CN104987699A - Preparation method for polyurethane chip for high-temperature-resistant fibers - Google Patents
Preparation method for polyurethane chip for high-temperature-resistant fibers Download PDFInfo
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- CN104987699A CN104987699A CN201510407574.5A CN201510407574A CN104987699A CN 104987699 A CN104987699 A CN 104987699A CN 201510407574 A CN201510407574 A CN 201510407574A CN 104987699 A CN104987699 A CN 104987699A
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Abstract
The invention discloses a preparation method for polyurethane chip for high-temperature-resistant fibers. The preparation method is characterized in that the polyurethane chip is prepared by reacting the mixture of newly-synthesized aliphatic/aromatic hybrid polyester polyol and polyether polyol, aliphatic diol and diisocyanate in a double-screw extruder. The polyurethane chip has the characteristics of high molecular weight and narrow molecular weight distribution. Melt-spun polyurethane fibers produced by using the polyurethane chip prepared by the preparation method disclosed by the invention approach to or exceed over spandex produced by using a dry spinning process in performance.
Description
Technical field
The present invention relates to a kind of preparation method of urethane section of novel fire resistant fiber.
Background technology
Spandex is as a kind of highly elastic fiber material, have been widely used at textile industry tool, at present, spandex mainly adopts dry-spinning (dry-spinning) and melt-spinning (melt-spun) two kinds of explained hereafter, the advantages such as melt spun spandex facility investment is few, production cycle is short, Production Flow Chart is simple, output is high, cost is low, especially pollution-free are subject to the common concern of people, are called as green spandex in the world.
Because melt spun spandex processing temperature is high, compared with dry spinning spandex, rebound resilience and thermotolerance are all weaker, in order to improve the performance need of melt spun spandex to its upstream product---modification is carried out in urethane section, to improve the finished product performance, Chinese patent application CN01115739 add in spandex section nano-powder blended after, for spinning, thermal characteristics and the mechanical property of melt spun spandex can be improved; Chinese patent application CN200410065487 adopts the method being mixed into the auxiliary agent such as linking agent, thermo-stabilizer in polyester slice to improve the performance of melt spun spandex; But the blended uniformity such as urethane section and auxiliary agent are restive, and melt spun spandex quality control is more difficult.
Summary of the invention
The object of the invention is to provide a kind of section close to the polyurethane high temperature resistant fiber of dry spinning spandex in mechanical property, resistance toheat.
Concrete technical scheme is as follows:
A kind of preparation method of urethane section of high-temperature fibre, it is according to 1:(0.5 ~ 2 by polymer polyatomic alcohol, aliphatic diol, isocyanic ester and inorganic nano-filler): it is in the response type twin screw extruder of 45 ~ 85 that the mol ratio of (1.4 ~ 3) adds length-to-diameter ratio, the urethane section of obtained high-temperature fibre, preferably, the inorganic nano-filler accounting for raw material gross weight 1 ~ 2% is also comprised in raw material.
Preferably, described polymer polyatomic alcohol is the mixture of polyether glycol and polycarbonate polyol, and the massfraction of described polyether glycol is 25 ~ 30%, and the massfraction of described polycarbonate polyol is 70 ~ 75%.
Preferably, the molecular weight of described polyether glycol is 1000-3000, and the molecular weight of described polycarbonate polyol takes from 500-5000.
Preferably, described polycarbonate polyol preparation method is as follows:
A) be (10 ~ 25) by mol ratio: (25 ~ 40): the aromatic diacid of (55 ~ 75), aliphatic diacid and 1,4-butyleneglycol adds in slurrying still, under nitrogen protection, pull an oar at the temperature of 20 ~ 60 DEG C, until mix;
B) product press-in esterifying kettle step a) obtained, under nitrogen protection under normal pressure, in 100 ~ 270 DEG C of stirring reactions 1 ~ 4 hour, and the water condensation that will produce is discharged, and obtains clear liquid;
C) by step b) the clear liquid nitrogen that obtains is pressed into polycondensation vessel, and under the vacuum tightness of 100Pa ~ 40kPa, in 200 DEG C ~ 250 DEG C reaction 0.5h ~ 12h, blowing, obtains polyester polyol.
Preferably, described aromatic diacid comprises one or more of phthalic acid, terephthalic acid, m-phthalic acid and naphthalene diacid.
Preferably, described aliphatic diacid comprise oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, sebacic acid one or more.
Preferably, described polycarbonate polyol takes from 1, one or more in 6 hexylene glycol polycarbonate diols, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane polycarbonate diol, BDO polycarbonate diol, 1,5-PD polycarbonate diol.
Preferably, described aliphatic diol is one or both in BDO, 1,4 cyclohexane dimethanol.
Preferably, described isocyanic ester is 4, one or more of 4 '-diphenylmethanediisocyanate, toluene diisocynate, hexamethylene-diisocyanate, isoflurane chalcone diisocyanate and (4,4 '-dicyclohexyl-methane) vulcabond.
Preferably, at least one in the nano silicon that described inorganic nano-filler is, prepared by nano-sized magnesium hydroxide, nano-calcium carbonate, vapor phase process.
Advantage of the present invention is the slicing product weight-average molecular weight >=500kDa of preparation, and molecular weight distribution≤1.9, with other melt spun spandex conferred elasticity response rates are higher on the market, performance is close to dry spinning spandex, as shown in table 1.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
Embodiment 1
Under nitrogen protection, by terephthalic acid: hexanodioic acid: the ratio of BDO 10:40:70 is in molar ratio stirred to evenly under 50 DEG C of conditions; With nitrogen, hydraulic hybrid is caused esterifying kettle, rapid temperature increases to 100 DEG C starts reaction, in 2h, temperature is risen to 235 DEG C, and discharges generation moisture, obtains clarified liq; By this liquid press-in polycondensation vessel, keep temperature 230 DEG C, explosive decompression, to 30kPa, keeps temperature-resistant, pressure is progressively reduced to 100Pa in 1h, and reaction terminates, and obtains polyester polyol, weight molecule amount 3000Da.
With measuring the ratio of pump massage that than 1.03:0.97:2 by polycarbonate polyol, 1,4-butyleneglycol, hexamethylene-diisocyanate, nano silicon, nano silicon is prepared by vapor phase process, its addition is 1% of raw material gross weight, squeezing into length-to-diameter ratio is in the reaction double screw rod of 65, temperature of reaction 120 ~ 190 DEG C, granulation underwater, the product after drying, packaging.Weight-average molecular weight 650kDa, molecular weight distribution: 1.7.
Utilize the section in the present embodiment in spinning-drawing machine, spin the fiber of 15D.
Embodiment 2
Under nitrogen protection, by phthalic acid: succinic acid: the ratio of BDO 15:35:60 is in molar ratio stirred to evenly under 60 DEG C of conditions; With nitrogen, hydraulic hybrid is caused esterifying kettle, rapid temperature increases to 100 DEG C starts reaction, in 2h, temperature is risen to 260 DEG C, and discharges generation moisture, obtains clarified liq; By this liquid press-in polycondensation vessel, keep temperature 245 DEG C, explosive decompression, to 30kPa, keeps temperature-resistant, pressure is progressively reduced to 100Pa in 1h, and reaction terminates, and obtains polyester polyol, weight molecule amount 4000Da.
With measuring the ratio of pump massage that than 1.03:0.97:2 by polycarbonate polyol, 1,4-cyclohexanedimethanol, 4, it is in the reaction double screw rod of 75 that 4 '-diphenylmethanediisocyanate, nano-sized magnesium hydroxide squeeze into length-to-diameter ratio, temperature of reaction 120 ~ 190 DEG C, granulation underwater, the product after drying, packaging.Weight-average molecular weight 500kDa, molecular weight distribution: 1.9.
Utilize the section in the present embodiment in spinning-drawing machine, spin the fiber of 20D.
Embodiment 3
Under nitrogen protection, by terephthalic acid: pentanedioic acid: the ratio of BDO 55:55:75 is in molar ratio stirred to evenly under 60 DEG C of conditions; With nitrogen, hydraulic hybrid is caused esterifying kettle, rapid temperature increases to 100 DEG C starts reaction, in 2h, temperature is risen to 240 DEG C, and discharges generation moisture, obtains clarified liq; By this liquid press-in polycondensation vessel, keep temperature 235 DEG C, explosive decompression, to 30kPa, keeps temperature-resistant, pressure is progressively reduced to 100Pa in 1h, and reaction terminates, and obtains polyester polyol, weight molecule amount 2000Da.
With measuring the ratio of pump massage that than 1.03:0.97:2 by polycarbonate polyol, 1,4-cyclohexanedimethanol and 1,4-mixture of butanediols, 4, it is in the reaction double screw rod of 85 that 4 '-diphenylmethanediisocyanate, nano-calcium carbonate squeeze into length-to-diameter ratio, temperature of reaction 120 ~ 190 DEG C, granulation underwater, the product after drying, packaging.Weight-average molecular weight 520kDa, molecular weight distribution: 1.9.
Utilize the section in the present embodiment in spinning-drawing machine, spin the fiber of 40D.
Embodiment 1 ~ 3 the performance index of spun fiber as shown in table 1.
Table 1
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (10)
1. the preparation method of the urethane section of a high-temperature fibre, it is characterized in that, according to 1:(0.5 ~ 2 by polymer polyatomic alcohol, aliphatic diol, isocyanic ester and inorganic nano-filler): it is in the response type twin screw extruder of 45 ~ 85 that the mol ratio of (1.4 ~ 3) adds length-to-diameter ratio, the urethane section of obtained high-temperature fibre.
2. preparation method according to claim 1, it is characterized in that: described polymer polyatomic alcohol is the mixture of polyether glycol and polycarbonate polyol, the massfraction of described polyether glycol is 25 ~ 30%, and the massfraction of described polycarbonate polyol is 70 ~ 75%.
3. preparation method according to claim 1 and 2, is characterized in that: the molecular weight of described polyether glycol is 1000-3000, and the molecular weight of described polycarbonate polyol takes from 500-5000.
4. the preparation method according to Claims 2 or 3, is characterized in that: described polycarbonate polyol preparation method is as follows:
A) be (10 ~ 25) by mol ratio: (25 ~ 40): the aromatic diacid of (55 ~ 75), aliphatic diacid and 1,4-butyleneglycol adds in slurrying still, under nitrogen protection, pull an oar at the temperature of 20 ~ 60 DEG C, until mix;
B) product press-in esterifying kettle step a) obtained, under nitrogen protection under normal pressure, in 100 ~ 270 DEG C of stirring reactions 1 ~ 4 hour, and the water condensation that will produce is discharged, and obtains clear liquid;
C) by step b) the clear liquid nitrogen that obtains is pressed into polycondensation vessel, and under the vacuum tightness of 100Pa ~ 40kPa, in 200 DEG C ~ 250 DEG C reaction 0.5h ~ 12h, blowing, obtains polyester polyol.
5. preparation method according to claim 4, is characterized in that: described aromatic diacid comprises one or more of phthalic acid, terephthalic acid, m-phthalic acid and naphthalene diacid.
6. preparation method according to claim 4, is characterized in that: described aliphatic diacid comprise oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, sebacic acid one or more.
7. preparation method according to claim 2, it is characterized in that: described polycarbonate polyol takes from 1,6 hexylene glycol polycarbonate diols, 1,4-hydroxymethyl-cyclohexane polycarbonate diol, 1, one or more in 4-butyleneglycol polycarbonate diol, 1,5-PD polycarbonate diol.
8. preparation method according to claim 1, is characterized in that: described aliphatic diol is one or both in BDO, 1,4 cyclohexane dimethanol.
9. preparation method according to claim 1, it is characterized in that: described isocyanic ester is 4, one or more of 4 '-diphenylmethanediisocyanate, toluene diisocynate, hexamethylene-diisocyanate, isoflurane chalcone diisocyanate and (4,4 '-dicyclohexyl-methane) vulcabond.
10. preparation method according to claim 1, it is characterized in that: in raw material, also comprise the inorganic nano-filler accounting for raw material total amount 1 ~ 2%, described inorganic nano-filler be nano-sized magnesium hydroxide, at least one in nano silicon prepared by nano-calcium carbonate, vapor phase process.
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| CN201510407574.5A CN104987699A (en) | 2015-07-13 | 2015-07-13 | Preparation method for polyurethane chip for high-temperature-resistant fibers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977929A (en) * | 2018-05-30 | 2018-12-11 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of skin-core structure moisture absorbing and sweat releasing polyurethane elastomeric fiber |
| CN114790275A (en) * | 2022-05-16 | 2022-07-26 | 金俊平 | High-temperature-resistant melt-spun spandex slice with excellent mechanical properties and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166502A (en) * | 1996-03-12 | 1997-12-03 | 花王株式会社 | Method of making polyurethane foam |
| CN101148494A (en) * | 2007-10-26 | 2008-03-26 | 张勇 | Method for producing urethane elastomer and application |
| CN103588945A (en) * | 2012-08-16 | 2014-02-19 | 南通华盛高聚物科技发展有限公司 | Low melting point spandex slice and preparation method thereof |
-
2015
- 2015-07-13 CN CN201510407574.5A patent/CN104987699A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166502A (en) * | 1996-03-12 | 1997-12-03 | 花王株式会社 | Method of making polyurethane foam |
| CN101148494A (en) * | 2007-10-26 | 2008-03-26 | 张勇 | Method for producing urethane elastomer and application |
| CN103588945A (en) * | 2012-08-16 | 2014-02-19 | 南通华盛高聚物科技发展有限公司 | Low melting point spandex slice and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 刘益军: "《聚氨酯原料及助剂手册》", 30 April 2005, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977929A (en) * | 2018-05-30 | 2018-12-11 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of skin-core structure moisture absorbing and sweat releasing polyurethane elastomeric fiber |
| CN108977929B (en) * | 2018-05-30 | 2020-12-15 | 浙江华峰氨纶股份有限公司 | Preparation method of moisture-absorbing and sweat-releasing polyurethane elastic fiber with skin-core structure |
| CN114790275A (en) * | 2022-05-16 | 2022-07-26 | 金俊平 | High-temperature-resistant melt-spun spandex slice with excellent mechanical properties and preparation method thereof |
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Application publication date: 20151021 |