CN100537859C - A kind of melt spinning method of making polyurethane elastomeric fiber - Google Patents
A kind of melt spinning method of making polyurethane elastomeric fiber Download PDFInfo
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- CN100537859C CN100537859C CNB03133735XA CN03133735A CN100537859C CN 100537859 C CN100537859 C CN 100537859C CN B03133735X A CNB03133735X A CN B03133735XA CN 03133735 A CN03133735 A CN 03133735A CN 100537859 C CN100537859 C CN 100537859C
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Abstract
The invention provides a kind of melt spinning method of polyurethane elastomeric fiber, it is characterized in that in extruder type spinning machine, adding and be equipped with mixing refining head and clarifying mixer, isocyanate group (NCO) is increased a course of reaction that adds sealing and deblocking, and finally to the elastomer heat treatment of being annealed, with heat endurance and other the main performance indications that improve polyurethane elastomeric fiber, make it to be particularly suitable for the elastic fabric of better quality requirement and the application of fibre.
Description
Technical field
The invention belongs to the technical field of chemical synthetic fiber production method, the new method of a kind of production of linear polyurethane elastomer and polyurethane elastomeric fiber promptly is provided.Specifically, the invention provides a kind of innovative technology of producing polyurethane elastomeric fiber with melt spinning method.
Background technology
Polyurethane elastomeric fiber, China names and is spandex fibre.Usually be divided into polyester-type and polyether-type two big classes.From molecular structure, it is to be formed by amorphism low melting point polymer (soft segment) and high crystalline high-melting-point polymer (rigid chain segment) block polymerization.Its " soft segment " is made up of molecular weight 500-5000 polyester or polyethers; " rigid chain segment " then is made up of urethane bonds, amido link, urea key etc.United States Patent (USP) 3009762 discloses the method for american rubber company manufacturing PAUR elastomer, it is characterized in that making molecular weight with polyol condensating reaction is about 1900 polyester, with excessive isocyanate reaction generation performed polymer, add appropriate solvent and make polyurethane elastomeric fiber again with chemical spinning.United States Patent (USP) 2726219 and 3094374 discloses the method for du pont company production EU elastomer, it is characterized in that: make raw material with polyether polyol and isocyanates, process prepolymerization reaction, chain extending reaction and three processes of cessation reaction are made has the polyurethane elastomer that ether structure is arranged, make solution again, through the orifice of spinneret of extruding out, and dry up solvent with heated nitrogen, form polyurethane elastomeric fiber.Above-mentioned two kinds of methods, because its complex process, equipment investment are big, thereby the production cost height.And their employed solvents (as dimethyl formamide or dimethylacetylamide) toxicity is very big, seriously jeopardizes the healthy of direct labor, and environment is also had bigger pollution, these effects limit the development of polyurethane elastomeric fiber.
In recent years, Ri Ben Kanebo Ltd and a kind of new technology of day having spun (Nishin Spinning) enterprise development of etc.ing clearly with melt spinning method production polyurethane elastomeric fiber.This technology through behind the vacuum drying, directly at high temperature extrude from orifice of spinneret with molten condition with screw extruder, and air cooling is configured as the linear polyester elastomer polyurethane elastomeric fiber.Plurality of advantages such as the melt-spun method has environmentally safe, equipment investment is few, energy consumption is low, the production staffing is few, the easy adjustment of technology have obtained various countries company of the same trade and have paid attention to greatly.Yet, relatively poor with present its heat endurance (being heat resistance) of polyurethane elastomeric fiber that the melt-spun method is produced, elastic restoration ratio is also lower behind the high temperature deformation, and its production technology is stable not enough and ripe, thereby this technology awaits to improve and further improve.
Summary of the invention
The objective of the invention is to seek a kind of comparatively easy, the economic and nontoxic production of linear polyurethane elastomer and the new method of polyurethane elastomeric fiber, should reduce production costs and improve direct labor's working condition, can guarantee the superperformance of product again, open up the new way of development China spandex fibre industry with this.
The invention provides a kind of melt spinning method of making polyurethane elastomeric fiber, it makes main raw material with polyester or polyether polyol and isocyanates, adopt chain extender to make a polyalcohol and isocyanates step synthesizing linear polyurethane elastomer in double screw extruder, and make polyurethane elastomeric fiber with extruder type spinning machine heating, extruding, drawing-off, it is characterized in that: (1) makes the isocyanate group of polyurethane with blocked polyurethane addition product (end-capping reagent) (-NCO) the synthetic a kind of stable derivative of sealing in advance promptly forms the polyurethane elastomer of band end-blocking; (2) deblocking when spinning, make (-NCO) base activation, after the activation freely-the NCO group takes place crosslinked with polyurethane macromolecular in fiber curing molding process; (3) suitable position at extruder type spinning machine is equipped with the mixing refining head that injects end-capping reagent, and adds the clarifying mixer that the peace deblocking is used at the front end that enters orifice of spinneret; (4) carry out unwinding behind the fiberizing, remake annealing heat treatment.
The melt spinning method of manufacturing polyurethane elastomeric fiber provided by the present invention, the first step are to make polyalcohol (as PolyTHF) and isocyanates synthesizing linear polyurethane elastomer in double screw extruder with chain extender; Second step through after the vacuumize, was carried out spinning with extruder type spinning machine with above-mentioned elastomer, with an amount of end-capping reagent reaction, made the elastomer closed at both ends in the mixing refining head that the suitable position of extruder type spinning machine is installed; In the 3rd clarifying mixer of step before spinning machine enters orifice of spinneret, make the elastomer deblocking, be spun into polyurethane elastomeric fiber rapidly because temperature further raises; The 4th step further was improved fibre quality index the polyurethane elastomeric fiber unwinding heat treatment of annealing.
Chain extender of the present invention can be 1,4-butanediol (being called for short BDO), also can be trimethylolpropane (TMP); Can also be 3,3 '-dichloro-4,4 '-diphenyl methane diamines (MOCA) or other diamine compounds.Its optimum range of the addition of chain extender is calculated as by the molal quantity proportioning: polyalcohol: chain extender: isocyanates=1:(1-3): (2-4).
Blocked polyurethane addition product of the present invention can be alcohol (ROH) or a phenol (ArOH), they and isocyanate group (-NCO) reaction is as follows:
Above-mentioned reaction is reversible reaction.When temperature raises, help reacting right-to-left and carry out.
The alcohol as the blind end agent that the present invention says can be primary alconol, secondary alcohol or the tertiary alcohol, and its optimal addn is pressed the molal quantity proportioning and calculated, and can be alcohol: polyurethane=(1-3): (1-6).
The said phenol as end-capping reagent of the present invention can be monohydric phenol, dihydric phenol, also can be polyhydric phenols.Its optimal addn is pressed the molal quantity proportioning and is calculated, and can be phenol: polyurethane=(1-6): (3-1).
The melt spinning method of manufacturing polyurethane elastomeric fiber provided by the present invention when adding end-capping reagent, can also add the compounding ingredient of some.Heat endurance and photostability that the adding of compounding ingredient can increase the linear polyester elastomer effectively play age inhibiting effect.The compounding ingredient that is added can be a phenol antiager in the present invention, also can be the derivative of p-phenylenediamine (PPD), can also be benzophenone or benzotriazole derivatives.The optimal addn of compounding ingredient is 0.05-1% by the total weight (percentage by weight) of polyurethane.
Method with traditional production spandex fibre (as " viral mattress " or " Lycra ") is compared, adopt method of the present invention, not only can make the workman need not to contact noxious material such as dimethyl formamide (DMF) or dimethylacetylamide (DMAC), the environment of factory and workman's working condition all can improve again; And owing to no longer contain residual toxic solvent in the polyurethane elastomeric fiber of being produced, this health for the people that guarantee to wear and use these elastomers also is useful.And because the investment of wanting required for the present invention only is 1/10th of the E.I.Du Pont Company of identical scale " dry method " amount of investment, consider that polyurethane elastomeric fiber application prospect in textile industry is very considerable, so method of the present invention after applying, will have a tremendous social and economic benefits.
Description of drawings
Fig. 1 is a process chart of the present invention.
Fig. 2 is a device schematic diagram of making polyurethane elastomeric fiber with method of the present invention.
In Fig. 2, the parts and the function of each label representative are as follows: 1, linear elastomer vacuum drying tank; 2, elastomer medial launder; 3, spinning machine screw rod; 4, mixing refining head; 5, clarifying mixer; 6, orifice of spinneret; 7, cooling air channel; 8, slinning cabinet; 9, spinning oil inlet; 10, first breast wheel; 11, second breast wheel; 12, up-coiler.
Specific embodiments
Embodiment 1:
It with molecular weight 1000 oxolane polyethers (DTMG), 1,4-butanediol, diphenyl methane-4,4 '-vulcabond (MDI) injects double screw extruder by measuring pump metering through mixing head by mole proportioning 1:1:2 and makes the section of linear polyester elastomer, with above-mentioned section resin after vacuumize, add in the extruder type spinning machine and in mixing refining head, react with the end-capping reagent primary alconol, further in clarifying mixer, be heated to 215 ℃-230 ℃, separate end-blocking, be drawn into fiber through orifice of spinneret rapidly, primary alconol: the mole proportioning of polyurethane is 2:1.After annealing in process, fibre strength was 1.04 gram/dawn through polyurethane fiber that spinning machine is spun into, and breaking elongation is 702.7%.
Embodiment 2:
It with molecular weight 2000 polyethylene glycol adipate, 1,4-butanediol, diphenyl methane-4,4 '-vulcabond and 80/20 toluene di-isocyanate(TDI) (TDI-80) are by a mole proportioning 1:1:1.8:0.2, inject double screw extruder by measuring pump, through fully reacting and making polyurethane section resin through underwater cutpellet.After vacuumize, add above-mentioned section resin in the extruder type spinning machine, the screw axial Temperature Distribution is: 145 ℃-165 ℃-200 ℃-215 ℃-215 ℃, enter mixing refining head with the end-capping reagent monohydric phenol 215 ℃ of reactions, monohydric phenol: the mole proportioning of polyurethane is 4: 2, in clarifying mixer with 220 ℃ of-230 ℃ of deblockings after orifice of spinneret, cooling air channel, slinning cabinet, after be wound into fiber, fiber is after annealing in process, its main performance index is: 0.6-0.7 gram/dawn of intensity; Breaking elongation 450-500%, 100% extends rebound degree 95.3% surely; 300% extends rebound degree 92.7% surely.
Embodiment 3:
To cut into slices with the linear polyester elastic resin that double screw extruder is made, after vacuumize, inject extruder type spinning machine, the axial temperature of screw rod is distributed as 175 ℃-185 ℃-200 ℃-205 ℃-205 ℃, entering mixing refining head reacts at 205 ℃ with the end-capping reagent polyalcohol, polyalcohol is 2:5 with the mole proportioning of polyurethane, add 0.05% compounding ingredient N-phenyl-N '-and propyl paraphenylenediamine simultaneously, extrude by weaving silk behind 215 ℃ of following deblockings through clarifying mixer, and through cooling air channel, slinning cabinet, miscible oil and through first breast wheel, on up-coiler, be wound into tube after the second breast wheel drawing-off.Make annealing in process generating polyurethane elastomer again after unwinding, its main performance index is: 0.78 gram/dawn; Breaking elongation 550%.
Can also enumerate more specific embodiments, these schemes all are to spin polyurethane elastomeric fiber with one-step method synthesizing linear polyurethane elastomer with melt spinning method, it is characterized in that in the spinning process, the suitable position of screw rod to isocyanate group (-NCO) increase a course of reaction that adds end-blocking and deblocking, and finally elastomer is annealed heat treatment to improve performance indications, it is reached can compare beautiful level by same E.I.Du Pont Company " dry method " fiber-Lycra.
Claims (10)
1, a kind of melt spinning method of making polyurethane elastomeric fiber, it makes main raw material with polyester or polyether polyol and isocyanates, adopt chain extender to make a polyalcohol and isocyanates step synthesizing linear polyurethane elastomer in double screw extruder, and with extruder type spinning machine heating, extrude and drawing-off generating polyurethane elastomer, it is characterized in that:
A, with blocked polyurethane addition product (end-capping reagent) make isocyanate group in the polyurethane (-NCO) seal into a kind of stable derivative in advance;
B, when spinning elder generation's deblocking, make (-NCO) base activation, after the activation freely-the NCO group is crosslinked with polyurethane macromolecular in fiber curing molding process;
C, add the mixing refining head that peace can be injected end-capping reagent, and add the clarifying mixer that the peace deblocking is used at the front end that enters orifice of spinneret at the suitable position of extruder type spinning machine;
Carry out unwinding behind d, the fiberizing, and do annealing heat treatment.
2,, it is characterized in that said end-capping reagent can be alcohol (ROH) or a phenol (ArOH) by the melt spinning method of the described manufacturing polyurethane elastomeric fiber of claim 1.
3, press the melt spinning method of claim 1,2 described manufacturing polyurethane elastomeric fibers, it is characterized in that said alcohol as end-capping reagent can be primary alconol, secondary alcohol or the tertiary alcohol, its optimal addn is pressed the molal quantity proportioning and is calculated, and can be alcohol: polyurethane=(1-3): (1-6).
4, press the melt spinning method of claim 1,2 described manufacturing polyurethane elastomeric fibers, it is characterized in that said phenol as end-capping reagent, can be monohydric phenol, dihydric phenol, perhaps polyhydric phenols, its optimal addn is pressed the molal quantity proportioning and is calculated, and can be phenol: polyurethane=(1-6): (3-1).
5, a kind of melt spinning method of making polyurethane elastomeric fiber, it makes main raw material with polyester or polyether polyol and isocyanates, adopt chain extender to make a polyalcohol and isocyanates step synthesizing linear polyurethane elastomer in double screw extruder, and with extruder type spinning machine heating, extrude and drawing-off generating polyurethane elastomer, it is characterized in that:
A, with blocked polyurethane addition product (end-capping reagent) make isocyanate group in the polyurethane (-NCO) seal into a kind of stable derivative in advance;
B, when spinning elder generation's deblocking, make (-NCO) base activation, after the activation freely-the NCO group is crosslinked with polyurethane macromolecular in fiber curing molding process;
C, add a certain amount of compounding ingredient;
D, add the mixing refining head that peace can be injected end-capping reagent, and add the clarifying mixer that the peace deblocking is used at the front end that enters orifice of spinneret at the suitable position of extruder type spinning machine;
Carry out unwinding behind e, the fiberizing, and do annealing heat treatment.
6,, it is characterized in that said end-capping reagent can be alcohol (ROH) or a phenol (ArOH) by the melt spinning method of the described manufacturing polyurethane elastomeric fiber of claim 5.
7, press the melt spinning method of claim 5,6 described manufacturing polyurethane elastomeric fibers, it is characterized in that said alcohol as end-capping reagent can be primary alconol, secondary alcohol or the tertiary alcohol, its optimal addn is pressed the molal quantity proportioning and is calculated, and can be alcohol: polyurethane=(1-3): (1-6).
8, press the melt spinning method of claim 5,6 described manufacturing polyurethane elastomeric fibers, it is characterized in that said phenol as end-capping reagent can be monohydric phenol, dihydric phenol, perhaps polyhydric phenols, its optimal addn is pressed the molal quantity proportioning and is calculated, and can be phenol: polyurethane=(1-6): (3-1).
9, by the melt spinning method of the described manufacturing polyurethane elastomeric fiber of claim 5, it is characterized in that said compounding ingredient can be a phenol antiager, the derivative of p-phenylenediamine (PPD), perhaps benzophenone and benzotriazole derivatives.
10, by the melt spinning method of claim 5,9 described manufacturing polyurethane elastomeric fibers, it is characterized in that its optimal addn of said compounding ingredient by the total weight (percentage by weight) of polyurethane is: 0.05-1%.
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| CNB03133735XA CN100537859C (en) | 2003-07-16 | 2003-07-16 | A kind of melt spinning method of making polyurethane elastomeric fiber |
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| CN100537859C true CN100537859C (en) | 2009-09-09 |
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| CN102115919B (en) * | 2010-12-10 | 2013-02-13 | 太仓市金祥氨纶纤维有限公司 | Melting and direct-spinning superfine denier (4.6-5.5 denier) high-elastic modulus polyurethane fiber equipment |
| CN104911723A (en) * | 2015-05-21 | 2015-09-16 | 苏州富莱克斯氨纶有限公司 | Bi-component spandex preparing technology |
| CN111575817A (en) * | 2019-02-19 | 2020-08-25 | 海宁新高纤维有限公司 | Method for manufacturing thermoplastic polyurethane fiber |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5167899A (en) * | 1990-07-07 | 1992-12-01 | The Dow Chemical Company | Process for melt blowing microfibers of rigid polyurethane having hard segments |
| CN1068341A (en) * | 1991-07-03 | 1993-01-27 | 钟纺株式会社 | Polyurethane Thermoplastic Elastomer, its manufacture method and manufacturing installation and by its spandex fiber of making |
| CN1108705A (en) * | 1994-03-12 | 1995-09-20 | 陶宇 | Method for production of polyurethane elastic fibre |
| CN1180386A (en) * | 1995-02-13 | 1998-04-29 | 卡尔弗沙工业设备公司 | Process for melt spinning of polyurethane and/or polyurethane urea |
| CN2483399Y (en) * | 2001-06-15 | 2002-03-27 | 中山市新顺特种纤维有限公司 | Co-extruding apparatus for melting spun polyurethane and cross-linked agent |
| US6485665B1 (en) * | 1997-12-10 | 2002-11-26 | Rhodianyl S.N.C. | Method for producing polyurethane elastomer fibers and fibers produced according to this method |
| CN1410605A (en) * | 2001-10-09 | 2003-04-16 | 江苏南黄海实业股份有限公司 | Preparation method of melt spinning polyurethane fiber thin denier filament |
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2003
- 2003-07-16 CN CNB03133735XA patent/CN100537859C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167899A (en) * | 1990-07-07 | 1992-12-01 | The Dow Chemical Company | Process for melt blowing microfibers of rigid polyurethane having hard segments |
| CN1068341A (en) * | 1991-07-03 | 1993-01-27 | 钟纺株式会社 | Polyurethane Thermoplastic Elastomer, its manufacture method and manufacturing installation and by its spandex fiber of making |
| CN1108705A (en) * | 1994-03-12 | 1995-09-20 | 陶宇 | Method for production of polyurethane elastic fibre |
| CN1180386A (en) * | 1995-02-13 | 1998-04-29 | 卡尔弗沙工业设备公司 | Process for melt spinning of polyurethane and/or polyurethane urea |
| US6485665B1 (en) * | 1997-12-10 | 2002-11-26 | Rhodianyl S.N.C. | Method for producing polyurethane elastomer fibers and fibers produced according to this method |
| CN2483399Y (en) * | 2001-06-15 | 2002-03-27 | 中山市新顺特种纤维有限公司 | Co-extruding apparatus for melting spun polyurethane and cross-linked agent |
| CN1410605A (en) * | 2001-10-09 | 2003-04-16 | 江苏南黄海实业股份有限公司 | Preparation method of melt spinning polyurethane fiber thin denier filament |
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