste and radical initiator is blended makes polyurethane spinning solution, in polyurethane spinning solution, radical initiator is when high-temperature dry spinning, decompose and discharge free radical, initiation polyether polyols with reduced unsaturation is formed finally has micro-crosslinked polyurethane elastomeric fiber, wherein:
Polyurethane spinning solution forms 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 blended and obtained; Above-mentioned polyurethane spinning solution adopts dry spinning technology to be spun into final fiber;
Described PTMEG is polytetrahydrofuran diol, polyoxygenated olefin diols 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.
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, is characterized in that in described performed polymer, and vulcabond isocyanate groups and PTMEG oh group mol ratio are 1.65-2.50.
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, 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.
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 described polyether polyols with reduced unsaturation has the number-average molecular weight of 80000-500000.
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, it is characterized in that described radical initiator is 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.
6. the preparation method of the high temperature resistant polyurethane elastomeric fiber of a kind of high-strength and high-modulus according to claim 5, 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) hexane, cumyl t-butyl peroxide, cumyl peroxide or Isosorbide-5-Nitrae-two (the 2-tert-butyl peroxy base isopropyl) benzene of 5-;
2), ketone peroxide comprises t-butyl peroxy ketal or t-amyl peroxy ketal;
3), ester class peroxide comprises tert-butyl hydroperoxide trimethylacetic acid ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, the peroxylauric acid 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 benzoyl chloride.
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 other additive described comprises color inhibition 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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| CN105019052B (en) * | 2015-06-29 | 2018-02-02 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of high performance polyurethane elastomer |
| CN106213593B (en) * | 2016-09-30 | 2018-06-12 | 宏杰内衣股份有限公司 | A kind of comfortable cool underpants |
| 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 |
| MX2023001668A (en) | 2020-08-12 | 2023-03-08 | Kimberly Clark Co | Modified thermoplastic polyurethanes and methods of extruding same. |
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Address after: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee after: Huafeng Chemical Co.,Ltd. Address before: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee before: ZHEJIANG HUAFENG SPANDEX Co.,Ltd. |
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