阅读说明：本技术 一种tpu单丝 (TPU monofilament ) 是由 刘伟 于 2021-09-16 设计创作，主要内容包括：本申请属聚氨酯单丝技术领域,具体涉及一种TPU单丝,包括如下重量份的各组分：异氰酸酯90-100份、多元醇80-95份、扩链剂15-25份、有机抗静电剂2-10份、催化剂1.4-1.6份。本申请的TPU单丝将适当用量的有机抗静电剂添加到制备TPU单丝所用的聚氨酯体系中,有机抗静电剂与聚氨酯体系的相容性较好,可以相对较好地分散于整个体系中,起到长久的抗静电作用,可以有效避免TPU单丝在生产、后续加工和应用过程中因静电作用造成的不利影响。(The application belongs to the technical field of polyurethane monofilaments, and particularly relates to a TPU monofilament, which comprises the following components in parts by weight: 90-100 parts of isocyanate, 80-95 parts of polyol, 15-25 parts of chain extender, 2-10 parts of organic antistatic agent and 1.4-1.6 parts of catalyst. According to the TPU monofilament, the organic antistatic agent with a proper dosage is added into a polyurethane system for preparing the TPU monofilament, the organic antistatic agent and the polyurethane system are good in compatibility, can be relatively well dispersed in the whole system, plays a long-term antistatic role, and can effectively avoid adverse effects caused by the electrostatic effect in the production, subsequent processing and application processes of the TPU monofilament.)

1. A TPU monofilament characterized by: the paint comprises the following components in parts by weight: 90-100 parts of isocyanate, 80-95 parts of polyol, 15-25 parts of chain extender, 2-10 parts of organic antistatic agent and 1-1.6 parts of catalyst.

2. The TPU monofilament of claim 1 wherein: the isocyanate is aromatic diisocyanate.

3. The TPU monofilament of claim 1 wherein: the isocyanate is one or two of 2, 4-toluene diisocyanate and 4, 4' -diphenylmethane diisocyanate.

4. The TPU monofilament of claim 1 wherein: the polyol is polyester polyol or polyether polyol.

5. The TPU monofilament of claim 4 wherein: the polyester polyol is one or more of polyethylene glycol adipate glycol, polybutylene glycol adipate glycol and castor oil adipate glycol;

the polyether polyol is one or more of polyethylene glycol, polypropylene glycol, poly (1, 2-propylene glycol), poly (1, 3-propylene glycol) and polyethylene glycol-propylene glycol copolymer.

6. The TPU monofilament of claim 1 wherein: the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, triethylene glycol and neopentyl glycol.

7. The TPU monofilament of claim 1 wherein: the structural formula of the organic antistatic agent is as follows:

wherein R is C₁₀-C₃₀Normal alkyl of (a).

8. The TPU monofilament of claim 1 wherein: the catalyst is one or more of dibutyl tin dilaurate, dibutyltin maleate and dibutyltin maleate.

9. The TPU monofilament of any of claims 1 through 8, wherein: the preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding the organic antistatic agent and the catalyst into the polyhydric alcohol, uniformly stirring, and preheating to 90-100 ℃ to obtain a mixture A; respectively preheating isocyanate and a chain extender to 40-70 ℃;

(2) respectively driving the mixture A obtained in the step (1), isocyanate and a chain extender into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Technical Field

The application belongs to the technical field of monofilaments, and particularly relates to a TPU monofilament.

Background

TPU (thermoplastic polyurethanes) is thermoplastic polyurethane elastomer rubber, and is a high molecular material formed by jointly reacting diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), etc., with macromolecular polyol and low-molecular polyol (chain extender) and polymerizing. The molecular structure of the polyurethane elastomer is formed by alternately reacting a rigid block obtained by reacting diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI) with a chain extender and a flexible chain segment obtained by reacting diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI) with macromolecular polyol.

Because the TPU has the characteristics of high strength and good rebound resilience, the TPU is widely applied to the fabric textile industry, particularly to the vamp fly-woven fabric popular in recent years, and the addition of the TPU monofilament can effectively improve the integral stretching capacity of the vamp, so that the comfort level of the vamp is better. However, because the vamp is very close to the ground and the fly-woven fabric has a plurality of meshes, the fly-woven vamp is usually easy to be dusty and difficult to clean, so that the static electricity adsorption to dust can be effectively reduced by improving the antistatic effect of the TPU monofilament used in the fly-woven fabric, and the dust adhesion is further reduced.

Chinese patent document CN 104593900 a discloses an antistatic spandex fiber and a production method thereof, wherein titanium dioxide having a high surface coated with antimony-doped tin dioxide is used as an antistatic agent, and added into a polyurethane polymer solution for spinning to obtain the antistatic spandex fiber. The modified titanium dioxide is used as an auxiliary material to be added into the polymerization stock solution, and has no influence on performance indexes such as viscosity, spinnability and the like of the stock solution. However, since the antistatic agent is an inorganic material, poor compatibility with organic polymers results in uneven dispersion and easy penetration into the surface, which not only affects the appearance of the fiber, but also makes it difficult to exert a long-lasting antistatic effect.

In view of the above, there is a need to develop a TPU monofilament that can disperse an antistatic agent well in a polyurethane system, can exert a long-lasting antistatic effect, and does not affect the appearance of a product.

Disclosure of Invention

In order to solve the problems, the application discloses a TPU monofilament, wherein an organic antistatic agent is added into polyurethane to improve the dispersion effect of the antistatic agent, so that a good antistatic effect is achieved.

The application provides a TPU monofilament, adopts following technical scheme:

the TPU monofilament comprises the following components in parts by weight: 90-100 parts of isocyanate, 80-95 parts of polyol, 15-25 parts of chain extender, 2-10 parts of organic antistatic agent and 1-1.6 parts of catalyst.

The organic antistatic agent with proper dosage is added into a polyurethane system used for preparing the TPU monofilament, the organic antistatic agent has relatively good compatibility with the polyurethane system, can be relatively well dispersed in the whole system, plays a long-term antistatic role, and can effectively avoid adverse effects caused by electrostatic action in the production, subsequent processing and application processes of the TPU monofilament.

Preferably, the isocyanate is an aromatic diisocyanate.

Preferably, the isocyanate is one or both of 2, 4-tolylene diisocyanate and 4, 4' -diphenylmethane diisocyanate.

Preferably, the polyol is a polyester polyol or a polyether polyol.

Preferably, the polyester polyol is one or more of polyethylene glycol adipate glycol, polybutylene glycol adipate glycol and castor oil adipate glycol;

the polyether polyol is one or more of polyethylene glycol, polypropylene glycol, poly (1, 2-propylene glycol), poly (1, 3-propylene glycol) and polyethylene glycol-propylene glycol copolymer.

Preferably, the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, triethylene glycol and neopentyl glycol.

Preferably, the organic antistatic agent has a structural formula:

wherein R is C₁₀-C₃₀Normal alkyl of (a).

The isocyanate is aromatic isocyanate, the antistatic agent is an organic antistatic agent containing benzene rings and long-chain alkyl, and the introduction of the benzene rings in the antistatic agent can properly improve the compatibility between the antistatic agent and the aromatic isocyanate, so that the antistatic effect can be better exerted. In addition, the organic antistatic agent also comprises an antioxidant structure similar to 2, 5-di-tert-butylhydroquinone, so that a certain antioxidant effect can be achieved, and the durability of the TPU monofilament is improved.

The organic antistatic agent is prepared from hydroquinone and(R is C₁₀-C₃₀Normal alkyl) is prepared by friedel-crafts reaction, the reaction equation is:

preferably, the catalyst is one or more of dibutyl tin dilaurate, dibutyl tin maleate and dibutyl tin maleate.

Preferably, the TPU monofilament is prepared by the following method:

(1) weighing the components according to the formula ratio, adding the organic antistatic agent and the catalyst into the polyhydric alcohol, uniformly stirring, and preheating to 90-100 ℃ to obtain a mixture A; respectively preheating isocyanate and a chain extender to 40-70 ℃;

(2) respectively driving the mixture A obtained in the step (1), isocyanate and a chain extender into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

The application has the following beneficial effects:

(1) according to the TPU monofilament, an appropriate amount of organic antistatic agent is added into a polyurethane system for preparing the TPU monofilament, the organic antistatic agent has relatively good compatibility with the polyurethane system, can be relatively well dispersed in the whole system, plays a long-term antistatic role, and can effectively avoid adverse effects caused by electrostatic action in the production, subsequent processing and application processes of the TPU monofilament;

(2) the isocyanate used in the antistatic agent is aromatic isocyanate, the antistatic agent is an organic antistatic agent containing benzene rings and long-chain alkyl, and the introduction of the benzene rings in the antistatic agent can properly improve the compatibility between the antistatic agent and the aromatic isocyanate, so that the antistatic effect can be better exerted;

(3) the organic antistatic agent used in the application also comprises an antioxidant structure similar to 2, 5-di-tert-butylhydroquinone, so that a certain antioxidant effect can be achieved, and the durability of TPU monofilaments is improved.

Detailed Description

The present application will now be described in further detail with reference to examples.

The organic antistatic agents used in examples and comparative examples were prepared by the following methods: adding hydroquinone and a sulfuric acid catalyst into a reaction kettle, heating to 75 ℃ under stirring, adding 2-methyl-eicosyl-1-ene, carrying out alkylation reaction for 4 hours, washing the obtained product with hot water at 70 ℃, neutralizing with sodium carbonate, washing with hot water at 70-80 ℃ to be neutral, cooling to 10-15 ℃ for crystallization, carrying out centrifugal dehydration, dissolving in hot ethanol, and recrystallizing to obtain the organic antistatic agent. Wherein the molar ratio of hydroquinone to 2-methyl-eicosyl-1-ene is 1: 2.

Example 1

Preparing raw materials: 90 parts of 2, 4-toluene diisocyanate, 40 parts of polyethylene glycol, 40 parts of poly-1, 2-propylene glycol, 5 parts of ethylene glycol, 5 parts of propylene glycol, 5 parts of triethylene glycol, 3 parts of an organic antistatic agent and 1 part of dibutyl tin dilaurate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding the organic antistatic agent and dibutyl tin dilaurate into polyethylene glycol and poly (1, 2-propylene glycol), uniformly stirring, and preheating to 90 ℃ to obtain a mixture A; preheating 2, 4-toluene diisocyanate to 40 ℃, mixing ethylene glycol, propylene glycol and triethylene glycol, and preheating to 50 ℃;

(2) respectively pumping the mixture A obtained in the step (1), neopentyl glycol, ethylene glycol, propylene glycol and triethylene glycol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Example 2

Preparing raw materials: 100 parts of 4, 4' -diphenylmethane diisocyanate, 40 parts of polypropylene glycol, 55 parts of poly-1, 3-propylene glycol, 10 parts of ethylene glycol, 10 parts of 1, 6-hexanediol, 5 parts of neopentyl glycol, 8 parts of an organic antistatic agent and 1.5 parts of dibutyltin maleate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding the organic antistatic agent and dibutyltin maleate into polypropylene glycol and poly-1, 3-propylene glycol, uniformly stirring, and preheating to 100 ℃ to obtain a mixture A; preheating 4, 4' -diphenylmethane diisocyanate to 60 ℃, mixing ethylene glycol, 1, 6-hexanediol and neopentyl glycol, and preheating to 70 ℃;

(2) respectively driving the mixture A obtained in the step (1), 4' -diphenylmethane diisocyanate, ethylene glycol, 1, 6-hexanediol and neopentyl glycol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Example 3

Preparing raw materials: 95 parts of tetramethylene diisocyanate, 45 parts of polyethylene glycol, 45 parts of poly-1, 2-propylene glycol, 10 parts of ethylene glycol, 10 parts of 1, 4-butanediol, 5 parts of an organic antistatic agent and 1.3 parts of dibutyltin maleate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding the organic antistatic agent and dibutyltin maleate into polyethylene glycol and poly 1, 2-propylene glycol, uniformly stirring, and preheating to 95 ℃ to obtain a mixture A; preheating tetramethylene diisocyanate to 50 ℃, mixing ethylene glycol and 1, 4-butanediol and preheating to 60 ℃;

(2) respectively driving the mixture A obtained in the step (1), tetramethylene diisocyanate, ethylene glycol and 1, 4-butanediol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Example 4

Preparing raw materials: 95 parts of 4, 4' -diphenylmethane diisocyanate, 45 parts of polyethylene glycol, 45 parts of poly-1, 2-propylene glycol, 10 parts of ethylene glycol, 10 parts of 1, 4-butanediol, 5 parts of an organic antistatic agent and 1.3 parts of dibutyltin maleate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding the organic antistatic agent and dibutyltin maleate into polyethylene glycol and poly 1, 2-propylene glycol, uniformly stirring, and preheating to 95 ℃ to obtain a mixture A; preheating 4, 4' -diphenylmethane diisocyanate to 50 ℃, mixing ethylene glycol and 1, 4-butanediol and preheating to 60 ℃;

(2) respectively pumping the mixture A obtained in the step (1), 4' -diphenylmethane diisocyanate, ethylene glycol and 1, 4-butanediol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Comparative example 1

Preparing raw materials: 95 parts of 4, 4' -diphenylmethane diisocyanate, 45 parts of polyethylene glycol, 45 parts of poly-1, 2-propylene glycol, 10 parts of ethylene glycol, 10 parts of 1, 4-butanediol, 5 parts of octadecyl diethanol amine and 1.3 parts of dibutyltin maleate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding octadecyl diethanol amine and dibutyl tin maleate into polyethylene glycol and poly (1, 2-propylene glycol), uniformly stirring, and preheating to 95 ℃ to obtain a mixture A; preheating 4, 4' -diphenylmethane diisocyanate to 50 ℃, mixing ethylene glycol and 1, 4-butanediol and preheating to 60 ℃;

(2) respectively pumping the mixture A obtained in the step (1), 4' -diphenylmethane diisocyanate, ethylene glycol and 1, 4-butanediol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Comparative example 2

Preparing raw materials: 95 parts of 4, 4' -diphenylmethane diisocyanate, 45 parts of polyethylene glycol, 45 parts of poly-1, 2-propylene glycol, 10 parts of ethylene glycol, 10 parts of 1, 4-butanediol, 5 parts of 2, 5-di-tert-butylhydroquinone and 1.3 parts of dibutyltin maleate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding 2, 5-di-tert-butylhydroquinone and dibutyltin maleate into polyethylene glycol and poly-1, 2-propylene glycol, uniformly stirring, and preheating to 95 ℃ to obtain a mixture A; preheating 4, 4' -diphenylmethane diisocyanate to 50 ℃, mixing ethylene glycol and 1, 4-butanediol and preheating to 60 ℃;

(2) respectively pumping the mixture A obtained in the step (1), 4' -diphenylmethane diisocyanate, ethylene glycol and 1, 4-butanediol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

Comparative example 3

Preparing raw materials: 95 parts of 4, 4' -diphenylmethane diisocyanate, 45 parts of polyethylene glycol, 45 parts of poly-1, 2-propylene glycol, 10 parts of ethylene glycol, 10 parts of 1, 4-butanediol, 3 parts of octadecyl diethanolamine, 2 parts of 2, 5-di-tert-butyl hydroquinone and 1.3 parts of dibutyltin maleate.

The preparation method comprises the following steps:

(1) weighing the components according to the formula ratio, adding octadecyl diethanol amine, 2, 5-di-tert-butyl hydroquinone and dibutyl tin maleate into polyethylene glycol and poly (1, 2-propylene glycol), uniformly stirring, and preheating to 95 ℃ to obtain a mixture A; preheating 4, 4' -diphenylmethane diisocyanate to 50 ℃, mixing ethylene glycol and 1, 4-butanediol and preheating to 60 ℃;

(2) respectively pumping the mixture A obtained in the step (1), 4' -diphenylmethane diisocyanate, ethylene glycol and 1, 4-butanediol into a mixing head, and uniformly mixing to obtain a mixture B;

(3) continuously adding the mixture B obtained in the step (2) into a double-screw extruder, reacting and extruding, and granulating under water to obtain TPU master batches;

(4) and drying the TPU master batch, and then carrying out melt spinning to obtain the TPU monofilament.

The TPU monofilaments prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to various performance tests, the results of which are shown in Table 1.

TABLE 1

The method for testing the static value comprises the following steps: and testing the TPU monofilament by adopting an electronic constant tension conveying system, wherein the speed of an input roller is 100m/min, the speed of an output roller is 350m/min, and the voltage value of the generated static electricity is tested at the output roller by adopting a static potential tester.

The method for testing the electrostatic value after the aging resistance treatment comprises the following steps: irradiating with xenon arc light resistance tester at 45 deg.C and humidity of 65% RH for 168h (illumination of 42W/m)²) And then taking out the monofilament subjected to the aging resistance treatment, and testing the electrostatic value.

The method for testing the fracture strength after the aging resistance treatment comprises the following steps: irradiating with xenon arc light resistance tester at 45 deg.C and humidity of 65% RH for 168h (illumination of 42W/m)²) And then taking out the monofilament subjected to the aging resistance treatment, and testing the breaking strength.

As can be seen from Table 1, the TPU monofilaments prepared in the examples 1 to 4 have the breaking strength of more than 5.8N/mm, the elongation at break of more than 47.64 percent, the static value of less than 106V, good antistatic effect, the breaking strength of more than 4.7N/mm after aging treatment and certain aging resistance. The breaking strength of the example 3 is relatively poor, probably because the isocyanate used in the example 3 is tetramethylene diisocyanate and does not contain benzene ring, the breaking strength is poor, meanwhile, the electrostatic value is 85, which is better than that of the example 4, probably because the organic antistatic agent containing benzene ring used is not well compatible with the polyurethane system containing benzene ring, so that most of the antistatic agent exists on the surface, and the breaking strength of the TPU monofilament prepared in the example 3 is obviously reduced after aging treatment, and is reduced from 5.8N/mm to 4.7N/mm, and probably because the organic antistatic agent is poor in compatibility with the system. As can be seen from comparative example 1, when the organic antistatic agent in example 4 was replaced with the common aliphatic antistatic agent, octadecyl diethanol amine, the breaking strength of the prepared TPU monofilament was reduced, the elongation at break was increased, and the static value was reduced, which may be caused by the fact that octadecyl diethanol amine has poor compatibility with the system and is present on the surface of the monofilament, and in addition, the breaking strength after the aging treatment was significantly reduced, which may be caused by the fact that a structure similar to 2, 5-di-tert-butylhydroquinone antioxidant is not present in the system, resulting in the reduction of the aging resistance. As can be seen from comparative example 2, when the organic antistatic agent in example 4 was replaced with 2, 5-di-tert-butylhydroquinone, the breaking strength of the produced TPU monofilament increased, the elongation at break decreased somewhat, and the static value increased significantly, because of the lack of antistatic components in the system, while the breaking strength after aging resistance was still high. As can be seen from comparative example 3, when the organic antistatic agent in example 4 was replaced with octadecyl diethanolamine and 2, 5-di-tert-butylhydroquinone, both the antistatic agent component and the antioxidant component were present, the static value was slightly decreased, probably due to poor compatibility of the antistatic agent with the system, which was more present on the surface of the monofilament; the fracture strength is slightly reduced after the aging-resistant treatment, which shows that the 2, 5-di-tert-butyl hydroquinone plays a certain aging-resistant role; however, comparative example 3 shows a significant increase in the static value after the aging treatment, probably because the antistatic component on the surface of the monofilament was seriously deteriorated due to the aging treatment, thereby deteriorating the antistatic property after the aging treatment.

The present embodiment is merely illustrative and not restrictive, and various changes and modifications may be made by persons skilled in the art without departing from the scope of the present invention as defined in the appended claims. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of the claims.