CN113774507A - TPEE monofilament - Google Patents
TPEE monofilament Download PDFInfo
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- CN113774507A CN113774507A CN202111085428.7A CN202111085428A CN113774507A CN 113774507 A CN113774507 A CN 113774507A CN 202111085428 A CN202111085428 A CN 202111085428A CN 113774507 A CN113774507 A CN 113774507A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
Abstract
The application belongs to the technical field of monofilaments, and particularly relates to a TPEE monofilament, which is prepared by the following steps: melting and extruding the dried TPEE master batch through an extruder, cooling, drafting, heat setting and rolling to obtain TPEE monofilament; the TPEE master batch is an anti-ultraviolet modified TPEE master batch. According to the TPEE monofilament, the TPEE master batch used for preparing the TPEE monofilament is the ultraviolet-resistant modified TPEE master batch, the ultraviolet-resistant modified TPEE master batch is directly adopted, the ultraviolet-resistant effect of the TPEE monofilament is not required to be improved by adding a micromolecular ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent is effectively solved, the migration and precipitation problems in the long-term use process are solved, and the prepared TPEE monofilament has long-term and excellent ultraviolet-resistant effect.
Description
Technical Field
The application belongs to the technical field of monofilaments, and particularly relates to a TPEE monofilament.
Background
Thermoplastic polyester elastomer (TPEE), also called polyester rubber, is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segments and aliphatic polyester or polyether soft segments. TPEE has excellent elasticity of rubber and easy processability of thermoplastic plastics, has adjustable hardness and free design, and is a new variety which is concerned by the thermoplastic elastomer.
The polyether ester elastomer has excellent chemical stability under various conditions, such as water mist, ozone, outdoor atmospheric aging and the like. Like most TPEs, degrade under the influence of ultraviolet light, and therefore, for outdoor applications or conditions where the article is exposed to sunlight, an ultraviolet light protection aid should be added to the formulation.
Chinese patent document CN 104862815 a discloses an antibacterial and 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 base material during the compounding process. On one hand, the ultraviolet absorbent is added by blending, which may cause uneven dispersion of the ultraviolet absorbent in the matrix, thus being not beneficial to 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-octyloxy-benzophenone, 2, 4-dihydroxy-benzophenone and the like, and is easy to migrate and precipitate in the use process, so that the long-term ultraviolet resistance effect cannot be achieved.
In view of the above, there is a need to develop TPEE monofilaments that can solve the problems caused by the relatively poor dispersion effect of small-molecular uv absorbers and the migration and deposition 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 ultraviolet-resistant modified TPEE master batch, the ultraviolet-resistant modified TPEE master batch is directly adopted, the ultraviolet-resistant effect of the TPEE monofilament is not required to be improved by adding a micromolecular ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent is effectively solved, the migration and precipitation problems in the long-term use process are solved, and the prepared TPEE monofilament is favorable for having a long-term and excellent ultraviolet-resistant effect.
The application provides a TPEE monofilament, which adopts the following technical scheme:
a TPEE monofilament is prepared by the following steps: melting and extruding the dried TPEE master batch through an extruder, cooling, drafting, heat setting and rolling to obtain TPEE monofilament; the TPEE master batch is an anti-ultraviolet modified TPEE master batch.
The uvioresistant modified TPEE master batch is directly adopted, the uvioresistant effect of TPEE monofilament is improved without adding a micromolecular ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent is effectively solved, the migration and precipitation problems in the long-term use process are effectively solved, and the prepared TPEE monofilament has long-term and excellent uvioresistant effect
Preferably, the preparation method of the anti-ultraviolet modified TPEE comprises the following steps:
(1) adding dimethyl phthalate, 1, 4-butanediol, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and a catalyst into a reaction kettle, introducing nitrogen to exhaust air, heating to 185 ℃, and performing ester exchange reaction to obtain a prepolymer;
(2) and 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 anti-ultraviolet modified TPEE master batch.
The reaction process is as follows:
preferably, the molar ratio of 1, 4-butanediol, 4-hydroxyphenyl 2, 4-dihydroxybenzoate and dimethyl terephthalate in step (1) above is 1.8-2.0:0.1-0.3: 1.
The 2, 4-dihydroxy-4-hydroxyphenyl benzoate is added according to the molar ratio to realize better anti-ultraviolet effect, and if the addition amount of the 2, 4-dihydroxy-4-hydroxyphenyl benzoate 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 much, not only the ultraviolet resistance effect is not obviously improved, but also the elongation at break of the monofilament is obviously reduced and the toughness of the monofilament is insufficient due to the double benzene ring structure of the 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester. And the addition of a proper amount is beneficial to increasing the strength of the monofilament while not greatly influencing the toughness of the monofilament.
Preferably, the catalyst in the step (1) is magnesium acetate.
Preferably, in the step (1), the transesterification reaction is terminated when the amount of 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 for the polycondensation reaction under reduced pressure in the above step (2) is 2 to 3 hours.
Preferably, the preparation method of the TPEE monofilament comprises:
(1) drying the anti-ultraviolet modified TPEE master batch at 100 ℃ for 4h, then adding the dried anti-ultraviolet modified TPEE master batch into an extruder, wherein the temperature of a first zone of the extruder is 220-;
(2) drawing, heat setting and winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 29-31m/min, the temperature of the hot water tank is 85-95 ℃, the second pulling speed is 111-113m/min, the temperature of the hot drying oven is 95-105 ℃, the third pulling speed is 118-120m/min, the temperature of the setting drying oven is 170-180 ℃, and the fourth pulling speed is 122-124 m/min.
The application has the following beneficial effects:
(1) according to the TPEE monofilament, the TPEE master batch used for preparing the TPEE monofilament is the ultraviolet-resistant modified TPEE master batch, the ultraviolet-resistant modified TPEE master batch is directly adopted, the ultraviolet-resistant effect of the TPEE monofilament is not required to be improved by adding a micromolecular ultraviolet absorbent, the dispersion problem of the ultraviolet absorbent is effectively solved, the migration and precipitation problems in the long-term use process are solved, and the prepared TPEE monofilament has long-term and excellent ultraviolet-resistant effect.
(2) According to the preparation method, 2, 4-dihydroxy-benzoic acid-4-hydroxyphenyl ester is used as a raw material and is subjected to ester exchange reaction 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 prepolymer is different from an ultraviolet absorbent added in a mixed form.
Detailed Description
The present application will now be described in further detail with reference to examples.
Example 1
Preparing the anti-ultraviolet 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 of magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, carrying out transesterification, and finishing the transesterification when the amount of collected methanol reaches 80% of a theoretical value to obtain a prepolymer;
(2) heating the prepolymer to 230 ℃, adding 5.2kg of polytetrahydrofuran ether glycol and a catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to be below 100Pa, slowly heating to 260 ℃, and carrying out polycondensation reaction for 2 hours to obtain the ultraviolet-resistant modified TPEE master batch.
Preparation of TPEE monofilament:
(1) drying the prepared uvioresistant modified TPEE master batch at 100 ℃ for 4 hours, then adding the dried uvioresistant modified TPEE master batch into an extruder, wherein the temperature of a first zone of the extruder is 230 ℃, the temperature of a second zone of the extruder is 240 ℃, the temperature of a third zone of the extruder is 240 ℃, the temperature of a fourth zone of the extruder is 245 ℃, the temperature of a fifth zone of the extruder is 245 ℃, the temperature of a flange is 240 ℃, the temperature of a seventh zone 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 winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 29.8m/min, the temperature of the hot water tank is 90 ℃, the second pulling speed is 112m/min, the temperature of the hot oven is 100 ℃, the third pulling speed is 119m/min, the temperature of the setting oven is 175 ℃, and the fourth pulling speed is 123 m/min.
Example 2
Preparing the anti-ultraviolet 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 of magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, carrying out transesterification, and finishing the transesterification when the amount of collected methanol reaches 80% of a theoretical value to obtain a prepolymer;
(2) heating the prepolymer to 230 ℃, adding 5.5kg of polytetrahydrofuran ether glycol and a catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to be below 100Pa, slowly heating to 260 ℃, and carrying out polycondensation reaction for 3 hours to obtain the ultraviolet-resistant modified TPEE master batch.
Preparation of TPEE monofilament:
(1) drying the prepared uvioresistant modified TPEE master batch at 100 ℃ for 4 hours, then adding the dried uvioresistant modified TPEE master batch into an extruder, wherein the temperature of a first zone of the extruder is 235 ℃, the temperature of a second zone of the extruder is 245 ℃, the temperature of a third zone of the extruder is 245 ℃, the temperature of a fourth zone of the extruder is 250 ℃, the temperature of a fifth zone of the extruder is 250 ℃, the temperature of a flange is 245 ℃, the temperature of a seventh zone 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 winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 29m/min, the temperature of a hot water tank is 85 ℃, the second pulling speed is 111m/min, the temperature of a hot oven is 95 ℃, the third pulling speed is 118m/min, the temperature of a setting oven is 170 ℃, and the fourth pulling speed is 122 m/min.
Example 3
Preparing the anti-ultraviolet 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 of magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, carrying out transesterification, and finishing the transesterification when the amount of collected methanol reaches 80% of a theoretical value to obtain a prepolymer;
(2) heating the prepolymer to 230 ℃, adding 4.9kg of polytetrahydrofuran ether glycol and a catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to be below 100Pa, slowly heating to 260 ℃, and carrying out polycondensation reaction for 2 hours to obtain the ultraviolet-resistant modified TPEE master batch.
Preparation of TPEE monofilament:
(1) drying the prepared ultraviolet-resistant modified TPEE master batch at 100 ℃ for 4 hours, then adding the dried ultraviolet-resistant modified TPEE master batch into an extruder, wherein the temperature of a first zone of the extruder is 225 ℃, the temperature of a second zone of the extruder is 235 ℃, the temperature of a third zone of the extruder is 235 ℃, the temperature of a fourth zone of the extruder is 240 ℃, the temperature of a fifth zone of the extruder is 240 ℃, the temperature of a flange of the extruder is 235 ℃, the temperature of a seventh zone of the extruder is 235 ℃, the temperature of a metering pump of the extruder is 235 ℃, the temperature of a die head of the extruder is 235 ℃, and the temperature of a cold water tank of the extruder is room temperature;
(2) drawing, heat setting and winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 30m/min, the temperature of the hot water tank is 95 ℃, the second pulling speed is 113m/min, the temperature of the hot oven is 105 ℃, the third pulling speed is 120m/min, the temperature of the setting oven is 180 ℃, and the fourth pulling speed is 124 m/min.
Comparative example 1
Preparing TPEE master batch:
(1) adding 2.21kg of 1, 4-butanediol and 2.27kg of dimethyl terephthalate into a reaction kettle, adding a catalyst of magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, performing ester exchange reaction, and finishing the ester exchange reaction when the amount of collected methanol reaches 80% of a theoretical value to obtain a prepolymer;
(2) heating the prepolymer to 230 ℃, adding 5.2kg of polytetrahydrofuran ether glycol and a catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to be below 100Pa, slowly heating to 260 ℃, and carrying out polycondensation reaction for 2 hours to obtain the TPEE master batch.
Preparation of TPEE monofilament:
(1) drying the prepared TPEE master batch at 100 ℃ for 4 hours, adding the dried TPEE master batch into an extruder, wherein the temperature of a first zone of the extruder is 230 ℃, the temperature of a second zone of the extruder is 240 ℃, the temperature of a third zone of the extruder is 240 ℃, the temperature of a fourth zone of the extruder is 245 ℃, the temperature of a fifth zone of the extruder is 245 ℃, the temperature of a flange is 240 ℃, the temperature of a seventh zone 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 winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 29.8m/min, the temperature of the hot water tank is 90 ℃, the second pulling speed is 112m/min, the temperature of the hot oven is 100 ℃, the third pulling speed is 119m/min, the temperature of the setting oven is 175 ℃, and the fourth pulling speed is 123 m/min.
Comparative example 2
Preparing TPEE master batch:
(1) adding 2.21kg of 1, 4-butanediol and 2.27kg of dimethyl terephthalate into a reaction kettle, adding a catalyst of magnesium acetate, introducing nitrogen to exhaust air, heating to 185 ℃, performing ester exchange reaction, and finishing the ester exchange reaction when the amount of collected methanol reaches 80% of a theoretical value to obtain a prepolymer;
(2) heating the prepolymer to 230 ℃, adding 5.2kg of polytetrahydrofuran ether glycol and a catalyst tetrabutyl titanate, closing nitrogen, vacuumizing until the pressure in the kettle is reduced to be below 100Pa, slowly heating to 260 ℃, and carrying out polycondensation reaction for 2 hours to obtain the TPEE master batch.
Preparation of TPEE monofilament:
(1) drying the prepared TPEE master batch at 100 ℃ for 4 hours, adding the dried TPEE master batch and 0.25kg of phenyl salicylate into an extruder together, wherein the temperature of a first zone of the extruder is 230 ℃, the temperature of a second zone of the extruder is 240 ℃, the temperature of a third zone of the extruder is 240 ℃, the temperature of a fourth zone of the extruder is 245 ℃, the temperature of a fifth zone of the extruder is 245 ℃, the temperature of a flange of the extruder is 240 ℃, the temperature of a seventh zone of the extruder is 240 ℃, the temperature of a metering pump of the extruder is 240 ℃, the temperature of a die head of the extruder is 240 ℃, and the temperature of a cold water tank of the extruder is room temperature;
(2) drawing, heat setting and winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 29.8m/min, the temperature of the hot water tank is 90 ℃, the second pulling speed is 112m/min, the temperature of the hot oven is 100 ℃, the third pulling speed is 119m/min, the temperature of the setting oven is 175 ℃, and the fourth pulling speed is 123 m/min.
The TPEE monofilaments prepared in examples 1-3 and comparative examples 1-2 were subjected to various performance tests, and the test results are shown in table 1.
TABLE 1
The ultraviolet-resistant treatment for 168 hours is to irradiate the TPEE monofilament for 168 hours in an ultraviolet aging test box by adopting UV-B ultraviolet; the ultraviolet resistance treatment is 336h, and TPEE monofilament is irradiated for 336h by adopting UV-B ultraviolet light in an ultraviolet aging test box.
As can be seen from Table 1, the breaking strength of the TPEE monofilament prepared in the embodiments 1 to 3 is more than 5.7N/mm, the breaking elongation is more than 42.63%, the breaking strength can reach more than 5.2N/mm after ultraviolet treatment for 168 hours, and the breaking strength can still reach more than 4.6N/mm after ultraviolet treatment for 336 hours, which indicates that the TPEE monofilament prepared in the embodiments has good and long-lasting ultraviolet resistance. As can be seen from comparative example 1, the breaking strength of the TPEE monofilament prepared in comparative example 1 is only 4.8N/mm, the breaking elongation is 57.27%, probably because no phenyl salicylate structure is introduced into the TPEE main chain, the integral chain segment strength is reduced, the breaking elongation is increased, and because no phenyl salicylate structure with anti-ultraviolet performance is introduced, the breaking strength of the monofilament is already reduced to 3.1N/mm after ultraviolet treatment for 168 hours, the reduction is serious, and the anti-ultraviolet effect is poor. As can be seen from comparative example 2, although the small-molecule phenyl salicylate used as the ultraviolet absorber in comparative example 2 is added in a blending manner, the breaking strength and the elongation at break are not greatly different from those of example 1, and the breaking strength is only slightly reduced after 168 hours of ultraviolet resistance treatment, but the breaking strength is obviously reduced after 336 hours of ultraviolet resistance treatment, probably because the small-molecule phenyl salicylate is added in a blending manner, although a certain ultraviolet resistance effect can be achieved, after a certain period of time, the small-molecule phenyl salicylate is easy to migrate and separate out, so that the ultraviolet resistance effect is reduced.
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.
Claims (9)
1. A TPEE monofilament characterized in that: the preparation method of the TPEE monofilament comprises the following steps: melting and extruding the dried TPEE master batch through an extruder, cooling, drafting, heat setting and rolling to obtain TPEE monofilament; the TPEE master batch is an anti-ultraviolet modified TPEE master batch.
2. The TPEE monofilament of claim 1 wherein: the preparation method of the ultraviolet-resistant modified TPEE master batch comprises the following steps:
(1) adding dimethyl phthalate, 1, 4-butanediol, 2, 4-dihydroxybenzoic acid-4-hydroxyphenyl ester and a catalyst into a reaction kettle, introducing nitrogen to exhaust air, heating to 185 ℃, and performing ester exchange reaction to obtain a prepolymer;
(2) and 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 anti-ultraviolet modified TPEE master batch.
3. The TPEE monofilament of claim 2 wherein: in the step (1), the molar ratio of 1, 4-butanediol, 4-hydroxyphenyl 2, 4-dihydroxybenzoate and dimethyl terephthalate is 1.8-2.0:0.1-0.3: 1.
4. The TPEE monofilament of claim 2 wherein: the catalyst in the step (1) is magnesium acetate.
5. The TPEE monofilament of claim 2 wherein: in the step (1), when the amount of the collected methanol reaches 80% of the theoretical value, the transesterification reaction is terminated.
6. The TPEE monofilament of claim 2 wherein: the catalyst in the step (2) is tetrabutyl titanate.
7. The TPEE monofilament of claim 2 wherein: the pressure of the reduced-pressure polycondensation reaction in the step (2) is 100Pa or less.
8. The TPEE monofilament of claim 1 wherein: the time of the decompression polycondensation reaction in the step (2) is 2-3 h.
9. The TPEE monofilament of claim 1 wherein: the preparation method specifically comprises the following steps:
(1) drying the anti-ultraviolet modified TPEE master batch at 100 ℃ for 4h, then adding the dried anti-ultraviolet modified TPEE master batch into an extruder, wherein the temperature of a first zone of the extruder is 220-;
(2) drawing, heat setting and winding the filaments extruded in the step (1) to obtain TPEE monofilaments, wherein the specific conditions are as follows: the first pulling speed is 29-31m/min, the temperature of the hot water tank is 85-95 ℃, the second pulling speed is 111-113m/min, the temperature of the hot drying oven is 95-105 ℃, the third pulling speed is 118-120m/min, the temperature of the setting drying oven is 170-180 ℃, and the fourth pulling speed is 122-124 m/min.
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| DE2921846A1 (en) * | 1979-05-29 | 1980-12-11 | Du Pont | Oxidation resistant co:polyetherester compsn. - contg. phenolic antioxidant and having chemically bound hindered amine photostabiliser units |
| KR910009761A (en) * | 1989-11-21 | 1991-06-28 | 이수환 | Method for producing block copolymer of polyester |
| JPH10251389A (en) * | 1997-03-17 | 1998-09-22 | Asahi Chem Ind Co Ltd | Polyether-ester polycondensate |
| CN1249787A (en) * | 1997-03-04 | 2000-04-05 | 纳幕尔杜邦公司 | UV resistant elastomeric monofilament |
| CN1254731A (en) * | 1998-11-25 | 2000-05-31 | 莫顿国际股份有限公司 | Latent thiol stabilizer for improving ageing nature of transparent composition containing helogen polymer |
| CN103709612A (en) * | 2013-11-29 | 2014-04-09 | 金发科技股份有限公司 | Ultraviolet light-resistant thermoplastic polyester elastomer and its preparation method and use |
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2021
- 2021-09-16 CN CN202111085428.7A patent/CN113774507B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2921846A1 (en) * | 1979-05-29 | 1980-12-11 | Du Pont | Oxidation resistant co:polyetherester compsn. - contg. phenolic antioxidant and having chemically bound hindered amine photostabiliser units |
| KR910009761A (en) * | 1989-11-21 | 1991-06-28 | 이수환 | Method for producing block copolymer of polyester |
| CN1249787A (en) * | 1997-03-04 | 2000-04-05 | 纳幕尔杜邦公司 | UV resistant elastomeric monofilament |
| JPH10251389A (en) * | 1997-03-17 | 1998-09-22 | Asahi Chem Ind Co Ltd | Polyether-ester polycondensate |
| CN1254731A (en) * | 1998-11-25 | 2000-05-31 | 莫顿国际股份有限公司 | Latent thiol stabilizer for improving ageing nature of transparent composition containing helogen polymer |
| CN103709612A (en) * | 2013-11-29 | 2014-04-09 | 金发科技股份有限公司 | Ultraviolet light-resistant thermoplastic polyester elastomer and its preparation method and use |
Non-Patent Citations (1)
| Title |
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| 周静宜: ""TPEE纺丝成型及纤维结构性能"" * |
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