TWI530598B - Method for manufacturing melt spun thermoplastic polyurethane fibers - Google Patents

Description

Method for producing melt-spun thermoplastic polyurethane fiber

The invention relates to a method for manufacturing a melt-spun thermoplastic polyurethane (TPU) fiber, and the melt-spun thermoplastic polyurethane fiber obtained by the method of the invention is solvent-free and belongs to an environmentally friendly material. .

Thermoplastic polyurethanes are typically made by reacting a hydroxyl terminated polyester or polyether, a chain extender, and an isocyanate. Thermoplastic polyurethanes are segment polymers with flexible segments and hard segments, which is characterized by the excellent elastic properties of thermoplastic polyurethanes. The soft segment consists of a hydroxyl terminated intermediate which is typically a polyester or a polyether. The rigid segment consists of a diol chain extender and an isocyanate. U.S. Patent No. 5,959,059 discloses a thermoplastic polyurethane made from a hydroxyl terminated polyether, a diol chain extender and a diisocyanate. This thermoplastic polyurethane can be used in the manufacture of fibers, golf ball cores, SUV tires, and other applications.

The prior art utilizes polytetramethylene ether glycols (PTMEG 2000), 1,4-butanediol (1,4-Butanediol, 1,4-BD), and diphenylmethane-4. 4'-diisocyanate (Methylene diphenyl 4,4'-diisocyanate, MDI) is reacted in dimethylformamide (DMF) or dimethylacetamide (DMAc) to obtain 50% thermoplastic polyurethane A stock solution of the ester. The stock solution is then subjected to spinning, drying (solvent removal), and then crimped into ingots to form thermoplastic polyurethane fibers. However, the thermoplastic polyurethane fiber obtained by the prior art has not only the problem of residual toxic solvent, but also the solvent volatilization during the manufacturing process, which causes environmental pollution, operator injury and the like.

How to avoid the problem of adding a toxic solvent in the process of manufacturing a thermoplastic polyurethane fiber is a subject of research and development of the present invention.

Accordingly, the object of the present invention is to provide a method for producing a melt-spun thermoplastic polyurethane fiber, and no solvent is used in the process of the manufacturing method, so that the present invention does not cause harm to the environment or the human body, and thus The problem of contamination caused by the addition of a solvent in the process of manufacturing thermoplastic polyurethane fibers can be completely solved.

In order to achieve the above object, the present invention provides a method for producing melt-spun thermoplastic polyurethane fibers, comprising the steps of: (a) combining a polyol, a chain extender and an isocyanate to a molar ratio of 2 to 5: 0.1 to 0.5: 2~6 mixed reaction, then subjected to aging, pulverization, granulation step to form a plurality of melt-spun thermoplastic polyurethane granules; and (b) melt-spun thermoplastic polyurethane granules and one After the polyurethane cross-linking agent is uniformly blended, it is spun to form a melt-spun thermoplastic polyurethane fiber, wherein the polyurethane cross-linking agent is a polyol, a chain extender and an isocyanate-Imoler ratio of 1 to 5:0~ 0.5:2~10 is formed after mixing reaction.

In the process of the manufacturing method of the present invention, since no solvent is used, it does not cause harm to the environment and the human body, and the melt-spun thermoplastic polyurethane fiber of the present invention contains no solvent, is an environmentally friendly material, and at the same time can be attained. The physical properties of conventional melt-spun thermoplastic polyurethane fibers. In addition, the conventional technical equipment has high cost (the conventional production line costs about 100 million yuan, the production line of the invention only needs about one tenth of the conventional production line cost), and the conventional technology production line equipment occupies space, and the production line of the invention The device is more space efficient.

The above and other objects, features and advantages of the present invention will become more apparent from

The invention provides a method for manufacturing a melt-spun thermoplastic polyurethane fiber, comprising the following steps: (a) mixing a polyol, a chain extender and an isocyanate to a molar ratio of 2 to 5: 0.1 to 0.5: 2 to 6; The reaction is agglomerated and subjected to a ripening step at 50 ° C to 100 ° C for 15 to 30 hours, followed by pulverization and granulation to form melt-spun thermoplastic polyurethane colloidal particles; (b) polyol, chain extender and isocyanate After mixing with Imol ratio of 1~5:0~0.5:2~10, reacting in reactor of 50°C to 120°C 6~24 Forming a polyurethane cross-linking agent in an hour; and (c) adding the melt-spun thermoplastic polyurethane colloidal particles formed as described above and the polyurethane cross-linking agent to an extruder, fusing together, and spinning by a textile machine to form Melt-spun thermoplastic polyurethane fibers.

The polyol used in the steps (a) and (b) in the method for producing the melt-spun thermoplastic polyurethane fiber of the present invention is, for example, ethylene glycol (EG) and 1,3-butylene glycol (1, 3). -BG), 1,4-butanediol (1,4-BG), 2-methyl-1,3-propanediol, hexanediol (HG), 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol (CHDM), polytetramethylene ether glycol (PTMEG) (MW=650~2000), polypropylene glycol (PPG) (MW=200~2000), with adipic acid, phthalic anhydride A polyester or polyether polyol produced by reacting terephthalic acid, azelaic acid or the like (having a weight average molecular weight of MW=700 to 3000).

The chain extender used in the steps (a) and (b) in the method for producing the melt-spun thermoplastic polyurethane fiber of the present invention comprises ethylene glycol, propylene glycol, 1,3-butylene glycol, and 1,4-butane. Short-chain alcohols such as alcohol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanediol.

The isocyanate used in the steps (a) and (b) in the method for producing the melt-spun thermoplastic polyurethane fiber of the present invention comprises diphenylmethane-4,4'-diisocyanate (4,4'-MDI), two Phenylmethane-2,4-diisocyanate (2,4-MDI), MDI-50 (4,4'-MDI/2,4-MDI=50%), p-phenylene diisocyanate (PPDI), hydrogenated diphenyl Methane diisocyanate (H12MDI), hexamethylene diisocyanate (HDI) and benzene dimethylene diisocyanate (XDI).

The embodiments provided below are merely illustrative of the technical means of the present invention and are not intended to limit the technical scope of the present invention.

Embodiment 1

1000 grams of poly(adipate)-1,3-butylene glycol ester (PBA, Mn=2000), 135 grams of 1,6-hexanediol (1,6-HD as a chain extender) and 427 grams of diphenyl Methylene diphenyl 4,4'-diisocyanate (MDI) was mixed and stirred into a disk to form a paste. Then, the paste is poured into a conveyor belt (rotary disk) through the filling port of the filling machine, and the conveyor belt will convey the paste into a drying tunnel of 100 ° C (heated by infrared rays), and the paste will pass through the drying tunnel. Become a block. Next, the block was conveyed by a cart to a ripening chamber at about 80 to 90 ° C for 24 hours. After the block reaction is fully matured, it is pulverized and granulated by a pulverizer and a granulator, and then dried to form melt-spun thermoplastic polyurethane rubber particles.

Secondly, polyadipate-1,3-butylene glycol ester, 1,6-hexanediol and diphenylmethane The -4,4'-diisocyanate is mixed with 1 to 5:0 to 0.5:2 to 10, and then reacted in a reactor at 50 to 120 ° C for 6 to 24 hours to form a polyurethane crosslinking agent.

Next, the melt-spun thermoplastic polyurethane colloid particles and the cross-linking agent formed above are added to an extruder and uniformly blended, and then spun by a spinning machine to form a melt-spun thermoplastic polyurethane fiber.

The invention has the advantages that the manufacturing method of the melt-spun thermoplastic polyurethane fiber has the following advantages: 1. The manufacturing process of the invention does not use a solvent, and thus does not cause human injury and environmental pollution; 2. The melt-spun thermoplastic polyamine prepared by the invention The formic acid fiber has no residual solvent and is an environmentally friendly material; 3. The physical properties of the melt-spun thermoplastic polyurethane fiber obtained by the present invention are comparable to those of the thermoplastic polyurethane fiber prepared by the prior art; Silk equipment investment is small.

It will be apparent to those skilled in the art that various modifications and changes can be made without departing from the spirit and scope of the invention. Therefore, the present invention includes such modifications and variations, and is included in the scope of the appended claims and their equivalents.

Claims (10)

A method for producing melt-spun thermoplastic polyurethane fibers, comprising the steps of: (a) mixing a polyol, a chain extender and an isocyanate to a molar ratio of 2 to 5: 0.1 to 0.5: 2 to 6; Reacting, further pulverizing, pulverizing, and granulating steps to form a plurality of melt-spun thermoplastic polyurethane colloidal particles; and (b) fusing the melt-spun thermoplastic polyurethane colloidal particles and a polyurethane crosslinking agent After homogenization, spinning is carried out to form melt-spun thermoplastic polyurethane fibers. The method for producing a melt-spun thermoplastic polyurethane fiber according to claim 1, wherein the polyol, the chain extender and the isocyanate in the step (a) are at about 100 ° C to 150 ° C. The reaction is carried out at a temperature for 10 to 36 minutes. The method for producing a melt-spun thermoplastic polyurethane fiber according to claim 1, wherein the polyol of the step (a) is ethylene glycol (EG) or 1,3-butylene glycol ( 1,3-BG), 1,4-butanediol (1,4-BG), 2-methyl-1,3-propanediol, hexanediol (HG), 3-methyl-1,5-pentyl Glycol, 1,4-cyclohexanediol (CHDM), polytetramethylene ether glycol (PTMEG) and polypropylene glycol (PPG), reacted with adipic acid, phthalic anhydride, terephthalic acid and glutaric acid The resulting polyester or polyether polyol. The method for producing a melt-spun thermoplastic polyurethane fiber according to claim 1, wherein the chain extender of the step (a) is selected from the group consisting of ethylene glycol, propylene glycol, and 1,3-butylene glycol. A group of 1,4-butanediol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanediol. The method for producing a melt-spun thermoplastic polyurethane fiber according to claim 1, wherein the isocyanate in the step (a) is selected from the group consisting of diphenylmethane-4,4'-diisocyanate (4, 4'-MDI), diphenylmethane-2,4-diisocyanate (2,4-MDI), MDI-50 (4,4'-MDI/2,4-MDI=50%), p-phenylene diisocyanate (PPDI), hydrogenated diphenylmethane diisocyanate (H12MDI), hexamethylene diisocyanate (HDI) and benzene dimethylene diisocyanate (XDI). The method for producing melt-spun thermoplastic polyurethane fibers according to claim 1, wherein the ripening step in the step (a) is carried out at a temperature of from 50 ° C to 100 ° C for 15 to 30 hours. The method for producing a melt-spun thermoplastic polyurethane fiber according to the first aspect of the invention, wherein the polyurethane crosslinking agent is based on a polyol, a chain extender and an isocyanate Imol-1. After 5:0~0.5:2~10 mixing, it is formed by reacting in a reaction vessel of 50 ° C to 120 ° C for 6 to 24 hours. The method for producing a melt-spun thermoplastic polyurethane fiber according to claim 7, wherein the polyol is ethylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, polytetramethylene ether glycol, and polypropylene glycol, and A polyester or polyether polyol produced by the reaction of adipic acid, phthalic anhydride, terephthalic acid and glutaric acid. The method for producing a melt-spun thermoplastic polyurethane fiber according to claim 7, wherein the chain extender is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butylene glycol, and 1,4- A group consisting of butanediol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanediol. Melt-spun thermoplastic polyurethane as described in claim 7 A method for producing an ester fiber, wherein the isocyanate is selected from the group consisting of diphenylmethane-4,4'-diisocyanate (4,4'-MDI) and diphenylmethane-2,4-diisocyanate (2,4- MDI), MDI-50 (4,4'-MDI/2,4-MDI=50%), p-phenylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate and benzene dimethylene diisocyanate Grouped.