CN101100768A - Method for preparing nano TiO2 polyester ether elastic fiber - Google Patents
Method for preparing nano TiO2 polyester ether elastic fiber Download PDFInfo
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- CN101100768A CN101100768A CNA2007100438073A CN200710043807A CN101100768A CN 101100768 A CN101100768 A CN 101100768A CN A2007100438073 A CNA2007100438073 A CN A2007100438073A CN 200710043807 A CN200710043807 A CN 200710043807A CN 101100768 A CN101100768 A CN 101100768A
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Abstract
The invention relates to nanometer TiO2 polyether ester elastic fiber manufacturing method. It includes the following steps: preparing nanometer TiO2/1, 4-butanediol system that replacing the nanometer TiO2 by 1,4-butanediol as dispersion medium and vacuum pumping at 70-80 deg.C; preparing polyether ester elastic body that using dimethyl terephthalate, polytetrahydrofuran ether glycol, 1, 4-butanediol as material, adding 0.1-2.0% mass fraction nanometer TiO2, vacuum pumping at 50-100 deg.C, ester interchange reacting at 180-200 deg.C, condensation polymer reacting for 3-4h at 230-250 deg.C under 80Pa; melt spinning. This technology is simple. In addition, the prepared fiber has even nanometer particle disperse, good elastic recovery, low cost, suits for industrialization production.
Description
Technical field
The present invention relates to improve the preparation field of polyester ether elastic fiber, be specifically related to a kind of nano-TiO
2The preparation method of polyester ether elastic fiber.
Background technology
Thermoplastic polyether ester elastomer (TPEE) is the new crystalline thermoplastic elastomer of a class that occurs after s-B-S (S-B-S) thermoplastic elastomer (TPE), and it is a block polymer, and its macromolecular chain is formed by hard section and soft section.Its hard segment is a crystalline aromatic polyester, and soft chain segment is unformed aliphatic polyether or polyester.This line style segmented copolymer is micro phase separation structure, and the crystalline phase microcell by the hard segment polyester is formed plays the physical crosslinking effect, and soft chain segment polyethers or polyester molecule are fettered and are dispersed in the amorphous phase of soft section formation.Because crosslinked is the physical action that relies on crystalline phase, so be thermoplastic.
Utilize the elastomer of polyether ester melt spinning preparation, advantage such as it is simple to have a spinning technique, and production cost is low.But, the still too late spandex of the elastic recovery rate of this fiber, thus limited its application.
The method of improving the elastic recovery rate of TPEE body fiber generally has following several: the process conditions of a, change spinning and back processing, as spinneret draft ratio, after-drawing multiple and temperature, heat-setting time and temperature etc.; B, make more hard section crystal region is arranged in the fiber,, adopt PBT and TPEE co-blended spinning to pin down soft section big intermolecular slippage; C, interpolation nucleator.These methods all are that attempt utilization adds strong section physical crosslinking raising elastic recovery rate, still, and fail to solve well the problem that it is used.
The domestic researcher of having passes through at 4GT-PTMO
2000During polymerization, add polyfunctionality hydroxyl functional laurene (PM) or hydroxyl functional polybutadiene (PBD) and participate in copolymerization, obtain elasticity raising, slight crosslinked polyetherester copolymer.Patent (publication number: CN1480570A) disclose a kind of elastic polyester ether elastic fiber that improved, it by dicarboxylic acids, dihydroxylic alcohols, two or more number-average molecular weight 1000～4000 polyalkylene ether glycols copolymerization, and added 0.05～2% composite antioxidant and be prepared from, this polyester elastomer has good physics and mechanical performance, as toughness, fatigue resistance, ABRASION RESISTANCE etc.
Nano-TiO
2Have the super parents' character in high surface energy and surface, be dispersed in the TiO in the polymeric matrix
2Meeting adsorpting polymerization thing macromolecular chain is to reduce the surface energy of self.This type of effect is equal to TiO
2As the physical crosslinking point, can between macromolecular chain, form quasi-network structure, improve the elastic recovery of fiber thus.
Summary of the invention
Technical problem to be solved by this invention provides a kind of nano-TiO
2The preparation method of polyester ether elastic fiber, this method technology is easy, and nano particle is uniformly dispersed in the fiber of preparation, elastic recovery is greatly improved, and is fit to suitability for industrialized production.
A kind of nano-TiO of the present invention
2The preparation method of polyester ether elastic fiber comprises the following steps:
(1) nano-TiO
2/ 1, the preparation of 4-butanediol system
With the nano-TiO of Rotary Evaporators with aqueous dispersion
2Be replaced into 1,4-butanediol (BD) is a decentralized medium, preparation stabilized nano TiO
2/ BD system, under the condition of vacuumizing, temperature 70-80 ℃;
(2) preparation of polyester elastomer (situ aggregation method)
The a ester exchange reaction
With dimethyl terephthalate (DMT) (DMT), PTMG (PTM0), 1,4-butanediol BD is a raw material, adds mass fraction and be the nano-TiO of gained in 0.1～2.0% the step (1)
2Participate in copolymerization, vacuumize under 50-100 ℃ earlier and dewater, be warming up to 180-200 ℃ then and carry out ester exchange reaction, that treats that the methyl alcohol quantity of distillate is about theoretical amount thinks more than 90% that ester exchange reaction is complete;
The b polycondensation reaction
Elevated temperature is removed the liquid micromolecule earlier to about 230-250 ℃ under the low vacuum condition, guaranteeing vacuum less than under the 80Pa then, and polycondensation reaction 3-4h in the nitrogen protection bottom discharge, obtains polyester elastomer at last;
(3) melt spinning
With the polyester elastomer melt spinning of step (2) preparation, spinning speed 800-1000m/min obtains the modified polyether ester elastomer.
Described water dispersion nano TiO
2, Japanese Ishihara Sangyo company produces, primary particle size 7nm; Dimethyl terephthalate (DMT) (DMT), technical grade; PTMG (PTMO), technical grade, MIT produces; 1,4-butanediol (BD), chemical pure, reagent one factory in Shanghai produces.
In the step (2) in the prepared polyester elastomer soft section the preferred molecular mass of PTMEG be 2000g/mol, and account for 60～80% of polyether ester gross weight; Described nano-TiO
2Select 0.1～2.0% of the reasonable opinion of mass ratio output.
TiO in the polyester elastomer described in the step (2)
2Evenly disperse with nano-scale, and the polymer molecule quality need reach the requirement of spinning fibre, promptly inherent viscosity [η] is greater than 1.2dL/g.The test of inherent viscosity: in the metacresol solvent, (Φ 0.7～0.8mm) measures with Ubbelohde viscometer down in 30 ± 0.1 ℃.
The present invention adopts aqueous dispersion TiO
2System is TiO
2The source, by displacement method with TiO
2Be dispersed in the butanediol, this method is than directly adopting powdery TiO
2Be dispersed in and realize TiO in the butanediol easily
2Even dispersion.
The preparation method of polymer/inorganic nanometer particle system has sol-gel process, blending method, situ aggregation method and intercalation compounding etc., how to improve the dispersiveness of nano particle in polymer and be the emphasis and the difficult point of preparation nano composite material, the present invention adopts the i.e. adding TiO in polyether ester synthetic of situ aggregation method
2, when finishing polymerization, realize TiO
2The dispersion size of nano particle has been controlled in even dispersion in polymer effectively, and does not increase operation.
TiO in the polyester elastomer
2Dispersed method of testing: with the polyether ester brittle failure, adopt TiO in the JSM-5600LV type scanning electron microscopic observation section with liquid nitrogen
2The size and the pattern that disperse; The test of polyester ether elastic fiber elastic recovery: survey the stretching resilience with AGS-500ND type versatile material testing machine.The result shows: nano-TiO
2Optimum addition be 0.3～1.0%, high-load TiO
2In the polyether ester matrix, can cause difficulties in dispersion, agglomeration occur; Polyester ether elastic fiber elastic recovery rate in this content range can reach (100% fixed elongation) more than 98%
Nano-TiO of the present invention
2The elastic recovery that improves polyester ether elastic fiber is a kind of new method, has advantages such as technology is easy, fiber size is even, bases oneself upon existing industrial equipment.In the polyether ester system of situ aggregation method preparation, be between 0.3～1.0% at mass fraction, TiO
2Be evenly dispersed in the polyester elastomer with nano-scale., chemical property good with the fibrous elasticity recoverability that above-mentioned material is spun into stablized.
Description of drawings
Fig. 1 0.5%nano-TiO
2The SEM photo of/PEE system section
Fig. 2 1.5%nano-TiO
2The SEM photo of/PEE system section
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With dimethyl terephthalate (DMT) (DMT), PTMG (PTMO), 1,4-butanediol (BD) is a raw material, and the adding mass fraction is 0.3% nano-TiO
2Participate in copolymerization, vacuumize under 100 ℃ earlier and dewater, be warming up to 200 ℃ then and carry out ester exchange reaction, that treats that the methyl alcohol quantity of distillate is about theoretical amount thinks more than 90% that ester exchange reaction is complete; About elevated temperature to 250 ℃, remove the liquid micromolecule earlier under the low vacuum condition, guaranteeing vacuum less than under the 80Pa then, polycondensation reaction 3h in the nitrogen protection bottom discharge, obtains polyester elastomer at last;
With above-mentioned polyester elastomer melt spinning, spinning speed is 1000m/min, obtains polyester ether elastic fiber.Recording its elastic recovery rate with the versatile material testing machine is (100% fixed elongation) more than 97%, more than 84% (300% fixed elongation).
Embodiment 2
With dimethyl terephthalate (DMT) (DMT), PTMG (PTMO), 1,4-butanediol (BD) is a raw material, and the adding mass fraction is 0.5% nano-TiO
2Participate in copolymerization, vacuumize under 100 ℃ earlier and dewater, be warming up to 200 ℃ then and carry out ester exchange reaction, that treats that the methyl alcohol quantity of distillate is about theoretical amount thinks more than 90% that ester exchange reaction is complete; About elevated temperature to 250 ℃, remove the liquid micromolecule earlier under the low vacuum condition, guaranteeing vacuum less than under the 80Pa then, polycondensation reaction 3.5h in the nitrogen protection bottom discharge, obtains polyester elastomer at last;
With above-mentioned polyester elastomer melt spinning, spinning speed is 800m/min, obtains polyester ether elastic fiber.Recording its elastic recovery rate with the versatile material testing machine is (100% fixed elongation) more than 97%, more than 86% (300% fixed elongation).
Embodiment 3
With dimethyl terephthalate (DMT) (DMT), PTMG (PTMO), 1,4-butanediol (BD) is a raw material, and the adding mass fraction is 1.0% nano-TiO
2Participate in copolymerization, vacuumize under 100 ℃ earlier and dewater, be warming up to 200 ℃ then and carry out ester exchange reaction, that treats that the methyl alcohol quantity of distillate is about theoretical amount thinks more than 90% that ester exchange reaction is complete; About elevated temperature to 250 ℃, remove the liquid micromolecule earlier under the low vacuum condition, guaranteeing vacuum less than under the 80Pa then, polycondensation reaction 4h in the nitrogen protection bottom discharge, obtains polyester elastomer at last;
With above-mentioned polyester elastomer melt spinning, spinning speed is 1000m/min, obtains polyester ether elastic fiber.Recording its elastic recovery rate with the versatile material testing machine is (100% fixed elongation) more than 97%, more than 88% (300% fixed elongation).
Claims (7)
1. nano-TiO
2The preparation method of polyester ether elastic fiber comprises the following steps:
(1) nano-TiO
2/ 1, the preparation of 4-butanediol system
Use Rotary Evaporators, under the condition of vacuumizing with the nano-TiO of aqueous dispersion
2Be replaced into 1, the 4-butanediol is a decentralized medium, preparation stabilized nano TiO
2/ BD system, temperature 70-80 ℃;
(2) preparation of polyester elastomer
The a ester exchange reaction
With dimethyl terephthalate (DMT), PTMG, 1, the 4-butanediol is a raw material, adds mass fraction and be the nano-TiO of gained in 0.1～2.0% the step (1)
2Participate in copolymerization, elder generation vacuumizes under 50-100 ℃ and dewaters, and is warming up to 180-200 ℃ then and carries out ester exchange reaction;
The b polycondensation reaction
Elevated temperature is removed the liquid micromolecule earlier to about 230-250 ℃ under the low vacuum condition, guaranteeing vacuum less than under the 80Pa then, and polycondensation reaction 3-4h in the nitrogen protection bottom discharge, obtains polyester elastomer at last;
(3) melt spinning
Polyester elastomer melt spinning with step (2) preparation obtains the modified polyether ester elastomer.
2. a kind of nano-TiO according to claim 1
2The preparation method of polyester ether elastic fiber is characterized in that: step (2) nano-TiO
2The optimum addition mass fraction be 0.3～1.0%.
3. a kind of nano-TiO according to claim 1
2The preparation method of polyester ether elastic fiber is characterized in that: in the step (2) in the prepared polyester elastomer soft section PTMEG molecular mass be 2000g/mol, account for 60～80% of polyether ester gross weight.
4. a kind of nano-TiO according to claim 1
2The preparation method of polyester ether elastic fiber is characterized in that: described nano-TiO
2Select 0.1～2.0% of the reasonable opinion of mass ratio output.
5. a kind of nano-TiO according to claim 1
2The preparation method of polyester ether elastic fiber is characterized in that: prepared polyester elastomer inherent viscosity [η] is greater than 1.2dL/g in the step (2).
6. a kind of nano-TiO according to claim 1
2The preparation method of polyester ether elastic fiber is characterized in that: the polyester elastomer melt spinning described in the step (3), spinning speed are 800-1000m/min.
7. a kind of nano-TiO according to claim 1
2The preparation method of polyester ether elastic fiber is characterized in that: described polyester ether elastic fiber elastic recovery rate is greater than 98%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100438073A CN100516327C (en) | 2007-07-13 | 2007-07-13 | Method for preparing nano TiO2 polyester ether elastic fiber |
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|---|---|---|---|
| CNB2007100438073A CN100516327C (en) | 2007-07-13 | 2007-07-13 | Method for preparing nano TiO2 polyester ether elastic fiber |
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| CN100516327C CN100516327C (en) | 2009-07-22 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115532A (en) * | 2009-12-30 | 2011-07-06 | 上海杰事杰新材料(集团)股份有限公司 | Polyster elastomer foam material with high melt strength and preparation method thereof |
| CN103570928A (en) * | 2013-10-15 | 2014-02-12 | 南京聚隆科技股份有限公司 | Modified thermoplastic polyester elastomer and preparation method thereof |
| CN105585704A (en) * | 2014-10-23 | 2016-05-18 | 中国石油化工股份有限公司 | Bio-polyether ester elastomer and preparation method therefor |
| CN106757488A (en) * | 2016-12-20 | 2017-05-31 | 吴中区穹窿山福顺生物技术研究所 | A kind of nano modified polyurethane fibrous material and preparation method thereof |
| CN113755966A (en) * | 2021-09-24 | 2021-12-07 | 无锡市兴盛新材料科技有限公司 | Preparation method of PBT (polybutylene terephthalate) slice for memory-fiber-imitated fiber |
-
2007
- 2007-07-13 CN CNB2007100438073A patent/CN100516327C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115532A (en) * | 2009-12-30 | 2011-07-06 | 上海杰事杰新材料(集团)股份有限公司 | Polyster elastomer foam material with high melt strength and preparation method thereof |
| CN102115532B (en) * | 2009-12-30 | 2013-11-06 | 上海杰事杰新材料(集团)股份有限公司 | Polyster elastomer foam material with high melt strength and preparation method thereof |
| CN103570928A (en) * | 2013-10-15 | 2014-02-12 | 南京聚隆科技股份有限公司 | Modified thermoplastic polyester elastomer and preparation method thereof |
| CN105585704A (en) * | 2014-10-23 | 2016-05-18 | 中国石油化工股份有限公司 | Bio-polyether ester elastomer and preparation method therefor |
| CN106757488A (en) * | 2016-12-20 | 2017-05-31 | 吴中区穹窿山福顺生物技术研究所 | A kind of nano modified polyurethane fibrous material and preparation method thereof |
| CN106757488B (en) * | 2016-12-20 | 2019-05-17 | 南通俊成纺织品有限公司 | A kind of nano modified polyurethane fibrous material and preparation method thereof |
| CN113755966A (en) * | 2021-09-24 | 2021-12-07 | 无锡市兴盛新材料科技有限公司 | Preparation method of PBT (polybutylene terephthalate) slice for memory-fiber-imitated fiber |
| CN113755966B (en) * | 2021-09-24 | 2022-07-22 | 无锡市兴盛新材料科技有限公司 | Preparation method of PBT (polybutylene terephthalate) slice for memory-fiber-imitated fiber |
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