DE1669495A1 - Process for the production of spandex threads by extrusion of isocyanate polyaddition products - Google Patents

Description

MOBAY CHEMICAL COMPANY

Penn Lincoln Parkway West. Pittsburgh, Pennsylvania 15205

Leverkusen, September 22nd 1966

GM / Bn

Process for the production of spandex threads by extrusion of isocyanate polyaddition products

The manufacture of spandex threads by implementing a polyfunctional polymeric compound containing active hydrogen atoms with an organic diisocyanate and a chain extender into a polymer that is either spun or extruded using the wet or dry spinning process is known. When filaments are produced by extrusion, the properties are generally good. It however, it is desirable to produce threads with a higher tear strength and a higher heat resistance. Further it is desirable to use a starting material in the production of filaments by the extrusion method, which is the Storage is stable. To facilitate extrusion, it is also desirable to incorporate plasticizers into the reaction mixture.

It has now surprisingly been found that all of these Advantages can be achieved when a mixture of a polyurethane

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extruded with a capped polyisocyanate to form spandex threads will. The present invention thus relates to a process for the production of spandex threads by extrusion of isocyanate polyadducts, which consists in the fact that a mechanical mixture of a) by reacting one polymeric diol with a molecular weight of at least. and a glycol having a molecular weight less than 300 with an organic diisocyanate in an NCO χ OH ratio essentially linear polyurethane produced from 0.95 to 1.02 and from b) a blocked polyisocyanate in an amount of 1 to 10 percent by weight, based on the polyurethane, is converted into spandex threads by extrusion. To In a preferred method, the mechanical mixture contains blocked polyisocyanate in an amount of 2 to 6 percent by weight, based on the polyurethane used, and has a functionality of 2 to 4-.

The mechanical mixture used to make spandex threads is stable during storage because of the NCO to OH ratio of the polyurethane is almost 1 and therefore contains essentially no free NCO groups and because the

only cut the polyisocyanate when it was heated to release NCO groups puts. In the molten state, the blocked polyisocyanate also serves as a plasticizer. One disadvantage so far known crosslinked polymers used to produce filaments is that they are either unstable

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are or are difficult to process. In addition, the threads produced according to the invention show a higher thermal stability and improved permanent elongation. The threads also have a higher resistance to Solvents and heat. The blocked polyisocyanates act as plasticizers and when mixed in the extruder effect during the reaction and after the removal of the blocking substance Networking.

In the preparation of the above-mentioned mechanical mixture, a polyurethane, which consists of a polymeric diol having a molecular weight of at least 500, an organic diisocyanate and a glycol is used will. Polymeric diols as starting material are e.g. polyester diols, divalent polyalkylene ether glycols, polythio ether glycols, difunctional polyacetals. Dihydroxy polyesters, for example the reaction product, can also be used a dicarboxylic acid and a dihydric alcohol. The dicarboxylic acids used in the production of the hydroxypolyesters are e.g. adipic acid, succinic acid, sebacic acid, Suberic acid, oxalic acid, methyladipic acid, glutaric acid, Pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodipropionic acid, thiodibutyric acid, Sulfonyldibutyric acid, maleic acid, fumaric acid, citraconic acid, Itaconic acid application. Any dihydric alcohols can be used as the glycol component in the reaction with the

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Dicarboxylic acid can be used for polyester, e.g. ethylene glycol, Diethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, amylene glycol, hexanediol, hexahydroxylylene glycol, Bis-hydroxymethyl / cyclohexane. The hydroxy polyester can of course also urethane groups, urea groups, Contain amide groups or chalcogen groups, so that in addition to pure polyesters with terminal hydroxyl groups too Polyester amides, polyester urethanes, polyether esters and the like Compounds with terminal hydroxyl groups come into question. Polyester amides used in the present invention are, for example, the reaction product of a diamine or an amino alcohol with one of the above used to produce the polyester Link. Suitable amines used for the reaction are, for example, ethylenediamine, propylenediamine or tolylenediamine. The amino alcohols can also be chosen as desired, e.g. ß-hydroxyethylamine and similar compounds be used. Polyester urethanes can also be used are used, e.g. the reaction products of an above-mentioned polyester or polyester amide with a Deficiency of an organic diisocyanate. The diisocyanates will be explained later.

Polyether esters with terminal hydroxyl groups can also be used to produce the polyurethane polymer, for example the reaction product produced analogously to the production of polyesters from an ether glycol and one of the above

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mentioned dicarboxylic acids. Ethylene glycol, triethylene glycol, 1,4 ~ phenylene-bi3-hydroxyethyl ether, 2,2-diphenylpropane-4 _f 4'-bis-hydroxyethyl ether are suitable as ether glycols.

Polyalkylene ether glycols can also be used as ether glycols, e.g. the condensation product of an alkylene oxide with a small amount of a compound containing active hydrogen atoms, e.g. water, ethylene glycol, propylene glycol, Butylene glycol, amylene glycol. It can also use alkylene oxide condensates can be used, e.g. the condensates of ethylene oxide, propylene oxide, butylene oxide, amylene oxide and Mixtures of these. Polyalkylene ethers made from tetrahydrofuran can also be used. The polyhydroxypolyalkylene ethers can be prepared by any known method, such as the Encyclopedia of Chemical Technology ", Volume 7, pages 257 to 266, 1951 (Interscience Publishers) or * according to US Pat. No. 1,922,459.

Any polythioether glycols are also suitable as starting material for the production of the polyurethane, e.g. the reaction product of one of the alkylene oxides mentioned above in the production of the polyhydroxypolyalkylene ethers with a polyhydroxythioether, e.g. thiodiglycol, 3,3'-dihydroxypropyl sulfide, 4 _f 4 -'-dihydroxybutyl sulfide, 1, 4- (ß-hydroxyethyl) phenylenedithioether.
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Polyacetals can also be used to produce the polyurethane can be used, e.g., the reaction product of an aldehyde with a dihydric alcohol. As aldehydes are mentioned ι formaldehyde, paraldehyde, butyraldehyde, The alcohols mentioned above in connection with the manufacture of the hydroxypolyesters are used polyhydric alcohols in question. Furthermore, any glycols having a molecular weight can be used for the production of the polyurethane suitable below 300, e.g. ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, butenediol, butynediol, Xylylene glycol, amylene glycol, neopentyl glycol, 2,4-butanediol, 1 ^ -phenylene-bis-CS-hydroxyethyl ether), 1,3-phenylene-bis- (ß-hydroxyethyl ether), Bis (hydroxymethyl) cyclohexane, kexanediol, diethylene glycol, dipropylene glycol.

Organic diisocyanates for the production of the polyurethane used according to the invention may be mentioned, for example, Ethylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, Butylene diisocyanate, hexamethylene diisocyanate, cyclopentylene-1,3-diisocyanate, Cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimeric tolylene diisocyanate, 4,4'-diphenylmathane diisocyanate, 2,2-diphenylpropane-4,4 ^ dUSOCyBnBt, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate,

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m-xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, Biphenyl-4,4'-diisocyanate, azobenzene-4,4 '-diisocyanate, diphenylsulfone-4-, 4-diisocyanate, Dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene-2,4-diisocyanate. Aromatic diisocyanates are preferred. 4,4'-diphenylmethane diisocyanate or tolylene diisocyanate have proven to be particularly suitable for achieving very good results.

To produce the polyurethane, the isocyanate is expediently used in such an amount that the NGO to OH ratio is between 0.35 and 1.02. A ratio of NCO to OH of 1: 1 is preferred.

As a further starting material for the process according to the invention Any masked polyisocyanate that generally has a functionality can be used to produce spandex threads should have from 2 to 4, e.g. from one of the above isocyanates according to the American Patent No. 2,683,727 prepared reaction products with a secondary aromatic amine, reaction products prepared according to US Pat. No. 2,683,728 with a tertiary one Alcohol, reaction products synthesized according to US Pat. No. 2,683 with an enolizable Hydrogen-containing compound, furthermore reaction products which can be prepared according to US Pat. No. 2,698,845 a lactam or according to US Pat. No. 2,725,385

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bare reaction products with an imide. Further examples of the blocked polyisocyanate to be used according to the invention are reaction products obtained from one of the abovementioned isocyanates with a monohydric phenol, as described in US Pat. No. 2,733,261, and reaction products prepared according to US Pat. No. 2,764,592 with mercaptans or according to US Pat -Patent specification 2,797,232 prepared reaction products with hydroxyalkylcarbamic acid aryl esters, further reaction products with one of the polyalcohols described in the American patent specification 2,855,421, which are then reacted with a phenol. Reaction products of isocyanate-bisulfite adducts and formaldehyde, as described in US Pat. No. 2,746,988, and the capped polyisocyanates prepared according to US Pat. No. 2,952,665 and 3,080,368, may also be considered. In addition to the above-mentioned isocyanates, higher-functional polyisocyanates can also be used, for example 4,4 ', 4 ^M -triphenylmethane triisocyanate, 2,4,6-triisocyanatotoluene, naphthalene-1,3,7-triisocyanate, diphenylmethane -2,4,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ', 5 »5'-tetraisocyanate. A polyisocyanate that is preferably used is the reaction product of 3 moles of 2,4-tolylene diisocyanate with one mole of trimethylolpropane, which is then reacted with 3 moles of phenol. The capped polyisocyanate is used in an amount of from about 1 to about 10 percent by weight and preferably from about 2 to about 6 percent by weight of the polymer,

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The mechanical mixture of the polyurethane with the blocked polyisocyanate can by any method getting produced. According to one method, the solid polyurethane can be prepared by reacting the necessary ones described above Components are first produced and processed by suitable processes, e.g. by grinding or converting into Scales to be crushed. Da3 blocked polyisocyanate is then mechanically mixed with the solid parts of the polyurethane. Any equipment, e.g. mixers, roller mills and similar apparatus can be used. The blocked polyisocyanate can also be used in Be added at any stage during the manufacture of the polyurethane, as long as care is taken it is ensured that the temperature of the material does not exceed the temperature at that of the blocked polyisocyanate free NGO groups are formed. For example, the masked polyisocyanate can be used during manufacture of the polyurethane, the polymeric diol, the glycol, or the isocyanate either before mixing or during mixing can be added with the other respondents. This process provides a very intimate mechanical one Mixing and makes the mixing step, which is necessary after the first mentioned method, superfluous.

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example 1 1 A: Manufacture of the polyurethane

To 1000! Of a polyester with terminal hydroxyl groups, which was produced by reacting one mole of ethylene glycol and one mole of t, 4- ^T > ^ tanediol with 1.6 moles of adipic acid and a molecular weight of about 2000, a hydroxyl number of 55.2 in -I has an acid number of Q ₁ Z , 400 parts of 4.4 ^f -I ".phenylme thandiisocyanate and 101.5 parts of 1,4-butanediol are added so that the ratio of isocyanate groups to d- η hydroxyl groups is 0.98 . ^ as butanediol contains 0.03 f- Sisenace Cv U ^ -etonate to catalyze the isocyanate-hydroxyl reaction. When living together, the reaction components are brought to a temperature of

60 C heated. After de? Mixing, which takes about 1 f / 2 minutes, the reaction mixture is poured into a suitable mold and sprayed over with a mold release agent. The temperature is then 15 to 30 minutes at 80 - 110 ⁰ C and kept then cooled to room temperature. The reaction product is removed from the mold, cut and milled, and dried for two hours at 110 ⁰ G in vacuo.

Bi method according to the invention

100 parts of the polyurethane prepared under A «ground with 4 parts of a blocked polyisocyanate obtained by reacting 3 moles of 2,4-tolylene diisocyanate with one mole of trimethylolpropane and further reacting the adduct thus prepared with 3 moles of phenol. This Greatlsch is extruded at a temperature of 188 ° C and shows after a

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subsequent 16-hour Hitaebehandlung at 11O ⁰ C, a tensile strength of 1.21 g / den, a permanent elongation after fracture of 2 ^ and a heat deflection temperature 136-140 ⁰ C.

Cs comparison test ~ h

The polyurethane produced according to A is extruded for making a Moßofils at a temperature of 188 ⁰ C. The monofilament is subjected to the curing of a 16-hour heat treatment at 11O ⁰ C. The hardened monofilament has a tear strength of 0.53 g / den, a permanent elongation after break of 15 $> and a heat resistance of 95 to 115 ° C

example 2 \ A: Manufacture of dcg polyurethane

A polyurethane is prepared in analogy to the conditions of Example 1A, it will, however, 1,000 parts of the polyester, 300 parts of 4,4'-diphenylmethane diisocyanate and 99.5 parts of p-xylylenediol, containing 0.025 part of iron acetylacetonate at a temperature of 120 ⁰ C. implemented together. The reaction components are used in an NCO to OH ratio of 0.98. The solid polyurethane particles are dried in an oven ^{at 110 ° C. for two hours.}

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Bi method according to the invention

Two percent by weight of the masked polyisocyanate used under 1B are mixed dry with the polyurethane prepared under 2A and extruded under the conditions already mentioned to form a Jäonofil. The monofilaments obtained show a tear strength of 0.73 g / denier, a permanent elongation after breakage of 15 $ and a heat resistance of 88 to 92 ^° C.

If 4 # or 6 <$> of the same masked polyisocyanate are used and monofilaments are produced by extrusion, the monofilaments have the following properties: 0.35 g / denier or 0.73 g / denier, a permanent elongation after break of 10 # or . 5 # and a thermal stability of 90 to 94 ⁰ C or 126 to 134 ⁰ C.

Example 3 » Ai manufacture of polyurethane

To 1000 parts by weight of a polyester with terminal hydroxyl groups, the reaction of one mole Neopentyl glycol and one mole of 1,4-butanediol with 1.6 moles Adipic acid was produced and had a molecular weight of about 2000, a hydroxyl number of 56.4 and an acid number of about 0.7, 450 parts are 4,4'-diphenylmethane diisocyanate and 93 parts of ethylene glycol added,

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so that the ratio of isocyanate groups to hydroxyl groups is 1.00. The ethylene glycol contains 0.06 # iron acetylacetonate, which serves as a catalyst for the isoeyanate-hydroxyl reaction. The reaction components are heated to 60 G before mixing. After mixing for two minutes, the reaction mixture is poured into a suitable mold and sprayed or coated with a decolorizing agent. The temperature is held between 80 and 130 ^° C. for 30 to 60 minutes and then cooled to room temperature. The reaction material is removed from the mold, cut, ground and dried for two hours at 110 ° in a vacuum.

Bi method according to the invention

The mixed 100 parts of the polyurethane produced under 3A 4 parts of a according to the US Patent 2,952,665 dry from a Iaomerengemisch of $ 80> 2,4 and 20 $> 2,6-diisocyanate and cresol produced capped polyisocyanate. This mixture is extruded at a temperature of 200 ⁰ G. The monofilaments obtained are subjected to a 16-hour heat treatment at 110 ^° C. and show a tear strength of 0.84 g / den, a permanent elongation after break of 5 % and a heat resistance of 135 to HO ⁰ G.

Gt comparison test

The polyurethane produced according to 3A is extruded at a temperature of 200 ^° C. to form a monofilament. The mono-

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fil is subjected to a 16 hour heat treatment at 110 C to harden. The cured monofilament shows a tensile strength of 0.42 g / den, a permanent elongation after fracture of $ 20 and a heat deflection temperature of 125 to 13O ⁰ C.

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Claims (3)

Ps. Tcxitansprtlche: g * 1. Process for the production of spandex threads by extrusion of isocyanate polyaddition products, characterized in that a mechanical mixture of a) one by reacting a polymeric diol having a molecular weight of at least 500 and a glycol with a molecular weight of less than 300 with an organic diisocyanate in an FCO: OH ratio substantially linear polyurethane made from 0.95 to 1.02 and from b) a blocked polyisocyanate in an amount of 1 to 10 percent by weight, based on the polyurethane, is converted into spandex threads under extrusion. 2. The method according to claim 1, characterized in that the blocked Pclyisocyanat in an amount of 2 to 6 percent by weight, based on the polyurethane. 3. The method according to claim 1 and 2, characterized in that a capped polyisocyanate with a functionality from 2 to 4 is used. Mon 808 - 15 - ^109838/1613