CN113774507B - TPEE monofilament - Google Patents

Abstract

The application belongs to the technical field of monofilaments, and particularly relates to a TPEE monofilament, and a preparation method of the TPEE monofilament comprises the following steps: melt extrusion, cooling, drafting, heat setting and winding of the dried TPEE master batch through an extruder to obtain TPEE monofilaments; the TPEE master batch is an anti-ultraviolet modified TPEE master batch. The TPEE monofilament is prepared by adopting the anti-ultraviolet modified TPEE masterbatch, the anti-ultraviolet effect of the TPEE monofilament is improved by directly adopting the anti-ultraviolet modified TPEE masterbatch without adding a small-molecule ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent and the migration and precipitation problems in the long-term use process are effectively solved, and the prepared TPEE monofilament has long-term and excellent anti-ultraviolet effect.

Description

TPEE monofilament

Technical Field

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

Background

Thermoplastic polyester elastomers (TPEEs), also known as polyester rubbers, are a type of linear block copolymers containing hard segments of PBT (polybutylene terephthalate) polyester and soft segments of aliphatic polyesters or polyethers. TPEE has both excellent elasticity of rubber and easy processability of thermoplastic plastic, has adjustable hardness and free design, and is a new variety of thermoplastic elastomer which is attracting attention.

The polyether ester elastomer has excellent chemical stability under many different conditions, such as water mist, ozone, outdoor air aging and the like. Like most TPEs, degradation occurs under uv light, so uv protective aids should be added to the formulation for outdoor applications or articles exposed to sunlight.

Chinese patent document CN 104862815A discloses an antibacterial antistatic fiber based on polytrimethylene terephthalate, which improves the ultraviolet radiation protection function of the fiber by adding 0.5-2% of ultraviolet absorber to the matrix material during the mixing process. On the one hand, the ultraviolet absorber is added by blending, which may cause uneven dispersion of the ultraviolet absorber in the matrix, thereby being unfavorable for exerting the maximum ultraviolet resistance effect; on the other hand, the added ultraviolet absorbent is a small molecular ultraviolet absorbent such as a hydroxyphenyl triazine ultraviolet absorbent, a salicylic acid bisphenol A ester ultraviolet absorbent, 2-hydroxy-4-n-octoxy-benzophenone, 2, 4-dihydroxybenzophenone and the like, and the ultraviolet absorbent is easy to migrate and separate out in the use process, so that the ultraviolet absorbent cannot play a long-term ultraviolet resistance effect.

In view of this, there is a need to develop a TPEE monofilament to improve the problems caused by the relatively poor dispersion of the added small-molecule uv absorber and migration and precipitation that may occur during use.

Disclosure of Invention

In order to solve the problems, the application discloses a TPEE monofilament, wherein TPEE master batch used for preparing the TPEE monofilament is an anti-ultraviolet modified TPEE master batch, the anti-ultraviolet modified TPEE master batch is directly adopted, the anti-ultraviolet effect of the TPEE monofilament is improved without adding a small-molecule ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent and the migration and precipitation problems in the long-term use process are effectively solved, and the prepared TPEE monofilament has long-term and excellent anti-ultraviolet effect.

The application provides a TPEE monofilament, which adopts the following technical scheme:

a TPEE monofilament, the process of making the TPEE monofilament comprising: melt extrusion, cooling, drafting, heat setting and winding of the dried TPEE master batch through an extruder to obtain TPEE monofilaments; the TPEE master batch is an anti-ultraviolet modified TPEE master batch.

The anti-ultraviolet modified TPEE master batch is directly adopted, the anti-ultraviolet effect of the TPEE monofilament is improved without adding a small-molecule ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent and the migration and precipitation problems in the long-term use process are effectively solved, and the prepared TPEE monofilament has long-term and excellent anti-ultraviolet effect

Preferably, the preparation method of the ultraviolet resistant modified TPEE comprises the following steps:

(1) Dimethyl phthalate, 1, 4-butanediol, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and a catalyst are added into a reaction kettle, nitrogen is introduced to exhaust air, the temperature is raised to 185 ℃, and transesterification reaction is carried out to obtain a prepolymer;

(2) Heating the prepolymer to 260 ℃, adding polytetrahydrofuran ether glycol and a catalyst, carrying out reduced pressure polycondensation reaction, and carrying out water-cooling granulation on the polymer to obtain the ultraviolet-resistant modified TPEE master batch.

The reaction process is as follows:

preferably, the molar ratio of 1, 4-butanediol, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and dimethyl terephthalate in the step (1) is 1.8-2.0:0.1-0.3:1.

The 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester added according to the molar ratio can realize better anti-ultraviolet effect, and if the addition amount of the 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester is too small, the anti-ultraviolet effect is not obvious; if the addition amount of the 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester is too large, the ultraviolet-resistant effect is not obviously improved any more, and the excessive addition of the 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester also causes the obvious reduction of the breaking elongation of the monofilament and the insufficient toughness of the monofilament. And the proper addition is beneficial to increasing the strength of the monofilaments without greatly affecting the toughness of the monofilaments.

Preferably, the catalyst in the step (1) is magnesium acetate.

Preferably, in the step (1), the transesterification reaction is completed when the amount of the collected methanol reaches 80% of the theoretical value.

Preferably, the catalyst in the step (2) is tetrabutyl titanate.

Preferably, the pressure of the reduced pressure polycondensation reaction in the step (2) is 100Pa or less.

Preferably, the time of the reduced pressure polycondensation reaction in the above step (2) is 2 to 3 hours.

Preferably, the preparation method of the TPEE monofilament specifically comprises the following steps:

(1) Drying the ultraviolet resistant modified TPEE master batch for 4 hours at 100 ℃, and then adding the master batch into an extruder, wherein the temperature of a first area of the extruder is 220-240 ℃, the temperature of a second area of the extruder is 230-250 ℃, the temperature of a third area of the extruder is 230-250 ℃, the temperature of a fourth area of the extruder is 235-255 ℃, the temperature of a fifth area of the extruder is 235-255 ℃, the temperature of a flange is 230-250 ℃, the temperature of a seventh area of the extruder is 230-250 ℃, the temperature of a metering pump is 230-250 ℃, the temperature of a die head is 230-250 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 29-31m/min, the temperature of the hot water tank is 85-95 ℃, the second drawing speed is 111-113m/min, the temperature of the hot oven is 95-105 ℃, the third drawing speed is 118-120m/min, the temperature of the shaping oven is 170-180 ℃, and the fourth drawing speed is 122-124m/min.

The application has the following beneficial effects:

(1) The TPEE monofilament is prepared by adopting the anti-ultraviolet modified TPEE masterbatch, the anti-ultraviolet effect of the TPEE monofilament is improved by directly adopting the anti-ultraviolet modified TPEE masterbatch without adding a small-molecule ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent and the migration and precipitation problems in the long-term use process are effectively solved, and the prepared TPEE monofilament has long-term and excellent anti-ultraviolet effect.

(2) According to the preparation method, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester is used as a raw material, and is subjected to transesterification together with 1, 4-butanediol and dimethyl terephthalate to generate a prepolymer with a phenyl salicylate structure capable of absorbing ultraviolet rays on a main chain, and the phenyl salicylate structure is directly linked in the TPEE main chain in the ultraviolet resistant modified TPEE preparation mode unlike an ultraviolet absorbent added in a blending mode, so that the problem of dispersion of a micromolecular ultraviolet absorbent in a polymer is solved, and the phenyl salicylate structure is directly fixed on the main chain, so that the problem of failure caused by migration and precipitation of TPEE monofilaments in a long-term use process can be effectively avoided.

Detailed Description

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

Example 1

Preparation of ultraviolet resistant modified TPEE master batch:

(1) Adding 2kg of 1, 4-butanediol, 0.58kg of 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and 2.27kg of dimethyl terephthalate into a reaction kettle, adding a catalyst magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, and performing transesterification, wherein when the amount of the collected methanol reaches 80% of a theoretical value, the transesterification is finished to obtain a prepolymer;

(2) Heating the prepolymer to 230 ℃, adding 5.2kg of polytetrahydrofuran ether glycol and catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to below 100Pa, slowly heating to 260 ℃ at the same time, and carrying out polycondensation reaction for 2 hours to obtain the anti-ultraviolet modified TPEE master batch.

Preparation of TPEE monofilament:

(1) Drying the prepared anti-ultraviolet modified TPEE master batch for 4 hours at 100 ℃, then adding the master batch into an extruder, wherein the temperature of a first area of the extruder is 230 ℃, the temperature of a second area of the extruder is 240 ℃, the temperature of a third area of the extruder is 240 ℃, the temperature of a fourth area of the extruder is 245 ℃, the temperature of a fifth area of the extruder is 245 ℃, the temperature of a flange is 240 ℃, the temperature of a seventh area of the extruder is 240 ℃, the temperature of a metering pump is 240 ℃, the temperature of a die head is 240 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 29.8m/min, the hot water tank temperature is 90 ℃, the second drawing speed is 112m/min, the hot oven temperature is 100 ℃, the third drawing speed is 119m/min, the shaping oven temperature is 175 ℃, and the fourth drawing speed is 123m/min.

Example 2

Preparation of ultraviolet resistant modified TPEE master batch:

(1) Adding 2kg of 1, 4-butanediol, 0.91kg of 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and 2.39kg of dimethyl terephthalate into a reaction kettle, adding a catalyst magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, and performing transesterification, wherein when the amount of the collected methanol reaches 80% of a theoretical value, the transesterification is finished to obtain a prepolymer;

(2) Heating the prepolymer to 230 ℃, adding 5.5kg of polytetrahydrofuran ether glycol and catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to below 100Pa, slowly heating to 260 ℃ at the same time, and carrying out polycondensation reaction for 3 hours to obtain the anti-ultraviolet modified TPEE master batch.

Preparation of TPEE monofilament:

(1) Drying the prepared anti-ultraviolet modified TPEE master batch for 4 hours at 100 ℃, then adding the master batch into an extruder, wherein the temperature of a first area of the extruder is 235 ℃, the temperature of a second area of the extruder is 245 ℃, the temperature of a third area of the extruder is 245 ℃, the temperature of a fourth area of the extruder is 250 ℃, the temperature of a fifth area of the extruder is 250 ℃, the temperature of a flange is 245 ℃, the temperature of a seventh area of the extruder is 245 ℃, the temperature of a metering pump is 245 ℃, the temperature of a die head is 245 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 29m/min, the temperature of the hot water tank is 85 ℃, the second drawing speed is 111m/min, the temperature of the hot oven is 95 ℃, the third drawing speed is 118m/min, the temperature of the shaping oven is 170 ℃, and the fourth drawing speed is 122m/min.

Example 3

Preparation of ultraviolet resistant modified TPEE master batch:

(1) Adding 2kg of 1, 4-butanediol, 0.27kg of 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and 2.15kg of dimethyl terephthalate into a reaction kettle, adding a catalyst magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, and performing transesterification, wherein when the amount of the collected methanol reaches 80% of a theoretical value, the transesterification is finished to obtain a prepolymer;

(2) Heating the prepolymer to 230 ℃, adding 4.9kg of polytetrahydrofuran ether glycol and catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to below 100Pa, slowly heating to 260 ℃ at the same time, and carrying out polycondensation reaction for 2 hours to obtain the anti-ultraviolet modified TPEE master batch.

Preparation of TPEE monofilament:

(1) Drying the prepared anti-ultraviolet modified TPEE master batch for 4 hours at 100 ℃, then adding the master batch into an extruder, wherein the temperature of a first area of the extruder is 225 ℃, the temperature of a second area of the extruder is 235 ℃, the temperature of a third area of the extruder is 235 ℃, the temperature of a fourth area of the extruder is 240 ℃, the temperature of a fifth area of the extruder is 240 ℃, the temperature of a flange is 235 ℃, the temperature of a seventh area of the extruder is 235 ℃, the temperature of a metering pump is 235 ℃, the temperature of a die head is 235 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 30m/min, the temperature of a hot water tank is 95 ℃, the second drawing speed is 113m/min, the temperature of a hot oven is 105 ℃, the third drawing speed is 120m/min, the temperature of a shaping oven is 180 ℃, and the fourth drawing speed is 124m/min.

Comparative example 1

Preparation of TPEE master batch:

(1) Adding 2.21kg of 1, 4-butanediol and 2.27kg of dimethyl terephthalate into a reaction kettle, adding a catalyst magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, and performing transesterification, wherein when the amount of the collected methanol reaches 80% of a theoretical value, the transesterification is finished to obtain a prepolymer;

(2) Heating the prepolymer to 230 ℃, adding 5.2kg of polytetrahydrofuran ether glycol and catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to below 100Pa, slowly heating to 260 ℃ at the same time, and carrying out polycondensation reaction for 2 hours to obtain TPEE master batch.

Preparation of TPEE monofilament:

(1) Drying the prepared TPEE master batch for 4 hours at 100 ℃, then adding the master batch into an extruder, wherein the temperature of a first area of the extruder is 230 ℃, the temperature of a second area of the extruder is 240 ℃, the temperature of a third area of the extruder is 240 ℃, the temperature of a fourth area of the extruder is 245 ℃, the temperature of a fifth area of the extruder is 245 ℃, the temperature of a flange is 240 ℃, the temperature of a seventh area of the extruder is 240 ℃, the temperature of a metering pump is 240 ℃, the temperature of a die head is 240 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 29.8m/min, the hot water tank temperature is 90 ℃, the second drawing speed is 112m/min, the hot oven temperature is 100 ℃, the third drawing speed is 119m/min, the shaping oven temperature is 175 ℃, and the fourth drawing speed is 123m/min.

Comparative example 2

Preparation of TPEE master batch:

(1) Adding 2.21kg of 1, 4-butanediol and 2.27kg of dimethyl terephthalate into a reaction kettle, adding a catalyst magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, and performing transesterification, wherein when the amount of the collected methanol reaches 80% of a theoretical value, the transesterification is finished to obtain a prepolymer;

(2) Heating the prepolymer to 230 ℃, adding 5.2kg of polytetrahydrofuran ether glycol and catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to below 100Pa, slowly heating to 260 ℃ at the same time, and carrying out polycondensation reaction for 2 hours to obtain TPEE master batch.

Preparation of TPEE monofilament:

(1) Drying the prepared TPEE master batch for 4 hours at 100 ℃, then adding the master batch and 0.25kg of phenyl salicylate into an extruder, wherein the temperature of a first area of the extruder is 230 ℃, the temperature of a second area of the extruder is 240 ℃, the temperature of a third area of the extruder is 240 ℃, the temperature of a fourth area of the extruder is 245 ℃, the temperature of a fifth area of the extruder is 245 ℃, the temperature of a flange is 240 ℃, the temperature of a seventh area of the extruder is 240 ℃, the temperature of a metering pump is 240 ℃, the temperature of a die head is 240 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 29.8m/min, the hot water tank temperature is 90 ℃, the second drawing speed is 112m/min, the hot oven temperature is 100 ℃, the third drawing speed is 119m/min, the shaping oven temperature is 175 ℃, and the fourth drawing speed is 123m/min.

Various performance tests were conducted on the TPEE monofilaments prepared in examples 1-3 and comparative examples 1-2, and the test results are shown in table 1.

TABLE 1

The ultraviolet resistance treatment for 168 hours is to irradiate the TPEE monofilament in an ultraviolet aging test box by adopting UV-B ultraviolet light for 168 hours; the ultraviolet resistance treatment 336h is to irradiate the TPEE monofilament in an ultraviolet aging test box with UV-B ultraviolet light 336h.

As can be seen from Table 1, the breaking strength of the TPEE monofilament prepared in examples 1-3 of the present application is above 5.7N/mm, the breaking elongation is above 42.63%, the breaking strength after the ultraviolet-resistant treatment for 168 hours can be above 5.2N/mm, and the breaking strength after the ultraviolet-resistant treatment for 336 hours can still be above 4.6N/mm, which indicates that the TPEE monofilament prepared in the present application has good and long-term ultraviolet-resistant effect. As can be seen from comparative example 1, the breaking strength of the TPEE monofilament prepared in comparative example 1 was only 4.8N/mm, and the breaking elongation was 57.27%, probably because the phenyl salicylate structure was not introduced into the TPEE main chain, the overall segment strength was reduced, the breaking elongation was increased, and the breaking strength of the monofilament was already reduced to 3.1N/mm after the UV-resistant treatment for 168 hours, which was serious and the UV-resistant effect was poor. As can be seen from comparative example 2, although the comparative example 2 adopts a blending form to add the small molecule ultraviolet absorbent phenyl salicylate, the breaking strength and the breaking elongation are not greatly different from those of example 1, but the breaking strength is only slightly reduced after the ultraviolet resistant treatment for 168 hours, but the breaking strength is obviously reduced after the ultraviolet resistant treatment for 336 hours, probably because the phenyl salicylate is added as a blending, although the effect of resisting ultraviolet is certain, after a period of time, the small molecule phenyl salicylate is easy to migrate and separate out, so that the ultraviolet resistant effect is reduced.

The present embodiment is merely illustrative of the present application, and the present application is not limited thereto, and a worker can make various changes and modifications without departing from the scope of the technical idea of the present application. 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 claims.

Claims (7)

1. A TPEE monofilament characterized by: the preparation method of the TPEE monofilament comprises the following steps: melt extrusion, cooling, drafting, heat setting and winding of the dried TPEE master batch through an extruder to obtain TPEE monofilaments; the TPEE master batch is an anti-ultraviolet modified TPEE master batch;

the preparation method of the ultraviolet resistant modified TPEE master batch comprises the following steps:

(1) Dimethyl terephthalate, 1, 4-butanediol, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and a catalyst are added into a reaction kettle, nitrogen is introduced to exhaust air, the temperature is raised to 185 ℃, and transesterification reaction is carried out, so that a prepolymer is obtained;

(2) Heating the prepolymer to 260 ℃, adding polytetrahydrofuran ether glycol and a catalyst, carrying out reduced pressure polycondensation reaction, and carrying out water-cooling granulation on the polymer to obtain an ultraviolet-resistant modified TPEE master batch;

the reaction process is as follows:

the molar ratio of 1, 4-butanediol, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and dimethyl terephthalate in the step (1) is 1.8-2.0:0.1-0.3:1.

2. A TPEE monofilament as claimed in claim 1, wherein: the catalyst in the step (1) is magnesium acetate.

3. A TPEE monofilament as claimed in claim 1, wherein: in the step (1), the transesterification reaction is ended when the amount of the collected methanol reaches 80% of the theoretical value.

4. A TPEE monofilament as claimed in claim 1, wherein: the catalyst in the step (2) is tetrabutyl titanate.

5. A TPEE monofilament as claimed in claim 1, wherein: the pressure of the reduced pressure polycondensation reaction in the step (2) is 100Pa or less.

6. A TPEE monofilament as claimed in claim 1, wherein: the time of the decompression polycondensation reaction in the step (2) is 2-3h.

7. A TPEE monofilament as claimed in claim 1, wherein: the preparation method specifically comprises the following steps:

(1) Drying the ultraviolet resistant modified TPEE master batch for 4 hours at 100 ℃, and then adding the master batch into an extruder, wherein the temperature of a first area of the extruder is 220-240 ℃, the temperature of a second area of the extruder is 230-250 ℃, the temperature of a third area of the extruder is 230-250 ℃, the temperature of a fourth area of the extruder is 235-255 ℃, the temperature of a fifth area of the extruder is 235-255 ℃, the temperature of a flange is 230-250 ℃, the temperature of a seventh area of the extruder is 230-250 ℃, the temperature of a metering pump is 230-250 ℃, the temperature of a die head is 230-250 ℃, and the temperature of a cold water tank is room temperature;

(2) Drawing, heat setting and rolling the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first drawing speed is 29-31m/min, the temperature of the hot water tank is 85-95 ℃, the second drawing speed is 111-113m/min, the temperature of the hot oven is 95-105 ℃, the third drawing speed is 118-120m/min, the temperature of the shaping oven is 170-180 ℃, and the fourth drawing speed is 122-124m/min.