HK1068146B - Improved spandex compositions - Google Patents

Description

Improved spandex compositions

RELATED APPLICATIONS

This application claims priority to provisional application No. 60/307154 filed on 24/7/2001, the disclosure of which is incorporated herein by reference in its entirety.

Technical Field

The present invention relates to spandex, and in particular, the present invention provides spandex prepared from one or more polyols containing aromatic functionality. The spandex of the present invention has improved resistance to high temperatures, including high temperature dyeing, with minimal loss of desirable physical properties such as elastic recovery.

Background

Spandex is a long-chain polymeric synthetic fiber containing at least 85% by weight of polyurethane segments. As shown in fig. 1, spandex has two segments: a rubbery soft segment a and a hard segment B. The soft segments a are typically comprised of a polymeric diol that makes the fibers stretchable and capable of recovering original shape. The hard segment B is typically composed of polyurethane which provides rigidity and tensile strength to the fibers. Polyurethanes can be one subclass of these, namely polyurethaneureas.

Polyurethanes are typically prepared by reacting a polymer diol and a diisocyanate to form a capped polymer diol. If the desired polyurethane is urea-free, the capped polymer diol may be melt reacted with a diol chain extender and optionally a monofunctional chain terminator or dissolved in a solvent. If a polyurethaneurea is desired, the capped polymer diol can be dissolved in a solvent prior to reaction with the diamine chain extender and optionally with the monofunctional chain terminator.

Spandex is typically made by reaction spinning, melt spinning, dry spinning, or wet spinning a polyurethane solution into an elongated channel filled with a hot inert gas such as air, nitrogen, or steam, or by immersion in a water bath to remove the solvent, after which the fiber is wound up. Methods of reactive spinning, melt spinning, dry spinning, wet spinning are known in the art.

Dry spinning is a process in which a polymer solution is forced into a spinning orifice and extruded into a shaft to form a filament. Hot inert gas is flowed through the chamber to cause the solvent to evaporate from the filaments as they pass through the shaft. The resulting spandex is then wound around a cylindrical core to form a spandex supply package.

Because of its good elasticity and tensile strength, spandex has been used to make garments such as undergarments, swimwear, sportswear, stockings, socks, dresses, suits, outerwear, and the like. Spandex has also been used in disposable personal hygiene products such as baby diapers, feminine hygiene products, adult incontinence garments, protective masks, medical garments, industrial garments, and the like. Spandex is also used in upholstery and other commercial and industrial applications. Spandex is commonly blended with other natural or synthetic fibers such as nylon, polyester, cotton, wool, silk, and linen.

Spandex tends to lose elasticity when exposed to high temperatures during the dyeing process. In view of this, there is a need in the art to produce spandex that has excellent elasticity after the high temperatures of the dyeing process. The present invention is directed to this and other important ends.

Brief description of the invention

In one embodiment, the present invention provides a spandex comprising a polyol having at least one aromatic functional group, such as phenol.

In another embodiment, the present invention provides a spandex prepared from the reaction of a polymeric diol, a polyol having at least one aromatic functional group, an organic diisocyanate, and at least one chain extender.

In another embodiment, the present invention provides a process for preparing spandex: mixing a polymer diol and a polyol having aromatic functionality to form a resin mixture; the resin mixture and the organic diisocyanate are mixed to form a capped glycol, the capped glycol is polymerized to form polyurethane, and spandex is formed from the polyurethane.

In another embodiment, the present invention provides a spandex prepared from a polyurethane, wherein the polyurethane is prepared by a process comprising the steps of:

(a) mixing at least one polymeric glycol and at least one alkoxylated phenol;

(b) reacting the product obtained in step (a) with at least one organic diisocyanate.

(c) Polymerizing the product of step (b) with at least one diamine.

In another embodiment, the present invention provides a spandex dry spun from a solution of a polyurethaneurea in an organic solvent, wherein the polyurethaneurea is made by a process comprising: mixing 90% to 70% by weight of polytetrahydrofuran and 10% to 30% by weight of ethoxylated bisphenol a to form a resin; and reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) with a capping ratio of 1.5 to 2.

In another embodiment, the present invention provides a supply package comprising a core and a spandex dry spun from a solution of a polyurethaneurea in an organic solvent, wherein the polyurethaneurea is made by a process comprising: mixing 90% to 70% by weight of polytetrahydrofuran and 10% to 30% by weight of ethoxylated bisphenol a to form a resin; and reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) to obtain spandex with a blocking ratio of 1.5-2.

In another embodiment, the present invention provides a spandex dry spun from a solution of a polyurethaneurea in an organic solvent, wherein the polyurethaneurea is made by a process comprising: mixing 90% to 70% by weight of polytetrahydrofuran and 10% to 30% by weight of ethoxylated bisphenol a to form a resin; and reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) to form a capped glycol, wherein the capping ratio is 1.5-2; the capped glycol is reacted with a mixture comprising 83% to 92% by weight of ethylenediamine, 8% to 17% by weight of 1, 2-diaminopropane, and 5% to 15% by weight of diethylamine to form a polyurethaneurea.

In another embodiment, the present invention provides a supply package comprising a core and a spandex dry spun from a solution of a polyurethaneurea in an organic solvent, wherein the polyurethaneurea is made by a process comprising: mixing 90% to 70% by weight of polytetrahydrofuran and 10% to 30% by weight of ethoxylated bisphenol a to form a resin; and reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) to form a capped glycol, wherein the capping ratio is 1.5-2; reacting the capped glycol with a mixture comprising 83% to 92% by weight of ethylenediamine, 8% to 17% by weight of 1, 2-diaminopropane, and 5% to 15% by weight of diethylamine to form a polyurethane urea spandex.

In another embodiment, the present invention provides a spandex comprising alkoxylated bisphenol a as its structural unit.

In another embodiment, the present invention provides a process for preparing spandex comprising:

mixing at least one polymeric glycol and at least one alkoxylated phenol to form a resin mixture;

mixing the resin mixture and at least one organic diisocyanate to form an isocyanate-terminated diol;

polymerizing an isocyanate-terminated diol with at least one diamine to form a polyurethane; and

polyurethane is formed into spandex by reaction spinning, melt spinning, dry spinning or wet spinning.

In another embodiment, the present invention provides a garment comprising the various spandex fibers described above.

In another embodiment, the present invention provides a disposable personal hygiene article comprising a package comprising the various spandex fibers described above.

In another embodiment, the present invention provides a spandex prepared by solution spinning of a polyurethaneurea in a solvent, wherein the polyurethaneurea is prepared by a process comprising:

mixing 95% to 60% by weight of a polymeric diol with 5% to 40% by weight of an alkoxylated bisphenol a to form a resin;

reacting a resin and at least one organic diisocyanate to form a capped glycol;

the capped glycol is polymerized with at least one chain extender to form a polyurethane.

In another embodiment, the present invention provides a spandex prepared by dry spinning a solution of polyurethaneurea in an organic solvent, wherein the polyurethaneurea is prepared by a process comprising: mixing 95% to 60% by weight of polytetrahydrofuran with 5% to 40% by weight of alkoxylated bisphenol a to form a resin; the resin is reacted with 4, 4' -methylene-bis (phenyl isocyanate) with a blocking ratio of 1.5 to 3.

In another embodiment, the present invention provides a spandex prepared by dry spinning a solution of polyurethaneurea in an organic solvent, wherein the polyurethaneurea is prepared by a process comprising: mixing 95% to 60% by weight of polytetrahydrofuran with 5% to 40% by weight of alkoxylated bisphenol a to form a resin; reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) to form a capped glycol, wherein the capping ratio is 1.5 to 3; the capped glycol is polymerized with a mixture containing 83% to 92% by weight ethylenediamine, 8% to 17% by weight 1, 2-diaminopropane, and 5% to 15% by weight diethylamine to form a polyurethaneurea.

In another embodiment, the present invention provides a spandex containing ethoxylated bisphenol a as its structural unit.

The present specification will describe various aspects of the invention in detail.

Brief Description of Drawings

Fig. 1 is an example of the chemical structure of prior art spandex.

FIG. 2 is a graphical representation of the rebound modulus (return modulus) at 200% elongation of spandex of the present invention and comparative spandex after high pressure dyeing.

Figure 3 is a graphical representation of the modulus of restitution at 250% elongation after high pressure dyeing of spandex of the present invention and comparative spandex.

FIG. 4 is a graphical representation of the elongation modulus (out modules) at 200% elongation of spandex of the present invention and comparative spandex after high pressure dyeing.

Figure 5 is a graphical representation of the elongation modulus at 250% elongation of spandex of the present invention and comparative spandex after high pressure dyeing.

Detailed Description

The inventors of the present invention have unexpectedly found that spandex prepared from one or more polyols having aromatic functionality has significantly enhanced heat resistance and modulus retention. This finding is of great importance because spandex tends to lose its elasticity and strength after exposure to high temperatures, such as those experienced in dyeing processes.

The present invention provides polyurethane-derived spandex having soft segments comprising one or more polymeric diols (e.g., polycarbonate diols, polyester diols, polyether diols, or mixtures of two or more thereof) and one or more polyols having aromatic functionality. In one embodiment, the soft segment of the polyurethane comprises from about 95% to about 60% by weight of one or more polymeric diols and from about 5% to about 40% of one or more polyols having aromatic functionality. In another embodiment, the soft segment of the polyurethane comprises from about 90% to about 70% by weight of one or more polymeric diols and from about 10% to about 30% by weight of one or more polyols having aromatic functionality. In another embodiment, the soft segment of the polyurethane comprises from 90% to about 75% by weight of one or more polymeric diols and from about 10% to about 25% by weight of one or more polyols having aromatic functionality. In another embodiment, the soft segment of the polyurethane comprises from 85% to about 80% by weight of one or more polymeric diols and from about 15% to about 20% by weight of one or more polyols having aromatic functionality. "fiber" includes, for example, staple fibers and continuous filaments. The polymer diols are preferably polyether diols and polyester diols, more preferably polyether diols.

The soft segment of the polyurethane may be any polycarbonate diol known in the art. Typical polycarbonate diols include poly (pentane-1, 5-carbonate) diol and poly (hexane-1, 6-carbonate) diol.

The soft segment of the polyurethane may be any polyester diol known in the art. Typical polyester diols are the polycondensation products of those diols (e.g., ethylene glycol, 1, 4-butanediol, 2-dimethyl-1, 3-propanediol) and diacids (e.g., adipic acid, succinic acid, dodecanedioic acid, and copolymers thereof).

The soft segment of the polyurethane may be any polyether diol known in the art. Typical ofThe polyether glycol of (a) includes polymethyltetrahydrofuran, polytetramethylene glycol, Polytetrahydrofuran (PTHF); poly (tetramethylene ether) glycol (PTMEG); polypropylene Glycol (PPG); poly (3-methyl-1, 5-pentamethylene ether) glycol; poly (tetramethylene ether-co-3-methyltetramethylene ether) glycol, and mixtures of two or more thereof. Polyether diols are generally linear hydroxyl-terminated polyols having an average molecular weight (M)_n) From about 500 to about 10,000; or from about 500 to about 5000; or about 600 to about 2000. In one embodiment, the polyether diol has a molecular weight of from about 1750 to about 2250. In one embodiment, the polyether diol is polytetrahydrofuran.

The polyol having an aromatic functional group includes, for example, an alkoxylated phenol. Alkoxylated phenols include, for example, alkoxylated diphenols and alkoxylated dihydric phenols. Typical alkoxylated dihydric phenols include alkoxylated 2, 2-bis (4-hydroxyphenyl) propane (i.e., alkoxylated bisphenol A), alkoxylated bis (4-hydroxyphenyl) methane, alkoxylated 1, 1-bis (4-hydroxyphenyl) ethane, alkoxylated 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, alkoxylated 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, alkoxylated 2, 2-bis (4-hydroxy-3-methylphenyl) propane, alkoxylated bis (4-hydroxyphenyl) sulfide, and alkoxylated bis (4-hydroxyphenyl) sulfone. More preferred are alkoxylated bis (4-hydroxyphenyl) -alkane-type dihydric phenols, and most preferred is alkoxylated bisphenol A. Typical alkoxylated diphenols include alkoxylated diphenylphenol, alkoxylated bisphenol a, alkoxylated 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, alkoxylated 1, 1-bis (4-hydroxyphenyl) cyclohexane, alkoxylated 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, alkoxylated 4, 4 '-dihydroxydiphenyl sulfide, alkoxylated 4, 4' -dihydroxydiphenyl sulfone and their di-and tetrabrominated or chlorinated derivatives, such as alkoxylated 2, 2-bis (3-chloro-4-hydroxyphenyl) propane, alkoxylated 2, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane or alkoxylated 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane. In one embodiment, the alkoxylated phenol is an alkoxylated bisphenol a.

The term "alkoxylated" refers to the group (A), (B), (C), (OR)_xWherein R is a straight or branched chain C_1-22Alkyl, preferably C_1-6Alkyl, more preferably C₂An alkyl group; x is the number of moles of OR and is an integer from 1 to about 25, preferably from 2 to about 10.

Alkoxylated bisphenol a includes, for example, ethoxylated bisphenol a, propoxylated bisphenol a, and mixtures thereof. The ethoxylated bisphenol a may contain from about 2 to about 10 moles of ethylene oxide, preferably from about 4 to about 8 moles of ethylene oxide. The molecular weight of the alkoxylated bisphenol a is generally below 500. The alkoxylated bisphenol a is preferably of urethane grade, which means that it should have a low water content (e.g. moisture) and a low basicity (in terms of potassium (K) catalyst remaining from the alkoxylation process). For example, the water content can be about 600ppm or less; or about 500ppm or less; or about 300ppm or less; or about 250ppm or less; or about 100ppm or less. The potassium content may be about 40ppm or less; or about 25ppm or less; or about 20ppm or less; or about 15ppm or less; or about 10ppm or less.

Generally, a polymer diol is mixed with a polyol having an aromatic functional group to prepare a diol resin mixture. Thereafter, the resin mixture is reacted with an organic diisocyanate to produce a polyurethane.

The hard segment of the polyurethane comprises a polyurethane derived from an organic diisocyanate. In one embodiment, the polyurethane is a polyurethaneurea. Any organic diisocyanate known in the art may be used. Examples of organic diisocyanates include 4, 4' -methylene-bis (phenyl isocyanate) (MDI); 1, 1' -methylenebis (4-isocyanatocyclohexane); 4-methyl-1, 3-phenylene diisocyanate; 5-isocyanato-1- (isocyanatomethyl) -1, 3, 3-trimethylcyclohexane; 1, 6-hexamethylene-diisocyanate; toluene-2, 4-diisocyanate (TDI); and mixtures of two or more thereof. In one embodiment, the organic diisocyanate is 4, 4' -methylene-bis (phenyl isocyanate).

The spandex of the present invention can be prepared using processes known in the art. For example, as described herein, the glycol resin mixture may be mixed reacted (i.e., "capped") with one or more organic diisocyanates to form a capped glycol. The blocking ratio (isocyanate end groups (NCO)/OH) is generally from about 1.5 to about 3; from about 1.5 to about 2; or from about 1.6 to about 1.9; or from about 1.6 to about 1.8; or from about 1.6 to about 1.7. "blocking ratio" refers to the molar ratio of organic diisocyanate to polymeric glycol used in the reaction to form the blocked glycol.

In one embodiment, the diol resin mixture is reacted in admixture with an excess of one or more organic isocyanates to form a capped diol, as described herein. Typically, the excess NCO content in the capped glycol is about 2% to about 4%; or about 2.4% to 3.6%; or about 2.8% to 3.4%; or about 2.9% to 3.3%; or about 3% to 3.2%. "NCO content" refers to the isocyanate end group content of the isocyanate-terminated glycol prior to chain extension.

The capped glycol is then polymerized with one or more chain extenders and optionally with one or more chain terminators. In one embodiment, the capped glycol is chain extended with one or more diamines. In another embodiment, the capped glycol is chain extended with a mixture of two or more diamines.

Any chain extender known in the art may be used. Chain extenders typically include diols, diamines, amino alcohols, and mixtures of two or more thereof. Typically, the chain extender has a molecular weight of about 60 to about 500.

Any glycol known in the art may be used as the chain extender. Diols are commonly used to prepare polyurethanes. Examples of the diols include trimethylene glycol, ethylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 2-propanediol, 1, 4-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 4-bis (2-hydroxyethoxy) benzene, bis (2-hydroxyethyl) terephthalate, p-xylylene glycol and a mixture of two or more thereof. In one embodiment, the chain extender is an aliphatic diol having from 2 to about 14 carbon atoms. In another embodiment, the chain extender is 1, 4-butanediol.

Any diamine known in the art may be used as the chain extender. Diamines are commonly used to prepare polyurethaneureas. Examples of diamines include Ethylenediamine (EDA), 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 1, 3-diaminopropane, 1, 2-diaminopropane (PDA), 1, 3-diaminopentane, 2-methyl-1, 5-pentanediamine, Isophoronediamine (IPDA), 1-amino-3-aminoethyl-3, 5, 5-trimethylcyclohexane and mixtures of two or more thereof. The amount of diamine used is generally from about 7% to about 13%, preferably from about 9% to about 11%, of the total weight of the capped glycol. In one embodiment of the invention, the chain extension reaction is carried out with a mixture of from about 83% to about 92% ethylene diamine and from about 8% to 17% 1, 2-diaminopropane, expressed as molar concentration in the diamine mixture.

In the chain extension reaction, a chain terminator is generally used to control the molecular weight of the polyurethane. Any chain terminator known in the art may be used. Examples of chain terminators include Diethylamine (DEA), cyclohexylamine, butylamine, hexanol, butanol, and mixtures of two or more thereof.

In one embodiment, diethylamine is used as a chain terminator, while at least two diamines (e.g., ethylenediamine and 1, 2-diaminopropane) are used as chain extenders. For example, the diamine chain extender/chain terminator mixture may be ethylene diamine in an amount of about 83% to about 92% by weight, 1, 2-diaminopropane in an amount of about 8% to about 17% by weight, and diethylamine in an amount of about 5% to about 15% by weight.

The chain extension reaction may be carried out in one or more conventional solvents. Examples of the solvent include dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and a mixture of two or more thereof. In one embodiment, the solvent is dimethylacetamide.

After the polymerization reaction is complete, the concentration of polyurethane (or polyurethaneurea) in the solution is generally from about 30% to about 40% by weight of the total solution; or about 31% to about 38%; or about 32% to about 36%; or from about 33% to about 35%.

After the polymerization reaction is complete, spandex can be prepared by reaction spinning, melt spinning, dry spinning, or wet spinning as known in the art. In one embodiment, spandex is prepared by dry spinning using the same solvent as the polymerization reaction. For example, the resulting polyurethane is wound at a speed of at least 550 meters/minute to form spandex, preferably at least 700 meters/minute, and most preferably at least 900 meters/minute. The obtained product is high-speed spinning spandex.

Spandex can be spun as a monofilament or incorporated into a multifilament yarn by conventional techniques. Each filament has a decitex value for the fabric, for example from about 6 to about 25 decitex per filament.

The spandex of the present invention may also contain or be coated with conventional additives for specific uses, such as chlorine-resistant additives, antimicrobials, antioxidants, thermal stabilizers (e.g., IRGANOX ® MD 1024), ultraviolet light stabilizers (e.g., TINUVIN ® 328), air-resistant stabilizers, pigments (e.g., ultramarine blue, ultramarine green) and matting agents (e.g., titanium dioxide), anti-tack agents (e.g., ethylene bisstearamide, ethylene bisoleamide), heat-setting agents, dyes, emulsifiers, wetting agents, antistatic agents, pH adjusters, filament compactors, anti-corrosion agents, dispersants (e.g., ospnue ® 657) and lubricants (e.g., silicone oils) as are known in the art.

Chlorine resistant additives known in the art may be used in the present invention. Examples of chlorine-resistant additives include magnesium aluminum hydroxide carbonate hydrate; hydrotalcites such as DHT (i.e., Mg)₆Al₂(CO₃)(OH)₁₆·4(H₂O)); and hydrated magnesium carbonates such as hydromagnesite (i.e. Mg)₅(CO₃)₄(OH)₂·4(H ₂ O). In one embodiment, the hydrotalcite has one crystal water and is modified with C₁₀-C₃₀Fatty acids (e.g. capric acid, lauric acid, myristic acid, palmitic acid, stearic acid). Chlorine resistant additives are generally used in amounts of about 0.1 to 10% by weight of the polyurethane. In another embodiment, the polyurethane comprises 0.5 to 10 weight percent composite oxide particles comprising aluminum, and at least one of zinc and magnesium.

In another embodiment, the chlorine-resistant additive is a hydrotalcite and/or another alkali metal aluminum hydroxide, which compound coats the polyorganosiloxane and/or a mixture of polyorganosiloxane and polyorganohydrosiloxane.

When using hydromagnesite and huntite (CaMg) in combination₃(CO₃)₄) Zinc oxide and poly (N, N-diethyl-2-aminoethyl methacrylate), spandex has excellent resistance to yellowing and high mechanical resistance to chlorine.

The present invention may use antisticking agents known in the art. Examples of antisticking agents include metal stearates (e.g., calcium stearate, magnesium stearate, zinc stearate) and barium sulfate.

The present invention may use a heat setting agent known in the art. Examples of heat setting agents include quaternary amine additives. In one embodiment, the heat setting agent is a quaternary amine having a functionality of about 3 to 100 milliequivalents per kilogram.

Antioxidants provide high temperature stability and long term storage stability. Any antioxidant known in the art may be used, for example, aminic and phenolic antioxidants. Examples of the amine-based antioxidant include N, N '-di (nonylphenyl) amine, diaryldiamines (e.g., N' -diphenylethylenediamine, N '-ditolylethylenediamine), naphthylamines (e.g., N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine), aromatic amines (e.g., N' -diisobutylphenyldiamine, N-cyclohexyl-N '-phenylphenyldiamine, N' -dinaphthylphenylenediamine, N '-ditolylphenylenediamine, N' -diphenylparaphenyldiamine, 6-ethoxydihydroquinoline, 4-isopropoxydiphenylamine), and alkylated diphenylamines. Examples of phenolic antioxidants include bisphenols, monophenols, polyphenols and aminophenols. The phenol antioxidant includes 2, 2 '-methylenebis (4-methyl-6-tert-butylphenol), 4' -methylenebis (2, 6-di-tert-butylphenol), 4 '-butylidenebis (3-methyl-6-tert-butylphenol), 4' -thiobis (3-methyl-6-tert-butylphenol), 4-tert-butylcatechol, monomethyl ether of hydroquinone, 2, 6-di-tert-butyl-p-cresol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2, 4, 6-tert-aminophenol and the like. Preferred antioxidants include IRGANOX ® 245 (triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Ciba specialty Chemicals, Tarrytown, N.Y.) and bis (2, 4-dichlorobenzyl) hydroxylamine).

LuROL ® 6534(DSF-36) and LUROL ® SF 8973A (Goulston Technologies, Inc.), or Witcolube (an organo-modified polydimethylsiloxane) (Crompton Corporation), lubricants known in the art may also be used. Other lubricants include mineral oils, fatty acid esters having 8 to 22 carbon atoms in the fatty acid moiety and 1 to 22 carbon atoms in the alcohol moiety. Specific examples include methyl palmitate, isobutyl stearate and 2-ethylhexyl tallow fatty acid, esters of polyhydroxy carboxylic acids, esters of coconut fatty acid or glycerol and alkoxylated glycerol, silicones, dimethylpolysiloxanes, polyalkylene glycols and ethylene oxide/propylene oxide copolymers, and other mixtures of higher fatty acids including magnesium stearate and palmitic/stearic acids.

Spandex should preferably exhibit excellent lubricity, antistatic properties, and long-term storage stability. For example, spandex can be treated with a fiber treatment composition containing polydimethylsiloxane, polyoxyalkylene-diorganopolysiloxane, and an antioxidant. The antioxidant may have a linear or branched chain, and may be linear or cyclic. In the case of a linear structure, the terminal group of the molecular chain may be a trimethylsiloxy group or a dimethylhydroxysiloxy group. The fiber-treating composition may contain, for example, 100 parts by weight of a fiber-treating composition having a viscosity of 3 to 30mm at 25 ℃²Dimethyl polysiloxane per sec and 0.5 to 50 parts by weight of polyoxyalkylene-diorganopolysiloxane.

The invention also provides spandex feed packages containing a core (e.g., a cylindrical core) around which the spandex of the invention is wound.

In another embodiment, the present invention provides garments and disposable personal hygiene articles made from spandex.

Examples

The following examples are intended to illustrate the invention and do not limit the scope of the appended claims.

Example 1

160 grams of polytetrahydrofuran Polyol (PTHF) having a molecular weight of 2000 and 26 grams of Ethoxylated Bisphenol A (EBA) containing 4 moles of ethylene oxide were weighed into a 1 liter flask equipped with a stirrer, thermometer and nitrogen/vacuum inlet and heated to 110 ℉. Then, 58 g of 4, 4' -methylene-bis (phenyl isocyanate) (MDI) was added, which, after its exotherm, was heated to 160 ℉. After continuing the reaction for 1 hour at 160 ℃ 165 ℉ under vacuum, the excess NCO was checked. 244 grams of dimethylacetamide was added to make a 50% solution and cooled to 80 ℉ for chain extension. A chain extension solution was prepared with 75% ethylenediamine, 15% 1, 2-diaminopropane, 10% diethylamine, 0.4% CDSA hydroxylamine, 0.5% IRGANOX ® 245 (phenolic antioxidant, available from Ciba Specialty Chemicals, Tarrytown, NY), 0.25% IRGANOX ® MD 1024 (phenolic antioxidant, available from Ciba Specialty Chemicals, Tarrytown, NY) and an antiblocking agent. After mixing for 1 hour under vacuum, the spandex fiber solution was transferred into quart jars (quart jars). The film was cast on glass and dried in a nitrogen oven 150 ℉ for 1 hour. Tensile strength was measured on the film before and after 300 ℉ for 30 minutes respectively, and modulus was measured before and after 265 ℉ for 30 minutes respectively. The retention characteristics parameters for example 1 are listed in table 1.

Example 2

Example 2 the procedure used was the same as in example 1, but 156 g of polytetrahydrofuran polyol and 31 g of ethoxylated bisphenol a (eba) containing 6 moles of ethylene oxide were used. The retention characteristics parameters for example 2 are listed in table 1.

Example 3

Example 3 the procedure used was the same as in example 2, except that the reaction temperature in example 3 was 180-185 ℉. The retention characteristics parameters for example 3 are listed in table 1.

Example 4

Example 4 the same procedure was used as in example 1, but no antiblocking agent was used. The retention characteristics of example 4 are listed in table 1.

Comparative example A

Ethoxylated Bisphenol A (EBA) was not used in comparative example A. 200 g of polytetrahydrofuran Polyol (PTHF) having a molecular weight of 2000 and 45 g of 4, 4' -methylene-bis (phenyl isocyanate) (MDI) were reacted in a 1 l flask for 1 h at 200 ℃ 205 ℉. When the correct excess NCO was reached, the mixture was diluted with dimethylacetamide to a solids content of 50%, cooled to 80 ℉, and the desired amine was added along with stabilizers and antiblocking agents (as described in example 1). Tensile strength was measured on the dried film before and after 300 ℉ for 30 minutes, respectively, and modulus was measured before and after 265 ℉ was heated for 30 minutes, respectively. The retention characteristics for comparative example a are listed in table 1. The composition and reaction parameters for comparative example A are listed in Table 2.

TABLE 1

Characteristic parameter	Example 1	Example 2	Example 3	Example 4	Comparative example A
						Percent retention of tensile strength	92	131	120.3	187.3	124.9
Percent retention of elongation modulus at 200% elongation	110.5	112.5	107.7	133.3	87.2
						Percent retention of elongation modulus at 250% elongation	114.3	115.1	107.9	130.4	84.8
Percent retention of recovery modulus at 100% elongation	116.7	115.4	110.5	144.8	93.3
						Percent retention of recovery modulus at 200% elongation	108.7	113.8	103	191.7	88

TABLE 2

Premix Components weight (grams)	Example 5	Example 6	Example 7	Example 8	Example 9	Example 10	Comparative example A	Comparative example B	Comparative example C
										PTHF	156	156	156	148	160	156	200	200	200
EBA	31	31	31	37	26	31	-	-	-
										MDI	58	58	58	60	58	57	45	45	45
ITP characteristic parameter
										Theoretical NCO	3.12％	3.12％	3.12％	3.12％	3.07％	3.0％	2.74％	2.74％	2.74％
Actual NCO	2.84％	2.82％	2.81％	2.91％	3.42％	3.26％	2.65％	2.53％	2.86％

Examples 5, 6 and 7

Examples 5, 6, 7 were prepared according to the procedure described in example 1. In inventive examples 5-7, Ethoxylated Bisphenol A (EBA) contained 6 moles of ethylene oxide. The moisture/potassium levels for examples 5, 6, 7, expressed in parts per million (ppm), were 530/12, 250/6.2, and 250/15, respectively. The formulations used in examples 5, 6 and 7 are listed in Table 2. The characteristic parameters of examples 5, 6 and 7 are shown in Table 3.

Comparative example B

Comparative example B was prepared as described in example 1, without ethoxylated bisphenol a (eba). The formulation used in comparative example B is listed in Table 2. The characteristic parameters of comparative example B are listed in Table 3.

TABLE 3

	Example 5	Example 6	Example 7	Comparative example B
					Water (ppm)/K (ppm)	530/12	250/6.2	250/15
％EBA	16.6	16.6	16.6	0
					NCO/OH	1.645	1.645	1.645	1.8
Theoretical% NCO	3.12	3.12	3.12	2.74
					Viscosity of the oil	38,400	68,800	60,800	20,000
Percent retention of tensile strength after 300 ℉ 30 minutes	172.2	167.3	135.5	123.7
					200% elongation after 265 ℉ 30 minutesPercent retention of elongation modulus for long lengths	113.8	107.7	111.1	112.5
Percent retention of elongation modulus at 250% elongation after 265 ℉ 30 minutes	110	102.8	108.1	112.9
					Percent retention of recovery modulus at 100% elongation after 265 ℉ 30 minutes	125	110	109.1	122.2
Percent retention of recovery modulus at 200% elongation after 265 ℉ 30 minutes	115	105.6	111.1	106.7
					Percent retention of elongation modulus at 200% elongation after 390 ℉ 1 minutes	100	92.3	88.9	87.5

Examples 8, 9 and 10

Examples 8, 9, 10 were prepared similarly to the above examples using a 20% mixture of ethoxylated bisphenol A containing 6 moles of ethylene oxide, but with different levels of moisture and potassium (250/15; 250/6.2; 530/12, respectively). The formulations of examples 8, 9 and 10 are shown in Table 2. The characteristic parameters of examples 8, 9 and 10 are shown in Table 4.

Comparative example C

The formulation used in comparative example C is listed in Table 2. The characteristic parameters of comparative example C are listed in Table 4.

The improvement in percent retention characteristics of the present invention is clearly demonstrated in comparison to the results shown in comparative example C. These results show the effect of high potassium levels on the retention of the recovery modulus in example 8, and the better retention of the examples modified with ethoxylated bisphenol a (eba) compared to the comparative examples. FIGS. 2-5 provide graphical representations of the high recovery modulus and elongation modulus of examples 8-10.

FIG. 4

Premix component weight	Example 8	Example 9	Example 10	Comparative example C
					Water (ppm)/K (ppm)	250/15	250/6.2	530/12	Control
％EBA	20	20	20	0
					NCO/OH	1.61	1.61	1.61	1.8
Theoretical% NCO	3.12	3.12	3.12	2.74
					Viscosity of the oil	18,400	28,800	35,200	11,200
Percent elongation	650	667	650	700
					Retention of tensile strength
250 ℉ 60' rear	122.	97.1	117.9	125.5
					265 ℉ 60' rear	137.9	114.5	123.8	121.5
Percent retention of elongation modulus at 200% elongation
					250 ℉ 60' rear	133.3	124.3	127.0	88.2
265 ℉ 60' rear	112.6	128.8	118.0	102.9
					Percent retention of tensile modulus at 250% elongation
250 ℉ 60' rear	133.0	121.0	123.3	90.3
					265 ℉ 60' rear	115.0	126.8	120.6	107.3
Percent retention of recovery modulus at 200% elongation
					250 ℉ 60' rear	151.6	200.0	205.0	133.0
265 ℉ 60' rear	100.0	188.2	145.0	140.0
					Percent retention of recovery modulus at 250% elongation
250 ℉ 60' rear	144.6	148.8	153.1	105.6
					265 ℉ 60' rear	110.7	148.8	128.6	119.0

Test procedure

Viscosity of the oil

The viscosity was measured with a Brookfield viscometer model LV-DVII + with LV spindle 1-4. The viscosity of the high viscosity resin and prepolymer was measured at 25.6 ℃ using a SC4-25 rotator. After the test material has been on the viscometer for 20 minutes, readings are taken for the high viscosity resin and prepolymer at five minute intervals. The final measurement is determined when two consecutive readings agree.

Elongation test

A 1 inch reticle was printed on about 18 inches of the material to be tested, and the samples were marked in two places at 1 inch intervals. Care was taken to ensure that the sample was not previously stretched more than 300%. After placing the first mark at the zero point of a 12 inch ruler, the sample is stretched until it breaks. The position of the second mark on the straightedge was recorded at the moment of fracture and the length of the second mark at the point of fracture was subtracted from the initial length and multiplied by one hundred to calculate the percent elongation.

Modulus test

The sample material was cut with scissors or a 12 "shear to approximately 12 inches and immediately tested with a Sintech instrument equipped with a 1-500 gram range load cell. Care was taken to ensure that the test material was not stretched prior to testing.

Tensile test

The tensile strength of the material to be tested is determined by¹/₂"Global Force Gauge Stand measurement of a diametric axis of rotation and a vertically positioned spring load cell or digital load cell, Force values are recorded in ounces or pounds. The load cell has a pulley that must be located about 4 inches from the Force Gauge Stand axis.

The sample material to be tested is fitted over the pulley of the dynamometer or the like. Then, the Force Gauge Stand shaft starts to rotate. As the shaft rotates, the loose end of the sample winds around the shaft until the end is clamped and the sample begins to spin on its own. The maximum load is recorded in pounds.

Preparation of the film

An appropriate amount of polymer solution was cast onto a glass plate and the sample drawn to the desired length with a 0.060Gardner knife to produce a film. The resulting film was dried in a nitrogen oven 150 ℉ for 1 hour.

High pressure dyeing step

This step was performed on the slit of the film using a Polymat dyeing machine. The test samples were placed into respective stainless steel beakers of a dyeing machine, which had 200 ml of deionized water having a pH of 4.5-5.0, and then covered with lids. The test was conducted at three temperature points, 230 ℉, 250 ℉, and 265 ℉, for 1 hour. Thereafter, the sample was thoroughly dried and allowed to recover. Tensile strength, elongation at break and modulus were measured on the treated films to determine the retention of the above-mentioned characteristic parameters.

The patents, patent applications, and publications cited herein are incorporated by reference in their entirety.

Various modifications of the invention in addition to those described herein will be apparent to those skilled in the art. Such modifications are also intended to fall within the scope of the appended claims.

Claims (54)

1. A spandex prepared from a polyurethane, wherein the polyurethane is prepared by a process comprising:

(a) mixing at least one polymeric glycol and at least one alkoxylated phenol;

(b) reacting the product obtained in step (a) with at least one organic diisocyanate.

(c) Polymerizing the product of step (b) with at least one diamine.

2. The spandex of claim 1 wherein the polymeric glycol is polymethyltetrahydrofuran, polytetramethylene glycol, polytetrahydrofuran; poly (tetramethylene ether) glycol; polypropylene glycol; poly (3-methyl-1, 5-pentamethylene ether) glycol; poly (tetramethylene ether-co-3-methyltetramethylene ether) glycol, or a mixture of two or more thereof; wherein the alkoxylated phenol is alkoxylated bisphenol A, alkoxylated bis (4-hydroxyphenyl) methane, alkoxylated 1, 1-bis (4-hydroxyphenyl) ethane, alkoxylated 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, alkoxylated 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, alkoxylated 2, 2-bis (4-hydroxy-3-methylphenyl) propane, alkoxylated bis (4-hydroxyphenyl) sulfur and alkoxylated bis (4-hydroxyphenyl) sulfone, alkoxylated diphenylphenol, alkoxylated 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, alkoxylated 1, 1-bis (4-hydroxyphenyl) cyclohexane, alkoxylated bisphenol A, alkoxylated 2-bis (4-hydroxyphenyl) cyclohexane, alkoxylated 1-bis (4-hydroxyphenyl) propane, alkoxylated 2-bis (4-, Alkoxylated 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, alkoxylated 4, 4 '-dihydroxydiphenyl sulfide, alkoxylated 4, 4' -dihydroxydiphenyl sulfone, or a mixture of two or more thereof; wherein the organic diisocyanate is 4, 4' -methylene-bis (phenyl isocyanate); 1, 1' -methylenebis (4-isocyanatocyclohexane); 4-methyl-1, 3-phenylene diisocyanate; 5-isocyanato-1- (isocyanatomethyl) -1, 3, 3-trimethylcyclohexane; 1, 6-hexamethylene-diisocyanate; toluene-2, 4-diisocyanate; or a mixture of two or more thereof.

3. The spandex of claim 1, comprising combining at least one polymer diol in an amount from 70% to 90% by weight and at least one alkoxylated phenol in an amount from 10% to 30% by weight.

4. The spandex of claim 1, wherein the polymeric diol is a polycarbonate diol, a polyester diol, a polyether diol, or a mixture of two or more thereof.

5. The spandex of claim 1, wherein the polymer diol is poly (pentane-1, 5-carbonate) diol, poly (hexane-1, 6-carbonate) diol, or a mixture thereof.

6. Spandex according to claim 1, wherein the polymeric diol is a polycondensation product of a diol and a diacid.

7. Spandex according to claim 6, wherein the diol is ethylene glycol, 1, 4-butanediol, 2-dimethyl-1, 3-propanediol.

8. The spandex of claim 6 wherein the diacid is adipic acid, succinic acid, dodecanedioic acid, or a mixture of two or more thereof.

9. The spandex of claim 1, wherein the alkoxylated phenol is an alkoxylated 2, 2-bis (4-hydroxyphenyl) propane, an alkoxylated bis (4-hydroxyphenyl) methane, an alkoxylated 1, 1-bis (4-hydroxyphenyl) ethane, an alkoxylated 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, an alkoxylated 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, an alkoxylated 2, 2-bis (4-hydroxy-3-methylphenyl) propane, an alkoxylated bis (4-hydroxyphenyl) sulfide, an alkoxylated bis (4-hydroxyphenyl) sulfone, or a mixture of two or more thereof.

10. The spandex of claim 1 wherein the alkoxylated phenol is an alkoxylated diphenol or an alkoxylated dihydric phenol.

11. Spandex according to claim 1, comprising the step of polymerizing the product of step (b) with at least one diamine and at least one chain extender selected from the group consisting of diols and amino alcohols.

12. The spandex according to claim 1, further comprising at least one of the following compounds: chlorine-resistant additives, antibacterial agents, antioxidants, heat stabilizers, gas-resistant stabilizers, pigments, delustering agents, anti-blocking agents, heat-setting agents, dyes, emulsifiers, wetting agents, antistatic agents, pH regulators, thread compactors, anticorrosive agents, dispersants and lubricants.

13. A spandex dry-spun from a solution of a polyurethaneurea in an organic solvent, wherein the polyurethaneurea is prepared by a process comprising: mixing 90% to 70% by weight of polytetrahydrofuran and 10% to 30% by weight of ethoxylated bisphenol a to form a resin; and reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) with a capping ratio of 1.5 to 2.

14. Spandex according to claim 13 wherein the ethoxylated bisphenol a contains 2 to 10 moles of ethylene oxide.

15. Spandex according to claim 14 wherein the ethoxylated bisphenol a contains 4 to 8 moles of ethylene oxide.

16. The spandex according to claim 13, wherein the organic solvent comprises dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, or a mixture of two or more thereof.

17. The spandex of claim 13, further comprising a chlorine-resistant additive, an antimicrobial agent, an antioxidant, a heat stabilizer, a gas-resistant stabilizer, a pigment, a delustering agent, an anti-tack agent, a heat setting agent, a dye, an emulsifier, a wetting agent, an antistatic agent, a pH adjuster, an anti-blocking agent, a filament compacting agent, an anti-corrosive agent, a dispersant, a lubricant, or a mixture of two or more thereof.

18. A feed package comprising a core and the spandex of claim 13.

19. A spandex dry-spun from a solution of a polyurethaneurea in an organic solvent, wherein the polyurethaneurea is prepared by a process comprising: mixing 90% to 70% by weight of polytetrahydrofuran and 10% to 30% by weight of ethoxylated bisphenol a to form a resin; and reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) to form a capped glycol, wherein the capping ratio is 1.5-2; the capped glycol is reacted with a mixture comprising 83% to 92% by weight of ethylenediamine, 8% to 17% by weight of 1, 2-diaminopropane, and 5% to 15% by weight of diethylamine to form a polyurethaneurea.

20. The spandex of claim 19, wherein the ethoxylated bisphenol a contains 2 to 10 moles of ethylene oxide.

21. The spandex of claim 20, wherein the ethoxylated bisphenol a contains from 4 to 8 moles of ethylene oxide.

22. The spandex according to claim 19, wherein the organic solvent comprises dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, or a mixture of two or more thereof.

23. The spandex of claim 19, further comprising a chlorine-resistant additive, an antimicrobial agent, an antioxidant, a heat stabilizer, a gas-resistant stabilizer, a pigment, a delustering agent, an anti-tack agent, a heat setting agent, a dye, an emulsifier, a wetting agent, an antistatic agent, a pH adjuster, an anti-blocking agent, a filament compacting agent, an anti-corrosive agent, a dispersant, a lubricant, or a mixture of two or more thereof.

24. A supply package comprising a core and the spandex of claim 19.

25. A spandex comprising alkoxylated bisphenol a as its structural unit.

26. The spandex of claim 25, wherein said alkoxylated bisphenol a is an ethoxylated bisphenol a containing 2 to 10 moles of ethylene oxide.

27. The spandex of claim 25, wherein the alkoxylated bisphenol a has a water content of less than 550ppm and a potassium content of less than 25 ppm.

28. A process for preparing spandex comprising:

mixing at least one polymeric glycol and at least one alkoxylated phenol to form a resin mixture;

mixing the resin mixture and at least one organic diisocyanate to form an isocyanate-terminated diol;

polymerizing an isocyanate-terminated diol with at least one diamine to form a polyurethane; and

polyurethane is formed into spandex by reaction spinning, melt spinning, dry spinning or wet spinning.

29. The method of claim 28, wherein the polymeric glycol is polymethyltetrahydrofuran, polytetramethylene glycol, polytetrahydrofuran; poly (tetramethylene ether) glycol; polypropylene glycol; poly (3-methyl-1, 5-pentamethylene ether) glycol; poly (tetramethylene ether-co-3-methyltetramethylene ether) glycol, or a mixture of two or more thereof; wherein the alkoxylated phenol is alkoxylated bisphenol A, alkoxylated bis (4-hydroxyphenyl) methane, alkoxylated 1, 1-bis (4-hydroxyphenyl) ethane, alkoxylated 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, alkoxylated 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, alkoxylated 2, 2-bis (4-hydroxy-3-methylphenyl) propane, alkoxylated bis (4-hydroxyphenyl) sulfur, alkoxylated bis (4-hydroxyphenyl) sulfone, alkoxylated diphenylphenol, alkoxylated 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, alkoxylated 1, 1-bis (4-hydroxyphenyl) cyclohexane, alkoxylated bisphenol A, alkoxylated bisphenol B, alkoxylated bisphenol A, alkoxylated 2-bis (4-hydroxyphenyl) propane, alkoxylated 2, 2-bis (4-hydroxyphenyl) cyclohexane, alkoxylated 1-bis (4-hydroxyphenyl, Alkoxylated 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, alkoxylated 4, 4 '-dihydroxydiphenyl sulfide, alkoxylated 4, 4' -dihydroxydiphenyl sulfone, or a mixture of two or more thereof; wherein the organic diisocyanate is 4, 4' -methylene-bis (phenyl isocyanate); 1, 1' -methylenebis (4-isocyanatocyclohexane); 4-methyl-1, 3-phenylene diisocyanate; 5-isocyanato-1- (isocyanatomethyl) -1, 3, 3-trimethylcyclohexane; 1, 6-hexamethylene-diisocyanate; toluene-2, 4-diisocyanate; or a mixture of two or more thereof.

30. The method of claim 28, comprising mixing at least one polymer diol in an amount of 70% to 90% by weight and at least one alkoxylated phenol in an amount of 10% to 30% by weight to form a resin mixture.

31. The method of claim 28, wherein the isocyanate-terminated diol has a capping ratio of 1.5 to 2.

32. The method of claim 28, wherein the polymeric diol is polytetrahydrofuran, the alkoxylated phenol is alkoxylated bisphenol a, and the organic diisocyanate is 4, 4' -methylene-bis (phenyl isocyanate).

33. The method of claim 28 comprising polymerizing an isocyanate-terminated diol with at least two diamines to form a polyurethane.

34. The method of claim 28 comprising polymerizing the isocyanate terminated diol with ethylenediamine, 1, 2-diaminopropane, and diethylamine.

35. The method of claim 28, wherein the polymeric diol is a polycarbonate diol, a polyester diol, a polyether diol, or a mixture of two or more thereof.

36. The method according to claim 28, wherein the alkoxylated phenol is an alkoxylated biphenol or an alkoxylated dihydric phenol.

37. The method according to claim 28, comprising dry spinning the polyurethane to form spandex.

38. A garment comprising the spandex of claim 1, 13, 19, or 25.

39. A disposable personal hygiene article comprising the spandex of claim 1, 13, 19, or 25.

40. A spandex prepared by solution spinning of a polyurethaneurea in a solvent, wherein the polyurethaneurea is prepared by a process comprising:

mixing 95% to 60% by weight of a polymeric diol with 5% to 40% by weight of an alkoxylated bisphenol a to form a resin;

reacting a resin and at least one organic diisocyanate to form a capped glycol;

the capped glycol is polymerized with at least one chain extender to form a polyurethane.

41. The spandex of claim 40, wherein the polymeric diol is a polycarbonate diol, a polyester diol, a polyether diol, or a mixture of two or more thereof.

42. The spandex of claim 40, wherein the polymeric glycol is polymethyltetrahydrofuran, polytetramethylene glycol, polytetrahydrofuran, poly (tetramethylene ether) glycol, polypropylene glycol, poly (3-methyl-1, 5-pentamethylene ether) glycol, poly (tetramethylene ether-co-3-methyltetramethylene ether) glycol, or a mixture of two or more thereof.

43. A spandex according to claim 40 wherein the organic diisocyanate is 4, 4 '-methylene-bis (phenyl isocyanate), 1' -methylene-bis (4-isocyanatocyclohexane), 4-methyl-1, 3-phenylene diisocyanate, 5-isocyanato-1- (isocyanatomethyl) -1, 3, 3-trimethylcyclohexane, 1, 6-hexamethylene-diisocyanate, toluene-2, 4-diisocyanate, or a mixture of two or more thereof.

44. The spandex of claim 40, wherein the at least one chain extender is ethylenediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 1, 3-diaminopropane, 1, 2-diaminopropane, 1, 3-diaminopentane, 2-methyl-1, 5-pentanediamine, isophoronediamine, 1-amino-3-aminoethyl-3, 5, 5-trimethylcyclohexane, or a mixture of two or more thereof.

45. The spandex according to claim 40, wherein the polyurethaneurea is prepared by a process comprising: from 90% to 70% by weight of a polymeric diol is mixed with from 10% to 30% by weight of an alkoxylated bisphenol a to form a resin.

46. The spandex according to claim 45, wherein the polyurethaneurea is prepared by a process comprising: from 90% to 75% by weight of a polymeric diol is mixed with from 10% to 25% by weight of an alkoxylated bisphenol a to form a resin.

47. The spandex according to claim 46, wherein the polyurethaneurea is prepared by a process comprising: from 85% to 80% by weight of a polymeric diol is mixed with from 15% to 20% by weight of an alkoxylated bisphenol a to form a resin.

48. The spandex according to claim 40, wherein the end-capping ratio is from 1.5 to 3.

49. The spandex according to claim 48, wherein the end-capping ratio is from 1.5 to 2.

50. The spandex according to claim 49, wherein the end-capping ratio is from 1.6 to 1.9.

51. The spandex according to claim 40, wherein the spandex is dry spun from a solution of polyurethaneurea in a solvent.

52. A spandex prepared by dry spinning from a solution of polyurethaneurea in an organic solvent, wherein the polyurethaneurea is prepared by a process comprising: mixing 95% to 60% by weight of polytetrahydrofuran with 5% to 40% by weight of alkoxylated bisphenol a to form a resin; the resin is reacted with 4, 4' -methylene-bis (phenyl isocyanate) with a blocking ratio of 1.5 to 3.

53. A spandex prepared by dry spinning from a solution of polyurethaneurea in an organic solvent, wherein the polyurethaneurea is prepared by a process comprising: mixing 95% to 60% by weight of polytetrahydrofuran with 5% to 40% by weight of alkoxylated bisphenol a to form a resin; reacting the resin with 4, 4' -methylene-bis (phenyl isocyanate) to form a capped glycol, wherein the capping ratio is 1.5 to 3; the capped glycol is polymerized with a mixture containing 83% to 92% by weight ethylenediamine, 8% to 17% by weight 1, 2-diaminopropane, and 5% to 15% by weight diethylamine to form a polyurethaneurea.

54. A spandex containing ethoxylated bisphenol A as its structural unit.