CN101171276A - Spandex from poly(tetramethylene-co-ethyleneether) glycols having high ethyleneether content - Google Patents
Spandex from poly(tetramethylene-co-ethyleneether) glycols having high ethyleneether content Download PDFInfo
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Abstract
The invention provides a polyurethaneurea composition comprising poly(tetramethylene-co-ethyleneether) glycol having from about 37 to about 70 mole percent ethyleneether content and ethylene diamine as the extender. The invention further relates to the use of high ethyleneether content poly(tetramethylene-co-ethyleneether) glycol as the soft segment base material in spandex compositions. The invention also relates to new polyurethane compositions comprising poly(tetramethylene-co-ethyleneether) glycols with such high ethyleneether content, and their use in spandex.
Description
Background of invention
Invention field
The present invention relates to comprise poly-(tetramethylene-copolymerization-ethyleneether) glycol (poly (tetramethylene-co-ethyleneether) glycols) and as the new polyurethane urea compositions of the quadrol of chainextender, described poly-(tetramethylene-copolymerization-ethyleneether) glycol comprises that copolymerization obtains with oxyethane becomes subdivision by tetrahydrofuran (THF), and wherein the cell mesh derived from oxyethane gathers in (tetramethylene-copolymerization-ethyleneether) glycol to be present in this greater than the about 70 moles of % of about 37-.The invention further relates to have this high percent ethyleneether content poly-(tetramethylene-copolymerization-ethyleneether) glycol in Spandex (Spandex) composition as the purposes of soft chain segment raw material.The invention still further relates to the novel polyurethane compositions that comprises poly-(tetramethylene-copolymerization-ethyleneether) glycol with the high percent ethyleneether content of this class, and the purposes in Spandex.
Description of related art
Poly-(tetramethylene ether) glycol is also referred to as polytetrahydrofuran or tetrahydrofuran (THF) (THF, tetrahydrofuran) homopolymer, and its application as soft chain segment in polyurethane-urea is known.Poly-(tetramethylene ether) glycol is given polyurethane-urea elastomer or fiber with excellent dynamic performance.They have extremely low second-order transition temperature and are higher than the crystal melting temperature of room temperature.Thereby it is waxy solid at ambient temperature, need at high temperature preserve avoiding to solidify.
Adopted and the crystallinity of cyclic ethers copolymerization with the reduction polytetramethylene ether chains.The polymer melting temperature that this has reduced this copolyether glycol has improved simultaneously and has comprised this analog copolymer some dynamic property as the polyurethane-urea of soft chain segment.In these comonomers, be used for the especially oxyethane of this purpose, depend on this co-monomer content, it can be brought down below envrionment temperature with the melt temperature of described multipolymer.Use poly-(tetramethylene-copolymerization-ethyleneether) glycol also can improve some dynamic property such as toughness, elongation at break and the low-temperature performance of polyurethane-urea, this expects in some end-uses.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol is well known in the art.Its preparation method is recorded in United States Patent (USP) 4,139, in 567 and 4,153,786.This analog copolymer can adopt any known methods of cyclic ether polymerization preparation, as by P.Dreyfuss (Gordon ﹠amp; Breach, N.Y.1982) those that in " Polytetrahydrofuran ", describe.This class polymerization process comprises the katalysis by strong proton or Lewis acid, heteropolyacid and perfluorinated sulfonic acid or acidic resins.In some cases, using polymerization promotor may be favourable as carboxylic acid anhydride, as United States Patent (USP) the 4th, 163, in No. 115 record like that.In these cases, the primary polymer product is a diester, its then need be in step subsequently the polymer diol of hydrolysis to obtain expecting.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol is providing the advantage that is better than gathering (tetramethylene) ether glycol aspect some specific physical properties.When percent ethyleneether content surpasses 20 moles of %, poly-(tetramethylene-copolymerization-ethyleneether) glycol is appropriate heavy-gravity liquid under the room temperature, compare with poly-(tetramethylene ether) glycol of same molecular amount under the temperature that is higher than poly-(tetramethylene ether) glycol fusing point, it has lower viscosity.Be better than by the urethane of poly-(tetramethylene ether) glycol preparation or those character of polyurethane-urea by the urethane of poly-(tetramethylene-copolymerization-ethyleneether) glycol preparation or some physical properties of polyurethane-urea.
Spandex based on poly-(tetramethylene-copolymerization-ethyleneether) glycol also is well known in the art.Yet these great majority are based on poly-(tetramethylene-copolymerization-ethyleneether) of the common chainextender (co-extender) that comprises except that quadrol or chainextender.For example people's such as Pechhold United States Patent (USP) discloses for the 4th, 224, No. 432 and has used poly-(tetramethylene-copolymerization-ethyleneether) glycol with low cyclic ethers content to prepare Spandex and other polyurethane-urea.It is preferred that Pechhold has instructed the ethyleneether levels above 30%.But Pechhold does not instruct and uses chainextender altogether, can use amine mixt although it discloses.
People's such as Aoshima United States Patent (USP) discloses the use heteropolyacid catalyst for the 4th, 658, No. 065 and has prepared several THF copolyethers by THF and polyol reaction.Aoshima also discloses in polymerization process and but the cyclic ethers such as the oxyethane of copolymerization can have been combined with THF.Can be used for preparing Spandex though Aoshima discloses described copolyether glycol, do not comprise example by the Spandex of poly-(tetramethylene-copolymerization-ethyleneether) glycol preparation.
People's such as Axelrood United States Patent (USP) discloses the method that is had the polyether urethaneureas of oil-proofness and good low temperature properties by poly-(tetramethylene-copolymerization-ethyleneether) glycol preparation for the 3rd, 425, No. 999.Should have the 20-60 weight % percent ethyleneether content of (being equivalent to 29-71 mole %) by poly-(tetramethylene-copolymerization-ethyleneether) glycol.Axelrood is not disclosed in and uses these polyurethane-ureas in the Spandex.Axelrood discloses " the most useful in the present invention chainextender is the diamines that is selected from the group of being made up of uncle or secondary diamine and composition thereof ".Axelrood further discloses " most preferred diamines is the steric hindrance diamines, as dichlorobenzidine and methylene-bis (2-chloroaniline) ".There is not the public use quadrol.
People's such as Nishikawa United States Patent (USP) the 6th, 639, disclose for No. 041 have at low temperatures favorable elasticity comprise polyurethane-urea and in organic solvent the fiber of the polymkeric substance of solvation, wherein said polyurethane-urea is by polyvalent alcohol, vulcabond and the diamines preparation of the copolyether that comprises THF, oxyethane and/or propylene oxide.Nishikawa has instructed these compositions to have the improvement low-temperature performance that is better than standard homopolymer Spandex.Nishikawa also instructs " have when surpassing about 37 moles of % percent ethyleneether content, (unload power) is unacceptablely low for unloaded power under the low elongation, and elongation at break descends and setting is risen, although very slight " in this copolyether glycol.On the contrary, when Spandex of the present invention increases to 49 moles of % when the molecular fraction of ethyleneether part in the described copolyether by 27 moles of %, show the trend that elongation at break increases.
The applicant finds to have the Spandex of poly-(tetramethylene-copolymerization-ethyleneether) glycol (ethyleneether that is higher than the about 70 moles of % of about 37-) of high percent ethyleneether content as the soft chain segment raw material, with according to United States Patent (USP) the 6th, 639, No. 041 instruction is compared by the Spandex of poly-(tetramethylene-copolymerization-ethyleneether) glycol preparation that contains the about 37 weight % ethyleneethers of about 16-, and improved physicals is provided.High ethyleneether Spandex of the present invention is compared with the ethyleneether Spandex than low weight percentage ratio in the tubular tricot, shows lower carrying capacity (loadpower), higher unloaded power, higher elongation and the drawing-off potentiality (draftpotential) of Geng Gao.Therefore, in several final application, compare with low ethyleneether Spandex, high ethyleneether Spandex will be preferred.
Summary of the invention
The present invention relates to Spandex, the urethane or the polyurethane-urea reaction product that comprise following material: (a) comprise unitary poly-(tetramethylene-copolymerization-ethyleneether) glycol of the composition that is obtained by tetrahydrofuran (THF) and oxyethane copolymerization, wherein the cell mesh derived from oxyethane is present in this poly-(tetramethylene-copolymerization-ethyleneether) glycol to be higher than the about 70 moles of % of about 37 moles of %-; (b) at least a vulcabond; (c) have the 0-10 mole % quadrol chainextender of chainextender altogether, or have the about 10 moles of % of the 0-at least a diol chain-extension agent of chainextender altogether; (d) at least a chain terminator.
The invention still further relates to the method for the above-mentioned Spandex of preparation, comprise: (a) will comprise unitary poly-(tetramethylene-copolymerization-ethyleneether) glycol of the composition that obtains by tetrahydrofuran (THF) and oxyethane copolymerization, contact to form capped glycol with at least a vulcabond, wherein the cell mesh derived from oxyethane is present in described poly-(tetramethylene-copolymerization-ethyleneether) glycol to be higher than the about 70 moles of % of about 37 moles of %-; (b) randomly in the product of (a), add solvent; (c) product of (b) and at least a diamines or diol chain-extension agent and at least a chain terminator are contacted; (d) product of spinning (c) is to form Spandex.
Detailed description of the Invention
The present invention relates to novel Spandex composition, it promptly prepares greater than poly-(tetramethylene-copolymerization-ethyleneether) glycol of about 37 moles of about 70 moles of % percent ethyleneether content of %-, at least a vulcabond, ethylene glycol chainextender and at least a chain terminator such as diethylamine by having high percent ethyleneether content.Randomly, can use other vulcabond, have the highest 10 moles of % altogether quadrol chainextender and other chain terminator of chainextender.Based on the application's purpose, poly-(tetramethylene-copolymerization-ethyleneether) multipolymer that will contain high ethyleneether is defined as and comprises greater than the about 70 moles of % of about 37 moles of %-derived from those of the repeating unit of oxyethane.For example the cell mesh derived from oxyethane can be present in poly-(tetramethylene-copolymerization-ethyleneether) glycol with the about 58 moles of % of about 48-.If the amount of ethyleneether maintains and is higher than about 37 moles of % in poly-(tetramethylene-copolymerization-ethyleneether), for example be higher than about 40 moles of %, then compare with the Spandex with low percentage ratio ethyleneether of identical or similar molecular weight, this Spandex has improved physical properties, especially carrying capacity, unloaded power and elongation.Thereby for several final application, with respect to the Spandex of low percent ethyleneether content, the Spandex of high percent ethyleneether content will be preferred.
Block polyurethane of the present invention or polyurethane-urea are by poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild randomly polymer diols, at least a vulcabond and the preparation of difunctionality chainextender.Poly-(tetramethylene-copolymerization-ethyleneether) glycol can be formed for producing the urethane of Spandex or " soft chain segment " of polyurethane-urea.Should poly-(tetramethylene-copolymerization-ethyleneether) glycol or diol mixture at first with at least a di-isocyanate reaction, form the end capped prepolymer of NCO-(" capped glycol "), then it is dissolved in The suitable solvent such as N,N-DIMETHYLACETAMIDE, dimethyl formamide or the N-Methyl pyrrolidone, reacts with two functional chain extenders then.When chainextender forms urethane during for glycol.When chainextender forms polyurethane-urea during for diamines, polyurethane-urea is a group of urethane.In the preparation of the polyurethaneurea polymer that can be spun into Spandex, poly-(tetramethylene-copolymerization-ethyleneether) glycol is by the successive reaction chain extension of terminal hydroxy group and vulcabond and diamines.In each case, described poly-(tetramethylene-copolymerization-ethyleneether) glycol must experience chain extension, has the polymkeric substance that essential attributes comprises viscosity to provide.If desired, can use dibutyl tin laurate, stannous octoate, mineral acid, tertiary amine such as triethylamine, N, N '-lupetazin etc. and other known catalyzer are to promote termination procedure.
Be used to prepare disclosed method in No. the 4th, 139,567, the United States Patent (USP) that poly-(tetramethylene-copolymerization-ethyleneether) glycol of urethane of the present invention or polyurethane-urea can be by Pruckmayr, adopt solid perfluorinated sulfonic resin Preparation of Catalyst.Alternatively, can use any other acidic cyclic ether polymerization catalyst such as heteropolyacid to produce these poly-(tetramethylene-copolymerization-ethyleneether) glycol.Heteropolyacid that can use in the present invention practice and salt thereof can be disclosed those catalyzer that use in polymerization of cyclic ethers or copolymerization in No. the 4th, 658,065, people's such as Aoshima United States Patent (USP) for example.These polymerization processs can comprise promotor such as the diacetyl oxide that use is extra, maybe can comprise using the chain terminator molecule to regulate molecular weight.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to prepare urethane of the present invention or polyurethane-urea can comprise by what tetrahydrofuran (THF) and oxyethane copolymerization obtained and becomes subdivision, wherein the percentage ratio of ethyleneether part is greater than the about 70 moles of % of about 37 moles of %-, or the about 58 moles of % of about 48 moles of %-.Randomly, poly-(tetramethylene-copolymerization-ethyleneether) glycol that can be used for preparing polyurethane-urea of the present invention or urethane can comprise by what tetrahydrofuran (THF) and oxyethane copolymerization obtained and become subdivision that wherein ethyleneether percentage ratio partly is the about 70 moles of % of about 40 moles of %-.Be present in equating with the percentage ratio of ethyleneether part in being present in this glycol in this glycol derived from the unitary percentage ratio of oxyethane.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to prepare urethane of the present invention or polyurethane-urea can have the daltonian molecular-weight average of about 650 dalton-Yue 4000.For selected physical properties such as elongation, higher poly-(tetramethylene-copolymerization-ethyleneether) glycol molecular weight is favourable.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to prepare urethane of the present invention or polyurethane-urea can comprise on a small quantity the unit derived from the particularly non-cyclisation glycol of chain terminator glycol molecules.Non-cyclisation glycol is defined as and is not easy to the glycol that cyclisation forms cyclic ethers under reaction conditions.These non-cyclisation glycol can comprise ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butynediol and water.
Randomly comprise at least a additional component such as 3-methyltetrahydrofuran, derived from 1, poly-(tetramethylene-copolymerization-ethyleneether) of the ether of ammediol or a small amount of other glycol of adding as molecular weight regulator also can be used for preparing urethane of the present invention and polyurethane-urea, and is included in the implication of term " poly-(tetramethylene-copolymerization-ethyleneether) or poly-(tetramethylene-copolymerization-ethyleneether) glycol ".Described at least a additional component can be the comonomer of this polymer diol, maybe can be other material with poly-(tetramethylene-copolymerization-ethyleneether) glycol blend.This at least a additional component can exist with the amount of not damaging the useful aspect of the present invention.
Spendable vulcabond includes but not limited to 1-isocyanate group (isocyanato)-4-[(4-isocyanate group phenyl) methyl] benzene, the cyanate ester based phenyl of 1-isocyanate group-2-[(4-) methyl] benzene, two (4-isocyanate group cyclohexyl) methane, 5-isocyanate group-1-(isocyanic ester ylmethyl)-1,3,3-trimethyl-cyclohexane, 1,3-is diisocyanate based-4-methylbenzene, 2,2 '-tolylene diisocyanate, 2,4 '-toluenediisocyanate and their mixture.Preferred vulcabond is 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene, the cyanate ester based phenyl of 1-isocyanate group-2-[(4-) methyl] benzene and their mixture.Particularly preferred vulcabond is 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene.
When needs urethane, chainextender is a glycol.The example of spendable this class glycol includes but not limited to ethylene glycol, 1, ammediol, 1,2-propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1, ammediol, 2,2,4-trimethylammonium-1,5-pentanediol, 2-methyl-2-ethyl-1, ammediol, 1,4-two (hydroxy ethoxy) benzene, 1,4-butyleneglycol and their mixtures.This diol chain-extension agent can comprise the common chainextender of the about 10 moles of % of 0-.
When the needs polyurethane-urea, chainextender is a diamines.The example of spendable this class diamines includes but not limited to hydrazine, quadrol, 1, the 2-propylene diamine, 1, the 3-propylene diamine, 1,2-butanediamine (1, the 2-diaminobutane), 1,3-butanediamine (1, the 3-diaminobutane), 1,4-butanediamine (1, the 4-diaminobutane), 1,3-diamino-2,2-dimethylbutane, 4,4 '-methylene radical-dicyclohexyl amine, 1-amino-3,3,5-trimethylammonium-5-amino methyl hexanaphthene, 1, the 6-hexanediamine, 2,2-dimethyl-1, the 3-diaminopropanes, 2,4-diaminostilbene-methylcyclohexane, N-methylamino two (3-propyl group amine), the 2-methyl isophthalic acid, the 5-pentamethylene diamine, 1,5-diamino pentane, 1, the 4-cyclohexanediamine, 1,3-diamino-4-methylcyclohexane, 1, the 3-cyclohexane diamine, 1,1-methylene-bis (4,4 '-diamino hexane), 3-amino methyl-3,5, the 5-trimethyl-cyclohexane, 1,3-pentamethylene diamine (1,3-diamino pentane), m-xylylene amine and their mixture.Preferred quadrol is as chainextender.This quadrol chainextender can have the common chainextender of 0-10 mole %.
Randomly, can use chain terminator such as diethylamine, hexahydroaniline, normal hexyl Amine or monofunctional alcohol chain terminator such as butanols to come the molecular weight of controlling polymers.In addition, can use more the alcohol of high functionality " chain branching agent " to control soltion viscosity as diethylenetriamine as tetramethylolmethane or trifunctional " chain branching agent ".
Urethane of the present invention and polyurethane-urea can be used in the application of the urethane of this universal class of any employing or polyurethane-urea, but when preparation is used, require high elongation rate, especially useful during the goods of low modulus or good low-temperature performance.They are useful especially in producing Spandex, elastomerics, flexibility and rigid foam, coating (solvent base and water base), dispersion, film, tackiness agent and molding.
As here using, unless otherwise indicated, otherwise term " Spandex " is meant a kind of fiber of manufacturing, and wherein fiber formation material is the long-chain synthetic polymer that contains at least 85 weight % block polyurethanes or polyurethane-urea.Spandex also is called spandex fiber (elastane).
Spandex of the present invention can be used for producing knitting and woven stretch fabric, and the clothing or the textile fabrics that comprise this kind fabric.The example of stretch fabric comprises circular knitted fabric, stockinette and warp-knitted fabric and plain weave, twill and satin and sateen cloth.Term used herein " clothing " is meant cloth products, as shirt, pants, skirt, jacket, overcoat, working suit, work pants, uniform, coat, sportswear, swim suit, brassiere, socks and underwear, also comprise fittings such as waistband, gloves, boxing glove, cap, socks or footwear.As used herein; term " textile fabrics " is meant the goods that comprise fabric; as clothing, and further comprise the article of the protective guard of for example coverlet, pillowcase, sheet, cotton-wadded quilt, blanket, bedcover, quilt cover, sleeping bag, shower curtain, door curtain, curtain, tablecloth, napkin, rag, dish towel and decoration or furniture.
Spandex of the present invention can be used for woven fabrics, weft knitted fabric (comprising flat pin and annular), warp-knitted fabric and personal hygiene article such as diaper separately or with various other fiber combinations.This Spandex can be that expose, that be capped or with collaborative fiber (companion fiber) as windings such as nylon, polyester, cellulose acetate, cottons.
The fabric that comprises Spandex of the present invention also can comprise at least a fiber that is selected from by the group of protein, Mierocrystalline cellulose and synthetic polymeric fibers or combinations thereof.As used herein, " protein fibre " is meant the fiber that is made of protein, comprises animal fibre such as wool, silk, mohair, cashmere, Aloysia gratissima alpaca, mohair, vicugna, Pilus Cameli and other hair and the fur fiber of natural generation.As used herein, " cellulosic fibre " is meant the fiber of being produced by trees or textile material, comprises for example cotton, artificial silk, cellulose acetate, lyocell, flax fiber, ramee and other vegetable fibre.As used herein, " synthetic polymeric fibers " is meant regenerated fiber, this regenerated fiber is from the polymer production that is made up by chemical element or compound, comprises for example polyester, polymeric amide, acrylic fiber, Spandex, polyolefine and Kevlar.
They also the additive of various significant quantities can be used in the Spandex of the present invention, as long as can not weaken useful aspect of the present invention.Example comprises mixture, barium sulfate, hindered phenol and the zinc oxide of matting agent such as titanium dioxide and stablizer such as hydrotalcite, magnesium calcium carbonate and hydromagnesite stone, dyestuff and dyeing intensifier, antiseptic-germicide, release agent, silicone oil, hindered amine as light stabilizer, ultraviolet screening agent etc.
Spandex of the present invention or the fabric that comprises it can adopt normal dyeing and typography dyeing and printing, for example exhaust the method for dying by the enforcement of water dyeing liquid, pad material that comprises Spandex or the material that comprises Spandex by the injection of employing staining fluid by the employing staining fluid by under 20 ℃ of-130 ℃ of temperature, adopting.
When adopting matching stain, can follow ordinary method.For example in exhausting the method for dying, fabric can be introduced during the water dyeing of pH value between 3-9 bathe, it is stablized through about 10-80 minute by about 20 ℃ of temperature be heated to the 40-130 ℃ of temperature in the scope subsequently.Before the cooling described dye bath and fabric were kept 10-60 minute in 40-130 ℃ of temperature range then.Thereafter remove loose dyestuff from the fabric flushing.Be higher than 110 ℃ of exposure durations under the temperature by being minimized in, kept the stretching and the recoverability of Spandex best.When using dispersed dye, also can follow ordinary method.
As used herein, term " washing fastness (washfastness) " is meant anti-the fading property of DYED FABRICS when family or commercial laundering.Washing fastness can not cause not washable goods to fade (colorloss) completely, is also referred to as color loss (color bleed) sometimes.This can cause goods that variable color takes place when washing jointly with not wash-resistant goods.The human consumer expects that usually fabric or yarn show washing fastness.That washing fastness relates to is fibrous, textile dyeing and finishing technique and wash conditions.For current clothes, the Spandex with washing fastness of improvement is expected.
The washing fastness character of described Spandex can be supported and further enhancing by using conventional assistant chemical additive.Can use the negatively charged ion synthetic tanning agent to improve the washing fastness feature, and when needing minimum dyestuff to divide timing between this Spandex and collaborative yarn, described negatively charged ion synthetic tanning agent also can be used as dyeing inhibitor and blocker (blocking agent).Anionic sulfonated oil is when the needs level dyeing, is used to suppress the auxiliary agent of anionic dyestuff and the effect of Spandex that described dyestuff is had strong affinity more or collaborative fiber.Cationic fixing agent can use separately, or is used in combination to support improved washing fastness with the negatively charged ion laking agent.
The Spandex fiber can be formed by fiber spinning process such as dry-spinning or melt-spinning by urethane of the present invention or polyurethaneurea polymer solution.When the needs Spandex at this moment, polyurethane-urea is typically by dry-spinning or wet spinning.In the dry-spinning method, the polymers soln metering that comprises polymkeric substance and solvent enters spinning chamber (spin chamber) by the spinning nozzle orifice and forms wall scroll or many long filaments.Typically, with described polyurethaneurea polymer by with polyreaction in the solvent phase that uses with solvent be dry spun into long filament.Make air solidify described long filament with evaporating solvent by spinning chamber.Long filament is with at least 550 meters/minutes coiling speed dry-spinning.Spandex of the present invention is preferably with the spinning of the speed above 800 meters/minute.As used herein, term " spinning speed " is meant coiling speed, and it is by drive roll speed decision and identical with it.The good spinnability of Spandex long filament be characterised in that in spinning cell and scrolling in fracture of wire seldom.Described Spandex can be spun into monofilament or adopt routine techniques to be agglomerated into multifilament yarn.The fabric dtex (dtex) of every long filament is in 6-25 decitex/filament scope.
Increase the spinning speed of Spandex composition, and compare at the identical Spandex of more low rate spinning, will reduce its elongation and its carrying capacity of raising, this is well known to a person skilled in the art.Thereby, reduce spinning speed with the elongation that promotes Spandex with reduce its carrying capacity, thus increase its in annular knitting (circular knitting) but and the drawdown in other Spandex technological operation, be known practice.Yet, reduce spinning speed and reduced production efficiency.
Although have same %NCO number and approximately equalised molecular weight, the Spandex of being made by poly-(tetramethylene-copolymerization-ethyleneether) glycol with higher percent ethyleneether content provides visibly different physical properties.For example, though show to have similar %NCO and glycol molecular weight in the following table 1, embodiment 1 and Comparative Examples " a " with different percentage ratio ethyleneether numerical value have visibly different percentage ratio elongation values.When with Spandex composition of the present invention (589%, embodiment 1, table 2) and standard Spandex (549%, embodiment " b ", table 1) when comparing, this difference even bigger.But because the Spandex drawdown that promotes, it can be used for reducing Spandex content, thereby higher elongation performance makes the clothing manufacturer be benefited.
Because the more lower production cost of poly-(tetramethylene-copolymerization-ethyleneether) glycol of higher percent ethyleneether content (higher turnover ratio and still less by product formation) is so exist the remarkable economic motivation of poly-(tetramethylene-copolymerization-ethyleneether) glycol that uses higher percent ethyleneether content.Use or avoid using as far as possible common chainextender less and particularly mainly use quadrol to come the discovery of extend polymers, provide elongation, screen resilience (retractive force) and the lower carrying capacity of improving greatly with respect to prior art, and made it possible to the Spandex performance of using more cheap raw material to be improved.
In addition, the heat settability that comprises on a small quantity or do not contain the high percent ethyleneether content Spandex of common chainextender equates with poly-(tetramethylene ether) glycol-based (standard) Spandex that comprises common chainextender.Adding common chainextender in the Spandex composition is known to improve the thermal-setting performance, but also known its can reduce elongation.For example, compare with the standard Spandex with common chainextender of Comparative Examples " b ", (heat set efficiency) is lower for the heat-set efficiency of Comparative Examples " a " Spandex (27% percent ethyleneether content).Yet the per-cent elongation of Comparative Examples " a " is greater than Comparative Examples " b ".Ground beyond expectation, the Spandex of embodiment 1 is compared with Comparative Examples " a " or " b " all has higher heat-set efficiency and higher per-cent elongation.Thereby Spandex compositions table of the present invention reveals good thermal-setting performance, and does not have to use the performance and the cost defective of chainextender altogether, has kept outstanding elongation performance simultaneously.
Practice of the present invention is set forth by following examples, and described embodiment is not used in and limits the scope of the invention.The physical property data of embodiment 1-11 and Comparative Examples " a ", " b ", " c ", " d " and " e " is shown among the table 1-12.
As used herein, unless otherwise indicated, otherwise term " DMAc " expression dimethylacetamide solvent, the weight percentage of isocyanate end in term " %NCO " the expression capped glycol, term " MPMD " expression 2-methyl isophthalic acid, 5-pentamethylene diamine, term " EDA " expression 1,2-quadrol, and poly-(tetramethylene ether) glycol of term " PTMEG " expression.
As used herein, term " end-blocking ratio " is defined as the mol ratio of vulcabond and glycol, and its basis is defined as 1.0 moles of glycol.Thereby this end-blocking provides with single numerical value than typically, i.e. the vulcabond mole number of every mole of glycol.For polyurethane-urea of the present invention, preferred vulcabond is about 1.2-about 2.3 with the mol ratio of poly-(tetramethylene-copolymerization-ethyleneether) glycol.For urethane of the present invention, the mol ratio of preferred vulcabond and poly-(tetramethylene-copolymerization-ethyleneether) glycol is about 17 for about 2.3-, preferably about 2.9-about 5.6.
Material
THF and PTMEG (TERATHANE 1800) can be by Invista S. à r.l., Wilmington, and Delaware, USA obtains.NAFION perfluorinated sulfonic resin can be by E.I.DuPont de Nemours and Company, Wilmington, and Delaware, USA obtains.
Analytical procedure
Toughness is the rupture stress that stretches in the circulation the 6th, or in other words, is the fiber resistance to fracture when the ultimate elongation.Carrying capacity is at first stress under the specific elongation in the circulation that stretches, or in other words, for fiber to being stretched to the more resistance of high elongation rate.Unloaded power be the 5th shrink circulate in stress under specific extensibility, or in other words, be fiber screen resilience under given extensibility after being circulated to 300% extensibility 5 times.
The percent isocyanate of percent isocyanate-capped glycol (%NCO) is according to S.Siggia, " Quantitative Organic Analysis via Functional Group ", the third edition, Wiley ﹠amp; Sons, New York, the method for 559-561 page or leaf (1963) adopts potentiometric titration to measure.
In percent ethyleneether content-poly-(tetramethylene-copolymerization-ethyleneether) glycol the level of percent ethyleneether content by
1H NMR measures mensuration.To gather (tetramethylene-copolymerization-ethyleneether) glycol sample dissolution at suitable NMR solvent such as CDCl
3In, obtain
1H NMR spectrum.Merging-OCH that will be under 3.7-3.2ppm
2Under the integration at peak and the 1.8-1.35ppm merge-C-CH
2CH
2The integration at-C-peak compares.Should-OCH
2-peak is from the keyed jointing (O-CH based on EO
2CH
2-O-) with based on the keyed jointing (O-CH of THF
2CH
2CH
2CH
2-O-), and-C-CH
2CH
2-C-keyed jointing only comes from THF.The molar fraction of ethyleneether keyed jointing in poly-for drawing (tetramethylene-copolymerization-ethyleneether) glycol, from merge-OCH
2Deduct in the integration at-peak-C-CH
2CH
2The integration at-C-peak, then with the result divided by this-OCH
2The integration at-peak.
The number-average molecular weight of number-average molecular weight-described poly-(tetramethylene-copolymerization-ethyleneether) glycol is measured by the hydroxy number method.
Heat-set efficiency-for measuring heat-set efficiency, on yarn samples stuck-at-0cm framework, and stretching 1.5x.This framework (sample is housed) level is placed the baking oven 120 seconds that is preheated to 190 ℃.Make sample lax, and framework is cooled to room temperature.Then sample (still on framework and lax) was immersed in the ebullient softening water 30 minutes.Framework and sample are shifted out from described bath, and make it dry.Measure length of yarn, and according to following Equation for Calculating heat-set efficiency (HSE is with the percentage ratio form):
%HSE=(thermal-setting length-original length)/(tensile elongation-original length) * 100
For being used to comprise Spandex and fabric cotton or hair, need be at 175 ℃ at least about 85% Spandex heat-set efficiency.For using jointly, can obtain similar heat-set efficiency at 190 ℃ with stiff fibre such as nylon.
The intensity of intensity and elastic property-Spandex and elastic property are measured according to the general method of ASTM D2731-72.Use Instron tension measurement instrument to measure tensile property.For each measurement, use three long filaments, 2 inches (5cm) gauge lengths and 0-300% elongation cycle are carried out, and use in controlled environment in about 70 and 65% relative humidity (+/-2%) down after aging 24 hours, former state long filament from reel is implemented, promptly without flushing or other processing.Sample circulates 5 times with 50cm/ minute constant rate of elongation, keeps 30 seconds under 300% elongation after the 5th stretches then.Measure the stress under 300% elongation after the 5th elongation immediately, note is done " G1 ".The stress note that fiber obtains after keeping 30 seconds under 300% elongation is done " G2 ".Adopt following formula to determine stress relaxation:
Stress relaxation (%)=100 * (G1-G2)/G1
Stress relaxation is also referred to as stress decay (being abbreviated as Dec% in table 5).
Carrying capacity, the stress when promptly stretching for the first time on the Spandex is measured under 100%, 200% or 300% elongation in first circulation, is recorded in the table and with " LP " with gram/DENIER and represents; For example LP200 represents the carrying capacity under 200% elongation.Unloaded power, promptly the stress under 100% or 200% elongation in the 5th idle cycle is also put down in writing with gram/DENIER; Be expressed as " UP ".Elongation at break (" Elo ") and toughness (" ten ") use improved Instron anchor clamps to measure in the 6th stretching circulation, and these anchor clamps are attached with string rubber to reduce slip.
The per-cent distortion-unless otherwise indicated, otherwise the per-cent distortion is also measured on the sample that experiences 5 0-300% elongation/relaxation cycles.Per-cent distortion (" %SET ") following calculating:
％SET＝100(Lf-Lo)/Lo
Wherein Lo and Lf are respectively before five elongation/relaxation cycles and the back keeps stretching but long filament (yarn) length when not having pulling force.
Annular knitting (CK) drawing-off-in knitting, when Spandex by feeding winding when support plate transmits and follows downward pin place (knit stitch) and transmits, because pin uses speed different from the delivery rate of feeding winding with Spandex, thereby cause Spandex elongation (drawing-off).Hard yarn line delivery rate (meter/minute) is generally 2.5-4 doubly (2.5x-4x) with the ratio of Spandex delivery rate, and is called machine draft " MD ".This is corresponding with 150%-300% or bigger Spandex elongation.As used herein, term " hard yarn line " is meant inelastic relatively yarn, as polyester, cotton, nylon, artificial silk, cellulose acetate or wool.
The total draft of spandex yarn is that machine draft (MD) and package draft (PD) are long-pending, and described package draft is spandex yarn tensile amount in feeding winding.For specific DENIER (or dtex), Spandex content and total draft are inversely proportional in the fabric; Total draft is high more, and Spandex content is low more.PR is defined as 100* (length of yarn in the package-lax length of yarn)/(length of yarn in the package) for being called the measurement character of " package relax percentage ratio ".For the Spandex that uses in annular knitted elastic single jersey, PR typically observed value is 5-15.The PR that employing records, package draft (PD) is defined as 1/ (1-PR/100).Thereby total draft (TD) also can be calculated as MD/ (1-PR/100).Yarn with 4x machine draft and 5%PR should have the total draft of 4.21x, and the yarn with 4x machine draft and 15%PR should have the total draft of 4.71x.
Based on economic cause, annular knitting person manages to use the minimum Spandex content that is consistent with enough textile properties and homogeneity usually.As explained above, increasing the Spandex drawing-off is a method that reduces its content.The principal element of restriction drawing-off is the per-cent elongation at break, and the yarn that therefore has high per-cent elongation at break is most important factor.Defective in other factors such as fracture toughness, friction, yarn viscosity, DENIER homogeneity and the yarn can reduce actual attainable drawing-off.Knitting person will be by reducing the drawing-off amount by limit drawing-off amount (the per-cent elongation at break of measurement), for these limiting factors provide safety margin.Their typically logical following modes are determined this " the drawing-off amount that can bear ": increase the drawing-off amount and reach unacceptable degree such as 5 fractures of per 1000 rotations of knitting machine until knitting fracture, retreat then until obtaining acceptable performance once more.
Knitting needle tension force also is drawing-off quantitative limitation factor.Feed tension in the spandex yarn is directly relevant with the total draft amount of spandex yarn.It also is the function of the intrinsic modulus of spandex yarn (carrying capacity).For keep acceptable low-tension under high drawing-off amount in knitting, it is favourable that Spandex has low modulus (carrying capacity).
Therefore, but the ideal yarn of height drawdown should have high per-cent elongation at break, low modulus (carrying capacity) and sufficiently high toughness, low friction and viscosity, DENIER number and low-level defective uniformly.
Because its stress-strain property, along with the tension force that puts on Spandex increases, it is big that the drawing-off of Spandex (stretching) becomes; On the contrary, the drafted amount of Spandex is big more, and the tension force of yarn is high more.Typical Spandex path is as follows in the annular knitting machine.By feeding winding metered supply spandex yarn by or pass the broken end detector, by one or more break-in rollers, arrive support plate then, described support plate is with lead knitting needle and enter stitch (stitch) of Spandex.Because along with spandex yarn passes through each device or roller by feeding winding, there is cumulative tension force in the frictional force that each device that contacts with Spandex or roller are given in Spandex.Thereby, relevant with the tension force sum in whole Spandex path at the total draft of stitch place Spandex.
Remaining DMAc percentage ratio is by Duratech DMAc analysis-e/or determining in the residual DMAc-Spandex sample in the Spandex.Use the zellon (perclene) of known quantity from the Spandex of known weight, to extract DMAc.Absorb and will be worth by the UV that measures DMAc then and contrast the quantity of determining DMAc in the zellon with typical curve.
The wet creep (HWC) of the wet creep-Re of heat is by measuring the original length L of yarn
o, it is stretched to the sesqui (1.5L of its original length
o), under its stretching condition, its immersion maintained in the 97-100 ℃ of water-bath in the temperature range 30 minutes, it is shifted out from water-bath, remove tension force and also measuring final lengths L
fBefore sample was measured at least at room temperature lax 60 minutes.The wet creep percentage ratio of heat is calculated by following formula:
％HWC＝100×[(L
f-L
o)/L
o]
Fiber with low %HWC provides outstanding performance in hot wet finishing operation in dyeing.
The limiting viscosity of limiting viscosity (IV)-urethane and polyurethane-urea is according to ASTM D2515, in standard C annon-Fenske viscometer tube under 25 ℃, contrast the viscosity of this polymkeric substance in the DMAc dilute solution and the viscosity of DMAc itself (" relative viscosity " method) and measure, and with the dl/g record.
Washing fastness-for measuring washing fastness, test (American Association of Textile Chemists and ColoristsTest Method 61-1996 is infected with in painted 100% Spandex pieces of fabric implementation criteria washing, " Colorfastness to Laundering, Home and Commercial:Accelerated "; 2A version), it is used for imitating five kinds of typical low temperature-warm family or commercial laundering.This test exists down at the multifilament test fabric that comprises cellulose acetate, cotton, nylon 6,6, polyester, acrylic resin and wool fabric band to be implemented, and visual valuation degree of being infected with.In this was estimated, 1 and 2 for poor, and 3 are, 4 be to be excellent with 5 very.In this standard, the poorest being infected with of numerical value 1 expression, numerical value 5 expressions are not infected with.Tone (color shade) result of variations also adopts this identical standard test; 5 expressions do not change and 1 expression is maximum changes.
Color and luster stability on the Spandex fabric is also used Color-Eye 7000GretagMacbeth
TMThe colourimeter spectrum analyzer adopts the quantitative assay of Optiview Quality ControlVersion 4.0.3 software.The result is with the CIELAB unit record.Main light source is D
65Tonal variation result is by the color of the preceding fabric sample of contrast washing and the color measurenent of four washing back identical fabric samples.
Embodiment
By in remaining in 57-72 ℃ continuously stirring jar reactor, the solution of THF, oxyethane and water is contacted with Nafion resin catalyst, unreacted THF and oxyethane are removed in distillation subsequently, remove by filter the catalyst fines of any existence and then distillation remove the cyclic ethers by product and prepare respectively that to have 27 moles of % and 49 moles of % percent ethyleneether content and molecular weight be 2049 and 2045 daltonian random poly-(tetramethylene-copolymerization-ethyleneether) glycol samples.Preparation has random poly-(tetramethylene-copolymerization-ethyleneether) glycol of 38 moles of % ethyleneether units and 2535 number-average molecular weights in the same manner.Random poly-(tetramethylene-copolymerization-ethyleneether) glycol that has 37 moles of % ethyleneether units and have 1900 number-average molecular weights is bought by Sanyo ChemicalIndustries.
For each embodiment, make described poly-(tetramethylene-copolymerization-ethyleneether) glycol and 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene contacts, form end-blocking (isocyanate-terminated) glycol, then it is dissolved among the DMAc, use the quadrol chain extension, and use diethylamine to carry out chain termination to form the polyurethane-urea spinning solution.The consumption of DMAc is to make final spinning solution based on the solution gross weight, wherein contains the polyurethane-urea of 34-38wt%.In all compositions, add antioxidant, pigment and silicone spin finish aid.In the cylinder that provides drying nitrogen, coalescent long filament is reeled by godet wheel and with 840-880m/min with described spinning solution dry-spinning.This long filament has better spinnability.Unless otherwise indicated, otherwise the yarn of all embodiment all has " bright " gloss.The gloss that " becomes clear " passes through based on yarn weight, and the anti-chlorine additives of pigments that comprises about 4 weight % obtains.Unless otherwise indicated, otherwise the yarn of all embodiment is 40 DENIER (44 dtex), and comprises 4 long filaments.All Spandex fiber samples all spin in that all yarns are dried under the identical approximately dissolvent residual level conditions.
Embodiment 1 (Spandex that contains high ethyleneether)
Random poly-(tetramethylene-copolymerization-ethyleneether) glycol that will have 49 moles of % ethyleneether units and 2045 number-average molecular weights uses 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene, use the 100ppm mineral acids as catalyzer end-blocking 120 minutes at 90 ℃, obtain the 2.2%NCO prepolymer.The mol ratio of vulcabond and glycol (end-blocking ratio) is 1.64.Then this capped glycol is used the DMAc solvent cut, use the EDA chain extension and use diethylamine to carry out chain termination with preparation Spandex polymers soln.The consumption of DMAc wherein contains the 38wt% polyurethane-urea for making final spinning solution based on the solution gross weight.This spinning solution dry-spinning is advanced to provide in the cylinder of 440 ℃ of drying nitrogens, coalescent, by godet wheel and reel with 869m/min.This long filament has better spinnability.Fibrous property is shown in Table 1.
Comparative Examples " a " (Spandex that contains medium EO)
Random poly-(tetramethylene-copolymerization-ethyleneether) glycol that will have 27 moles of % ethyleneether units and 2049 number-average molecular weights uses 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene, use the even mineral acids of 100ppm (homogeneous mineral acid) as catalyzer end-blocking 120 minutes at 90 ℃, obtain the 2.2%NCO prepolymer.The mol ratio of vulcabond and glycol is 1.64.Then this capped glycol is used the DMAc solvent cut, use the EDA chain extension and use diethylamine to carry out chain termination with preparation Spandex polymers soln.The consumption of DMAc wherein contains the 36wt% polyurethane-urea for making final spinning solution based on the solution gross weight.This spinning solution dry-spinning is advanced to provide in the cylinder of 440 ℃ of drying nitrogens, coalescent, by godet wheel and reel with 869m/min.This long filament has better spinnability.Fibrous property is shown in Table 1.
Comparative Examples " b " (standard Spandex) with common chainextender
Poly-(tetramethylene ether) glycol that will have 1800 dalton's molecular-weight average is with 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene is 90 ℃ of end-blockings 90 minutes, obtains the 2.6%NCO prepolymer.The mol ratio of vulcabond and glycol is 1.69.This capped glycol DMAc solvent cut then with the mixture chain extension of 90/10 ratio of EDA and MPMD, and carries out chain termination with diethylamine, forms and the similar Spandex product of commercial Spandex with preparation.The consumption of DMAc is to make final spinning solution comprise the polyurethane-urea of 34.8wt% based on the solution gross weight.This spinning solution dry-spinning is advanced to provide in the cylinder of 438 ℃ of drying nitrogens, coalescent, by godet wheel and reel with 844m/min.This long filament has better spinnability.Fibrous property is shown in Table 1.
Table 1
| Embodiment | Chainextender | Ethyleneether in the % glycol | Glycol MW | ％NCO | Spinning speed (m/min) | Toughness (g/den) | elo(％) | Stress relaxation | MD(％) | PR(％) | Total draft (TD) | Heat-set efficiency |
| 1 Comparative Examples " a " Comparative Examples " b " | 100％EDA 100％EDA 90/10 EDA/MPMD | 49 27 0 | 2045 2049 1800 | 2.2 2.2 2.6 | 869 869 844 | 0.74 0.79 1.09 | 589 549 480 | 17.9 20.4 28.2 | 4.5 4.1 3.9 | 15.2 18.91 11.4 | 5.31 5.06 4.40 | 84.9 80.6 83.1 |
The analysis revealed of data in the his-and-hers watches 1, along with percent ethyleneether content increases to 49% by 27%, as reflecting in total draft value and higher heat-set efficiency, but Spandex of the present invention has the higher elongation of expectation, lower stress relaxation, higher annular knitting total drawdown.The heat-set efficiency of embodiment 1 Spandex surpasses the Spandex of the Comparative Examples " a " with low per-cent percent ethyleneether content and surpasses the Spandex of the Comparative Examples " b " of the commercially available acquisition that comprises common chainextender.In addition, above-mentioned data show that along with the molecular fraction partly of ethyleneether in the multipolymer increases to 49 moles of % by 27 moles of %, elongation at break has the trend of increase.
Comparative Examples " c " (the Spandex that contains high ethyleneether (lower end)) with common chainextender
Method according to Comparative Examples " a " prepares Comparative Examples " c ", but uses random poly-(tetramethylene-copolymerization-ethyleneether) glycol with 37 moles of % ethylene oxide units and 1900 number-average molecular weights.This Spandex is near the lower end that contains the Spandex of high ethyleneether.The mol ratio of vulcabond and glycol is 1.62.This glycol uses the EDA and the MPMD mixture chain extension of 90/10 ratio.This polymers soln has 34% solid, and dry-spinning advances to provide in the cylinder of 410 ℃ of drying nitrogens.In this spinning solution, do not add " becoming clear " pigment.
Embodiment 2 (Spandex that contains high ethyleneether (lower end) that does not have common chainextender)
Adopt the method for embodiment 1 to use random poly-(tetramethylene-copolymerization-ethyleneether) glycol to prepare embodiment 2 with 37 moles of % ethyleneether units and 1900 number-average molecular weights.The mol ratio of vulcabond and glycol is 1.60.This Spandex is near the lower end of containing the Spandex of high ethyleneether.Spinning solution has 36% solid, and dry-spinning advances to provide in the cylinder of 430 ℃ of drying nitrogens.In this spinning solution, do not add " becoming clear " pigment.
Table 2
| Embodiment | Ethyleneether in the % glycol | Chainextender | Glycol MW | ％ NCO | Spinning speed (m/min) | Toughness (g/den) | elo(％) | MD (％) | PR (％) | Total draft (TD) |
| Comparative Examples " c " 2 | 37 37 | 90/10 EDA/MPMD 100％EDA | 1900 1900 | 2.6 2.2 | 869 844 | 0.56 0.5 | 592 622 | 3.4 4 | 7.76 9.64 | 3.69 4.43 |
The analysis revealed of data in the his-and-hers watches 2, but the total drawdown of the attainable annular tricot of embodiment 2 Spandexs substantially exceeds the Comparative Examples " c " based on same poly-(tetramethylene-copolymerization-ethyleneether) glycol.What make attention is that embodiment 2 does not contain common chainextender.
Comparative Examples " d " (Spandex that contains medium ethyleneether)
Method according to Comparative Examples " a " prepares Comparative Examples " d ", but is to use random poly-(tetramethylene-copolymerization-ethyleneether) glycol with 27 moles of % ethyleneether units and 2049 number-average molecular weights.The mol ratio of vulcabond and glycol is 1.64.This polymers soln has 36.5% solid, and advances to provide in the cylinder of 440 ℃ of drying nitrogens as three filament yarn dry-spinning.
Table 3
| Embodiment | Ethyleneether in the % glycol | Chainextender | Glycol MW | ％ NCO | Spinning speed (m/min) | Long filament | Toughness (g/den) | elo(％) | MD (％) | PR (％) | Total draft (TD) |
| Comparative Examples " d " Comparative Examples " a " 1 | 27 27 49 | 100％EDA 100％EDA 100％EDA | 2049 2049 2045 | 2.2 2.2 2 2 | 844 869 869 | 3 4 4 | 0.61 0.79 0 74 | 649 549 589 | 4.1 4.14 4.5 | 14.72 18.91 15.2 | 4.81 5.11 5.31 |
The analysis revealed of data in the his-and-hers watches 3, along with the percentage composition of ethyleneether increases to 49% by 27%, Spandex of the present invention have expectation be higher than Comparative Examples " a " and " d " but annular knitting total drawdown.Comparative Examples " a " and " d " with same composition show that long filament number and spinning speed can influence final yarns character, even even give elongation or the toughness that yarn is higher than embodiment 1, Zong but also still have relatively poor annular knitting drawdown.In addition, above-mentioned data show that along with ethyleneether part molecular fraction in the copolyether increases to 49 moles of % by 27 moles of %, elongation at break has the trend of increase.
In another test, the long filament sample of embodiment 1, Comparative Examples " a " and Comparative Examples " b " is stretched to 200% elongation with 50cm/min speed, and makes it lax.Implement this stretching-relaxation cycles 5 times.Measurement in the 5th relaxation cycles two points (30% and 60% elongation, note is " UP respectively
30" and " UP
60") unloaded power (stress), and with gram/DENIER record.In the 6th stretches, measure the extension at break percentage.Also experienced the distortion of the sample of 5 0-200% elongation/relaxation cycles 22 ℃ of measurements.This distortion (" %S ") is calculated with percentage ratio:
％S＝100(L
a-L
b)/L
b
L wherein
aAnd L
bBe respectively before five elongation/relaxation cycles and the back keeps stretching but when not stretching, the length of long filament (yarn).Test three samples, by calculating mean value as a result.The physical properties of fiber is recorded in the table 4
Table 4:0-200% loop-around data
| Embodiment | Ethyleneether in the % glycol | Chainextender | Glycol MW | ％NCO | UP90 (g/den) | UP60 (g/den) | UP30 (g/den) | ELO％ | SET％ | LP200 (g/den) |
| Comparative Examples a 1 Comparative Examples b | 27 49 0 | 100％EDA 100％EDA 90/10 EDA/MPMD | 2049 2045 1800 | 2.2 2.2 2.6 | 0.0241 0.0247 0.0242 | 0.0178 0.0182 0.0189 | 0.0091 0.0090 0.0090 | 569 576 448 | 9.44 9.63 10.13 | 0.1045 0.1027 0.1476 |
The analysis revealed of data in the his-and-hers watches 4, when having the percent ethyleneether content that is higher than 37 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol, unloaded power under the low elongation both be not brought down below the unloaded power of low ethyleneether molar content, and did not have unacceptable low with respect to the commercial Spandex of Comparative Examples " b " yet.If use 100%EDA as the chainextender system, when percent ethyleneether content was higher than 37 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol, elongation at break did not descend.In addition, above-mentioned data show that along with the molecular fraction partly of ethyleneether in the copolyether increases to 49 moles of % by 27 moles of %, elongation at break has the trend of increase.In addition, in poly-(tetramethylene-copolymerization-ethyleneether) glycol, use the ethyleneether of higher molar content, reduced the carrying capacity under 200% elongation ideally.
Embodiment 3,4 and 5; Comparative Examples " e "
Adopt the method for embodiment 1 to use to form shown in the table 5 with random (tetramethylene-copolymerization-ethyleneether) glycol that gathers and prepare embodiment 3,4 and 5 and Comparative Examples " e ".Spinning solution has about 31% solid, and advances to provide in the cylinder of 415 ℃ of drying nitrogens with the drive roll speed dry-spinning of 872m/min.In this spinning solution, do not add " becoming clear " pigment
Table 5
| Embodiment | Ethyleneether in the % glycol | MW | The end-blocking ratio | Chainextender | LP200 (g/den) | UP200 (g/den) | UP100 (g/den) | Dec ％ | TEN (g/den) | ELO％ | SET ％ |
| 345 Comparative Examples e | 51 51 40 27 | 2500 2500 2000 2045 | 1.83 1.83 1.69 1.71 | 100％EDA 100％EDA 100％EDA 100％EDA | 0.1309 0.1328 0.1399 0.1727 | 0.0317 0.0326 0.0310 0.0348 | 0.0179 0.0186 0.0169 0.0195 | 23.45 23.24 24.41 25.54 | 0.979 0.951 0.967 0.988 | 581 551 531 502 | 21.2 21.5 23.0 24.1 |
The analysis revealed of data in the his-and-hers watches 5 has the Spandex greater than the percent ethyleneether content of 27 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol, have low carrying capacity ideally, decay and higher elongation than low-stress.Spandex by more high-molecular-weight poly (tetramethylene-copolymerization-ethyleneether) glycol preparation has low distortion ideally.In addition, above-mentioned data show that along with ethyleneether part molecular fraction in the copolyether increases to 49 moles of % by 27 moles of %, elongation at break has the trend of increase.
Embodiment 6
Random poly-(tetramethylene-copolymerization-ethyleneether) glycol that will have 38 moles of % ethyleneether units and 2535 number-average molecular weights uses 1-isocyanate group-4-[(4-isocyanate group phenyl) methyl] benzene, use the 100ppm mineral acids as catalyzer end-blocking 120 minutes at 90 ℃.The mol ratio of vulcabond and glycol is 1.70.Then this capped glycol is used the DMAc solvent cut, use the EDA chain extension and use diethylamine to carry out chain termination with preparation Spandex polymers soln.The consumption of DMAc wherein contains the 38wt% polyurethane-urea for making final spinning solution based on the solution gross weight.This spinning solution dry-spinning is advanced to provide in the cylinder of 440 ℃ of drying nitrogens, coalescent, by godet wheel and reel with 869m/min.This long filament has better spinnability.In this spinning solution, do not add " becoming clear " pigment.This Spandex has the toughness of 0.71g/den and 617% elongation.
Comparative Examples " f "
Comparative Examples " f " adopts the method use of Comparative Examples " b " to have poly-(tetramethylene ether) glycol preparation of 1800 dalton's molecular-weight average.Final spinning solution comprises 35% solid.Spin 40 DENIER, 3 long filament spandex yarns by this polymers soln with 844 meters/minute.This Spandex has the toughness of 1.11g/den and 470% elongation.
For the washing fastness test, fabric sample is in the last form production with annular knitted tube of the Model " FAK " of Lawson Knitting Unit (Lawson-Hemphill Company).40 DENIER Spandexs of a knitting charging form the fabric of 100% Spandex.Use a kind of matching stain (Nylanthrene blue GLF) and two kinds of dispersed dye (Intrasil Red FTS and Terasil Blue GLF) according to common process this Lawson pipe sample that dyes.
The washing fastness of this Spandex fabric the results are shown in the table 6,7 and 8.The tonal variation of this Spandex fabric the results are shown in the table 9.The color readings of this Spandex (colorreading) is shown in Table 10.
Table 6. uses the washing fastness grade of the painted Spandex of 1.5%Nylanthrene Blue GLF
| Embodiment | After described washing times | Cellulose acetate | Cotton | Nylon 6,6 | Dacron polyester | Orlon acrylic fiber | Wool |
| 6 | 1 | 4 | 3.5 | 1 | 4.5 | 4.5 | 1 |
| 1 | 1 | 3 | 3.5 | 1 | 4 | 5 | 1.5 |
| Comparative Examples " f " | 1 | 3.5 | 4.5 | 1.5 | 5 | 5 | 2 |
| 6 | 2 | 4 | 3.5 | 1.5 | 5 | 5 | 1 |
| 1 | 2 | 3 | 3.5 | 1.5 | 4.5 | 5 | 1.5 |
| Comparative Examples " f " | 2 | 3.5 | 4.5 | 2 | 5 | 5 | 2.5 |
| 6 | 3 | 4.5 | 4 | 1.5 | 5 | 5 | 2 |
| 1 | 3 | 3.5 | 4 | 1.5 | 5 | 5 | 2 |
| Comparative Examples " f " | 3 | 4 | 4.5 | 2 | 5 | 5 | 2.5 |
| 6 | 4 | 5 | 4.5 | 2 | 5 | 5 | 2.5 |
| 1 | 4 | 4 | 4.5 | 1.5 | 5 | 5 | 2.5 |
| Comparative Examples " f " | 4 | 4 | 4.5 | 2 | 5 | 5 | 2.5 |
Table 7. uses the washing fastness grade of the painted Spandex of 1%Intrasil Red FTS
| Embodiment | After described washing times | Cellulose acetate | Cotton | Nylon 6,6 | Dacron polyester | Orlon acrylic fiber | Wool |
| 6 | 1 | 2 | 3.5 | 2 | 3.5 | 4.5 | 2 |
| 1 | 1 | 2.5 | 4.5 | 2.5 | 4 | 5 | 2.5 |
| Comparative Examples " f " | 1 | 2.5 | 4 | 2.5 | 4 | 5 | 3 |
| 6 | 2 | 2 | 3.5 | 2 | 3.5 | 4.5 | 2 |
| 1 | 2 | 2.5 | 4.5 | 2.5 | 4 | 5 | 2.5 |
| Comparative Examples " f " | 2 | 2.5 | 4.5 | 2.5 | 4 | 5 | 3 |
| 6 | 3 | 2 | 4 | 2 | 3.5 | 4.5 | 2 |
| 1 | 3 | 2.5 | 4.5 | 2.5 | 4 | 5 | 2.5 |
| Comparative Examples " f " | 3 | 2.5 | 4.5 | 2.5 | 4 | 5 | 3 |
| 6 | 4 | 2.5 | 4.5 | 2.5 | 4.5 | 5 | 3 |
| 1 | 4 | 2 | 4 | 2 | 3.5 | 5 | 2 |
| Comparative Examples " f " | 4 | 2.5 | 4.5 | 2.5 | 4 | 5 | 3 |
Table 8. uses the washing fastness grade of the painted Spandex of 1%Terasil Blue GLF
| Embodiment | After described washing times | Cellulose acetate | Cotton | Nylon 6,6 | Dacron polyester | Orlon acrylic fiber | Wool |
| 6 | 1 | 4 | 4.5 | 1 | 4.5 | 5 | 1.5 |
| 1 | 1 | 4 | 3 | 1.5 | 5 | 5 | 2.5 |
| Comparative Examples " f " | 1 | 4.5 | 4.5 | 2 | 5 | 5 | 3 |
| 6 | 2 | 4 | 5 | 1 | 5 | 5 | 2 |
| 1 | 2 | 4 | 5 | 2 | 5 | 5 | 2.5 |
| Comparative Examples " f " | 2 | 4.5 | 4.5 | 2 | 5 | 5 | 3 |
| 6 | 3 | 4 | 5 | 1.5 | 5 | 5 | 2 |
| 1 | 3 | 4.5 | 5 | 2 | 5 | 5 | 2.5 |
| Comparative Examples " f " | 3 | 4 | 5 | 3 | 5 | 5 | 3 |
| 6 | 4 | 4.5 | 5 | 2 | 5 | 5 | 2.5 |
| 1 | 4 | 4.5 | 5 | 2.5 | 5 | 5 | 2.5 |
| Comparative Examples " f " | 4 | 4 | 5 | 3 | 5 | 5 | 3 |
The tonal variation result of the Spandex of four poststainings of table 9. washing
| Embodiment | Dyestuff | Tonal variation |
| 6 | Nylanthrene Blue GLF | 2 |
| 1 | Nylanthrene Blue GLF | 3 |
| Comparative Examples " f " | Nylanthrene Blue GLF | 1 |
| 6 | Intrasil Red FTS | 3 |
| 1 | Intfasil Red FTS | 4 |
| Comparative Examples " f " | Intrasil Red FTS | 3.0-4 |
| 6 | Terasil Blue GLF | 3 |
| 1 | Terasil Blue GLF | 2.0-3 |
| Comparative Examples " f " | Terasil Blue GLF | 2 |
Table 10. adopts the color readings on the colourimeter method Spandex fabric
| Embodiment | Washing times # | Dyestuff | L | A | B | DE | The K/S maximum | Colourity | Outward appearance |
| Comparative Examples " f " | 0 | Nylanthrene Blue GLF | 36.25 | -2.29 | -32.56 | 10.76 | |||
| Comparative Examples " f " | 4 | Nylanthrene Blue GLF | 58.7 | -8.48 | -14.06 | 29.74 | 1.66 | 15.43 | 18.91 |
| 6 | 0 | Nylanthrene Blue GLF | 36.2 | -1.6 | -32.59 | 10.48 | |||
| 6 | 4 | Nylanthrene Blue GLF | 48.32 | -7.42 | -26.54 | 14.75 | 4.23 | 40.42 | 41.48 |
| 1 | 0 | Nylanthrene Blue GLF | 39.98 | -4.11 | -28.62 | 7.49 | |||
| 1 | 4 | Nylanthrene Blue GLF | 44.74 | -6.23 | -28.01 | 5.25 | 5.5 | 73.42 | 72.83 |
| Comparative Examples " f " | 0 | Terasil Blue GLF | 34.9 | -8.99 | -20.47 | 10.23 | |||
| Comparative Examples " f " | 4 | Terasil Blue GLF | 43.55 | -12.68 | -17.54 | 9.85 | 5.97 | 57.7 | 58.03 |
| 6 | 0 | Terasil Blue GLF | 33.69 | -7.08 | -22.25 | 10.95 | |||
| 6 | 4 | Terasil Blue GLF | 37.23 | -10.62 | -21.4 | 5.07 | 9.59 | 87.18 | 84.22 |
| 1 | 0 | Terasil Blue GLF | 37.23 | -8.08 | -22.53 | 8.77 | |||
| 1 | 4 | Terasil Blue GLF | 39.1 | -11.79 | -20.09 | 4.83 | 8.64 | 96.45 | 94.69 |
| Comparative Examples " f " | 0 | Intrasil Red FTS | 34.29 | 45.05 | 11.99 | 17.74 | |||
| Comparative Examples " f " | 4 | Intrasil Red FTS | 33.33 | 39.02 | 9.94 | 6.47 | 15.6 | 87.93 | 91.74 |
| 6 | 0 | Intrasil Red FTS | 33.54 | 40.44 | 11.77 | 16.05 | |||
| 6 | 4 | Intrasil Red FTS | 38.02 | 39.67 | 8.03 | 5.89 | 11.14 | 69.42 | 65.19 |
| 1 | 0 | Intrasil Red FTS | 34.17 | 45.39 | 10.08 | 16.84 | |||
| 1 | 4 | Intrasil Red FTS | 34.07 | 43.11 | 10.85 | 2.4 | 16.08 | 95.49 | 97.08 |
These results show, for using the painted Spandex fabric of matching stain (Nylanthrene Blue GLF), when comparing with the Spandex fabric based on poly-(tetramethylene ether) glycol of Comparative Examples " f ", the fabric that comprises the Spandex of embodiment 6 after the washing has once provided mixing resultant, " f " compares with Comparative Examples, the result is relatively poor for part washing fastness, and a part is better identical with a part.Yet, the fabric that comprises embodiment 1 Spandex [Spandex that comprises poly-(tetramethylene-copolymerization-ethyleneether) glycol] with 49 moles of % ethyleneether units, washing once back all shows the washing fastness result who is equal to or better than Comparative Examples " f " except that the situation of cellulose acetate test film.After washing four times, the fabric that comprises embodiment 6 Spandexs [Spandex that comprises poly-(tetramethylene-copolymerization-ethyleneether) glycol] with 38 moles of % ethyleneether units, except that cellulose acetate and nylon test film, provided and the identical result of Comparative Examples " f ".The fabric that comprises embodiment 1 Spandex has provided and the identical performance of Comparative Examples " f " fabric except that the cellulose acetate testing plate.
These results show, for using the painted Spandex fabric of dispersed dye Intrasil Red, with compare based on the Comparative Examples " f " of poly-(tetramethylene ether) glycol, the once back two kinds of fabrics based on poly-(tetramethylene-copolymerization-ethyleneether) glycol of washing in all cases all show better properties.After washing four times, the fabric of embodiment 1 has provided and the identical result of Comparative Examples " f " except that the situation of polyester test film, and under polyester test film situation, Comparative Examples " f " shows less slightly being infected with.After washing four times, under the situation of acrylic acid or the like test film, the fabric of embodiment 6 Spandexs shows and the identical result of Comparative Examples " f " (and embodiment 1), but has provided the performance not as Comparative Examples " f " (with embodiment 1) in other cases.
These results show, for using the painted Spandex fabric of dispersed dye Terasil Blue, the fabric washing of embodiment 1 Spandex has provided and the identical or better result of Comparative Examples " f " after once.After the washing once, except that the situation of cotton test film, the fabric of embodiment 6 Spandexs has also provided and the identical or better result of Comparative Examples " f ".After washing four times, except that the cellulose acetate test film, the fabric of embodiment 1 Spandex is compared with Comparative Examples " f ", has provided the result of identical (under cotton, polyester and acrylic fiber situation) or better (under nylon and woolen situation).After washing four times, " f " compares with Comparative Examples, and the fabric of embodiment 6 has also provided identical (under cellulose acetate, cotton, polyester, acrylic fiber and woolen situation) or the result of better (under the situation at nylon).
The tonal variation result shows after washing four times, for dispersed dye, compares described embodiment with Comparative Examples " f " and shows tonal variation (promptly higher value) identical or still less.
Embodiment 7-11
Random poly-(tetramethylene-copolymerization-ethyleneether) glycol 1-isocyanate group-4-[(4-isocyanate group phenyl that will have 49 moles of % ethyleneether units and 2443 number-average molecular weights) methyl] benzene, adopt the even mineral acids of 100ppm as catalyzer end-blocking 120 minutes at 90 ℃, obtain the 3.5%NCO prepolymer.The mol ratio of vulcabond and glycol is 2.26.Use this capped glycol of DMAc solvent cut then, use BDO (1, the 4-butyleneglycol) chain extension with preparation Spandex polymers soln.Usually in the Spandex technology, also can in this prescription, add chain terminator, with control molecular weight and other character.Because urethane is tending towards more easily molten and has the tendency of hard segment association increase polymkeric substance apparent molecular weight still less, so chain terminator is not very important for polyurethane formulations.Above-mentioned general process is improved and is used to form embodiment 8,9,10 and 11.The consumption of DMAc wherein contains the urethane of 35wt% for making final spinning solution based on the solution gross weight.This spinning solution dry-spinning is advanced to provide in the cylinder of drying nitrogen, and coalescent long filament is reeled by godet wheel and with the speed of listing.This long filament has good spinnability.Spinning speed is 870 meters/minute.The fibrous property of embodiment 7 is shown in Table 11.Other character of embodiment 7-11 is shown in Table 12.
Table 11
| Embodiment | Ethyleneether in the % glycol | Chainextender % | Glycol MW | ％ NCO | LP1 (g/den) | LP2 (g/den) | LP3 (g/den) | ELO ％ | SET ％ | TEN (g/den) | UP1 | UP2 |
| 7 | 49 | 100％BD | 2443 | 3.5 | .0185 | .0342 | .0590 | 626 | 41 | .3218 | .0067 | .0195 |
Embodiment 7 is by the DMAc solvent spinning with 35% polymer solids
BDO is 1, the 4-butyleneglycol
Polyurethane film is cast according to following technology:
Solution-cast film-polymers soln is placed on the fixing Mylar film in the plane is with the film of film cutter (film knife) casting 0.005-0.015 inch.The Mylar film that then will be applies with polyurethane film shifts out from described plane, and places the film drying case, therein in 20-25 ℃ of drying 16-18 hour at least under nitrogen gas stream.
Melt press membrane-polyether polyols with reduced unsaturation is removed the DMAc solvent and is obtained by polyurethane solution by evaporating in by polymkeric substance under heating and nitrogen gas stream.The solid polyurethane polymkeric substance is placed between two Mylar sheet materials then.The Mylar sheet material that accompanies urethane betwixt is placed between the platen of two heating of Carver water pressure engine.Described platen is heated to 350 ℃+/-25 ℃ and be heated to 250 ℃+/-25 ℃ in another experiment in a test.With this water pressure engine platen is joined and apply 5000 pounds/square inch power mutually until platen.When urethane melted, this power/pressure was reduced to 2000 pounds/square inch rapidly.After about 30 seconds, discharge this pressure, and, make it to be cooled to room temperature from shifting out this Mylar sheet material between platen.Remove Mylar sheet material, obtain the thick transparent polyurethane film of 0.64mm.
Table 12
| Embodiment | Ethyleneether in the % glycol | Chainextender | Glycol MW | ％ NCO | Limiting viscosity (dl/g) | Film forms | Solid (%) |
| 7 | 49 | 100％BDO | 2443 | 3.5 | ---- | The melt compacting---transparent, good stretching and recovery, good tear strength is clamminess | 35.2 |
| 8 | 49 | 100％EG | 2443 | 3.5 | Cross low can't the measurement | Solution-cast---transparent, good stretching and recovery, the tear strength of difference is clamminess | 42.6 |
| 9 | 49 | 100％BDO | 2443 | 3.5 | 1.2 | Solution-cast---transparent, good stretching and recovery, good tear strength is not clamminess | 37.6 |
| 10 | 49 | 100％EG | 2443 | 10 | 0.29 | Solution-cast---White-opalescent, no stretchiness, the tear strength of extreme difference is not clamminess, wax shape sense of touch | 38.7 |
| 11 | 49 | 100％BDO | 2443 | 10 | 0.51 | Solution-cast---Lve is opaque, good stretching and recovery, and good tear strength is not clamminess | 37.7 |
Embodiment 7 and 9 is a same recipe.Embodiment 7 is used for the amplification form of solvent spinning for embodiment 9.
BDO is 1, the 4-butyleneglycol
EG is a 1.
Claims (20)
1. polyurethane-urea comprises the reaction product of following material:
(a) comprise unitary poly-(tetramethylene-copolymerization-ethyleneether) glycol of the composition that obtains by tetrahydrofuran (THF) and oxyethane copolymerization, wherein derived from the cell mesh of oxyethane with greater than the about 70 moles of % of about 37-, preferably be present in this poly-(tetramethylene-copolymerization-ethyleneether) glycol with the about 58 moles of % of about 48-;
(b) at least a vulcabond; With
(c) has the 0-10 mole % quadrol chainextender of chainextender altogether.
2. the Spandex that comprises the polyurethane-urea of claim 1.
3. the Spandex of claim 2, wherein said poly-(tetramethylene-copolymerization-ethyleneether) glycol has the daltonian molecular weight of about 650 dalton-Yue 4000.
4. the Spandex of claim 2, wherein said polyurethane-urea have the mol ratio of vulcabond with poly-(tetramethylene-copolymerization-ethyleneether) glycol of about 1.2-about 2.3.
5. the Spandex of claim 2, wherein this vulcabond is selected from by 1-isocyanate group-4-[(4-isocyanate group-phenyl) methyl] benzene, 1-isocyanate group-2-[(4-isocyanate group-phenyl) methyl] group formed of benzene and their mixture.
6. any one Spandex of claim 2-5, it under 300% elongation, has the carrying capacity of the about 0.24 gram/DENIER of about 0.11-in first elongation cycle.
7. any one Spandex of claim 2-5, it under 200% elongation, has the unloaded power of the about 0.043 gram/DENIER of about 0.027-in the 5th elongation cycle.
8. any one Spandex of claim 2-5, it under 200% elongation, has the carrying capacity of the about 0.165 gram/DENIER of about 0.075-in first elongation cycle.
9. any one Spandex of claim 2-5, it when keeping 120 seconds for 190 ℃, has the heat-set efficiency of about 77%-about 95% under stretching at 1.5x.
10. claim 6,7,8 or 9 Spandex, wherein this Spandex is to surpass about 800 meters/minute speed spinning.
11. Spandex that comprises the polyurethane-urea reaction product of following material:
(a) comprise unitary poly-(tetramethylene-copolymerization-ethyleneether) glycol of the composition that obtains by tetrahydrofuran (THF) and oxyethane copolymerization, wherein the cell mesh derived from oxyethane gathers in (tetramethylene-copolymerization-ethyleneether) glycol to be present in this greater than the about 70 moles of % of about 37-;
(b) at least a vulcabond;
(c) chainextender or their mixture;
(d) at least a chain terminator; With
Wherein, this Spandex when keeping 120 seconds for 190 ℃, has the heat-set efficiency at least about 85% under stretching at 1.5x.
12. a urethane, it comprises the reaction product of following material:
(a) comprise unitary poly-(tetramethylene-copolymerization-ethyleneether) glycol of the composition that obtains by tetrahydrofuran (THF) and oxyethane copolymerization, wherein the cell mesh derived from oxyethane gathers in (tetramethylene-copolymerization-ethyleneether) glycol to be present in this greater than the about 70 moles of % of about 37-;
(b) at least a vulcabond; With
(c) has the about 10 moles of % of the 0-at least a diol chain-extension agent of chainextender altogether.
13. comprise the Spandex of the urethane of claim 12.
14. a method for preparing Spandex comprises:
(a) will gather (tetramethylene-copolymerization-ethyleneether) glycol contacts with at least a vulcabond to form capped glycol, wherein said poly-(tetramethylene-copolymerization-ethyleneether) glycol comprises by what copolymerization tetrahydrofuran (THF) and oxyethane obtained and becomes subdivision, and gathers in (tetramethylene-copolymerization-ethyleneether) glycol to be present in this greater than the about 70 moles of % of about 37-derived from the cell mesh of oxyethane;
(b) randomly in the product of (a), add solvent;
The product of (b) is contacted with at least a diamines or diol chain-extension agent; With
(d) product of spinning (c) forms Spandex.
15. the method for claim 14, wherein said one or more diamine chain stretching agents are to have the 0-10mol% quadrol of chainextender altogether.
16. a fabric comprises claim 2,11 or 13 Spandex.
17. clothing or textile fabrics comprise the fabric of claim 16.
18. a dispersion, coating, film, tackiness agent, elastomerics or moulded products comprise the polyurethane-urea of claim 1.
19. a dispersion, coating, film, tackiness agent, elastomerics or moulded products comprise the urethane of claim 12.
20. a method for preparing the Spandex of the heat-set efficiency that has about 77%-about 95% under stretching at 1.5x when keeping 120 seconds for 190 ℃, this method comprises:
(a) will gather (tetramethylene-copolymerization-ethyleneether) glycol contacts with poly-(tetramethylene-copolymerization-ethyleneether) glycol mol ratio with the vulcabond of at least a vulcabond with about 1.2-about 2.3, wherein said poly-(tetramethylene-copolymerization-ethyleneether) glycol comprises by what copolymerization tetrahydrofuran (THF) and oxyethane obtained and becomes subdivision, and wherein the cell mesh derived from oxyethane gathers in (tetramethylene-copolymerization-ethyleneether) glycol to be present in this greater than the about 70 moles of % of about 37-;
(b) in the product of (a), add solvent;
The product of (b) is contacted with quadrol chainextender and at least a chain terminator with the common chainextender of the about 10 moles of % of 0-; With
(d) product of spinning (c) forms Spandex.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59481105P | 2005-05-09 | 2005-05-09 | |
| US60/594,811 | 2005-05-09 | ||
| US60/738,684 | 2005-11-22 | ||
| US60/738,733 | 2005-11-22 |
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| CNA2006800158860A Pending CN101171276A (en) | 2005-05-09 | 2006-05-08 | Spandex from poly(tetramethylene-co-ethyleneether) glycols having high ethyleneether content |
| CNA200680015888XA Pending CN101208464A (en) | 2005-05-09 | 2006-05-08 | Spandex compositions for high speed spinning |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102517688A (en) * | 2011-12-08 | 2012-06-27 | 烟台泰和新材料股份有限公司 | Preparation method of polyurethane elastomeric fiber possessing excellent heat setting performance |
| CN110627996A (en) * | 2019-10-08 | 2019-12-31 | 苏州大学 | Polyurethane urea, preparation method thereof and super-tough polyurethane urea based on polyurethane urea |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103710786B (en) * | 2013-12-18 | 2015-08-12 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of the polyurethane stock solution for high speed spinning |
| TWI751100B (en) * | 2014-05-05 | 2022-01-01 | 盧森堡商英威達技術有限公司 | Bio-derived polyurethane fiber |
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2006
- 2006-05-08 CN CNA2006800158860A patent/CN101171276A/en active Pending
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517688A (en) * | 2011-12-08 | 2012-06-27 | 烟台泰和新材料股份有限公司 | Preparation method of polyurethane elastomeric fiber possessing excellent heat setting performance |
| CN102517688B (en) * | 2011-12-08 | 2014-04-16 | 烟台泰和新材料股份有限公司 | Preparation method of polyurethane elastomeric fiber possessing excellent heat setting performance |
| CN110627996A (en) * | 2019-10-08 | 2019-12-31 | 苏州大学 | Polyurethane urea, preparation method thereof and super-tough polyurethane urea based on polyurethane urea |
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