CN1291080C - Method for preparing thermostable meltspun urethane elastic fiber - Google Patents
Method for preparing thermostable meltspun urethane elastic fiber Download PDFInfo
- Publication number
- CN1291080C CN1291080C CN 200410065487 CN200410065487A CN1291080C CN 1291080 C CN1291080 C CN 1291080C CN 200410065487 CN200410065487 CN 200410065487 CN 200410065487 A CN200410065487 A CN 200410065487A CN 1291080 C CN1291080 C CN 1291080C
- Authority
- CN
- China
- Prior art keywords
- thermoplastic elastomer
- meltspun
- thermostable
- polyurethane thermoplastic
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention provides a method for preparing melt spun spandex with good thermal stability, which belongs to the field of modifying chemical fibers and mainly solves the problem of poor thermal stability of melt spun spandex. The method comprises: additives, a crosslinking agent and slices of thermoplastic polyurethane elastomer are homogeneously mixed, treated by molten extrusion, wound and formed. By selecting appropriate additives, the acting forces among macromolecular chains of spandex and the degree of crystallization and the crystal grain size of a hard section phase can be improved so as to improve the thermal stability of the spandex.
Description
Technical field
The present invention relates to a kind of chemical fiber modification means, a kind of preparation method of thermostable meltspun urethane elastic fiber particularly is provided.
Background technology
In the prior art, spandex has another name called polyurethane elastomeric fiber, and the incomparable elasticity of other any fibers is arranged, and its elongation at break, reaches as high as more than 800% usually at 500-700% greater than 400%.Elastic recovery rate during deformation 300% reaches more than 95%, has good fatigue performance and elastic restoration ratio, and elasticity is lasting for form.The chemical-resistant of polyurethane elastomeric fiber and oil resistivity are good.The microphase-separated aggregated structure of stabilized polyurethane is the elastomeric polyurethane fiber basis.The driving force of microphase-separated process is the crystallization of thermodynamics incompatibility, the hydrogen bond in the hard section and dipolar interaction and hard section between the soft or hard section.Wherein, soft section is that polyester or polyethers by lower molecular weight constitutes, and its weight fraction is 60-85%, constitutes the continuous phase of fiber, mainly gives the high elongation rate of fiber.Hard section then is mainly the carbamate segment, and its polarity is big, crystallinity is strong, constitutes the physical crosslinking point, is evenly distributed in the continuous phase, gives fiber resilience and mechanical strength.The physical and mechanical properties of polyurethane microphase-separated degree direct influence spandex.In the dry spinning spandex macromolecular chain structure, there are urethano and urea groups simultaneously, and only have urethano in the melt spun spandex macromolecular chain structure.The cohesion energy density of urea groups is 0.981kJ/cm3, and the urethano cohesion energy density is 0.839kJ/cm3.In the dry spinning spandex between macromolecular chain the hydrogen bond number be twice than melt spun spandex, it is tightr to cause in the dry spinning spandex macromolecular chain structure hard section to be piled up, domain structure is more complete, the microphase-separated degree is more perfect.Like this, the degree of crystallinity of dry spinning spandex and crystallite dimension on the macroscopic view, show as the high characteristics of heat distortion temperature all apparently higher than melt spun spandex, thus with regard to pragmatize the melt spun spandex heat resistance than dry-spinning for the difference reason.
Summary of the invention
The object of the invention provides a kind of method for preparing thermostable meltspun urethane elastic fiber, by selecting suitable additive, the active force between increase spandex macromolecular chain and the degree of crystallinity and the crystallite dimension of hard section phase, and then improve the heat endurance of spandex, mainly solve the problem of melt spun spandex poor heat stability.
Technical scheme of the present invention is: a kind of preparation method of thermostable meltspun urethane elastic fiber, heat-resisting crosslinking agent and Polyurethane Thermoplastic Elastomer section are added screw extruder, section is owing to be heated and fusion, melt is extruded and is delivered to spinning part with certain pressure, with Spinning pumps melt quantitative is depressed into spinnerets equably then, the melt thread is extruded from the spinnerets aperture, cools off and solidificating fiber in the path, and oiling is wound into tube; Spinning temperature is 180-225 ℃, spinning speed be generally 300-1100 rice/minute, also be mixed with additive in the described Polyurethane Thermoplastic Elastomer section, described additive is one of fatty amine, nylon, benzene guanidine, thiocarbamide, epoxide modified soybean oil, coupling agent, silicone oil or its mixture, and the alkyl length of described fatty amine is between 12-18.
The present invention compared with prior art has following advantage: improved the deficiency of melt spun spandex aspect heat endurance, adding by additive, increase the interaction force between the degree of crystallinity of the hard section of spandex phase and crystallite dimension, the macromolecular chain and repaired the fracture macromolecular chain, and then improved the heat endurance of melt spun spandex.
The specific embodiment
A kind of preparation method of thermostable meltspun urethane elastic fiber, heat-resisting crosslinking agent and Polyurethane Thermoplastic Elastomer section are added screw extruder, section is owing to be heated and fusion, melt is extruded and is delivered to spinning part with certain pressure, with Spinning pumps melt quantitative is depressed into spinnerets equably then, the melt thread is extruded from the spinnerets aperture, cools off and solidificating fiber in the path, and oiling is wound into tube; Also be mixed with additive in the described Polyurethane Thermoplastic Elastomer section, described additive is one of fatty amine, nylon, benzene guanidine, thiocarbamide, epoxide modified soybean oil, coupling agent, silicone oil or its mixture.Coupling agent mainly refers to silane and titante coupling agent among the present invention, the siloxanes chain link that utilizes silane coupler to form can have certain compatibility and titanate coupling agent certain compatibility characteristics to be arranged with the soft polyester section with polyester soft segment, the hydroxyl isoreactivity radical reaction that this two classes coupling agent Chang Nengyu polyurethane elevated temperature heat degraded simultaneously forms, thereby the heat endurance of raising spandex.Silane coupler can comprise amino and two types of epoxy radicals; Titanate coupling agent then can be any or multiple combination in four types (alcoxyl esters of monoalkoxy aliphatic acid, phosphatic type, integrated and corrdination type), and perhaps two class coupling agents is used in combination.
The crosslinking agent of heat resistant type is that a class has good thermal stability structure (as bisphenol A-type and polysulfones segmented structure), polyfunctionality (end group such as isocyanates) oligomer, its effect is further to increase polyurethane macromolecular interchain interaction force by physical-chemical reaction, the outside tensile stress that opposing spandex silk bears, high elastic restoration ratio is provided, also improves the spandex silk heat endurance of (as last handling processes such as printing and dyeing) at high temperature simultaneously.Described additive is fatty amine (alkyl length is between 12-18), and its consumption is to account for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
Described additive is copolymer nylon and nylon 1010, and its consumption is to account for 1～15.0% of Polyurethane Thermoplastic Elastomer section weight.
Described additive is the benzene guanidine, and its consumption is to account for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
Described additive is a thiocarbamide, and its consumption is to account for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
Described additive is epoxide modified soybean oil, and its consumption is to account for 1～15.0% of Polyurethane Thermoplastic Elastomer section weight.
Described additive is made up of fatty amine and silicone oil, wherein fatty amine accounts for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight, silicone oil is amino, epoxy and hydroxyl modification silicone oil, can be single silicone oil or both are used in combination, it accounts for the 0.1-15.0% of Polyurethane Thermoplastic Elastomer section weight.
Described additive is made up of fatty amine and coupling agent, wherein fatty amine accounts for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight, coupling agent can be amino, epoxies silane coupler, also can be any or multiple combination in the titanate coupling agent (four types of the alcoxyl esters of monoalkoxy aliphatic acid, phosphatic type, chelating type and corrdination type), perhaps being used in combination of two class coupling agents, it accounts for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
Spandex structure and performance comparison sheet
| Project | Dry-spinning * (30D) | Melt-spun * (40D) | Example 1 (30D) | Example 2 (20D) | Example 3 (40D) | Comparative example (30D) |
| The line density coefficient of variation, cv% | 2.43 | 4.13 | 3.43 | 2.75 | 4.5 | 3.83 |
| Fracture strength, cN/tex | 13.3 | 12.6 | 12.1 | 12.8 | 11.4 | 12.4 |
| Elongation at break, % | 559.0 | 445.3 | 518.0 | 540.3 | 534.7 | 452.2 |
| Elastic recovery rate, % | 97.10 | 96.5 | 96.5 | 96.3 | 96.8 | 96.9 |
| Boiling water shrinkage, % | 9.80 | 6.4 | 5.8 | 4.5 | 6.8 | 10.4 |
| Degree of crystallinity, % | 51.3 | 22.2 | 27.2 | 25.8 | 27.5 | 21.5 |
| Grain size, | 39.1 | 22.6 | 23.9 | 23.8 | 24.3 | 22.1 |
| Xeothermic recovery rate, and % (130 ℃, 30min) | 63.0 | 58.0 | 60.2 | 59.8 | 61.5 | 56.2 |
Annotate: 1) * is the import sample;
2) example 1 is selected the melt spun spandex of octadecylamine for use for additive, and it accounts for 3% of section weight;
Example 2 is selected the melt spun spandex of octadecylamine and amido silicon oil for use for additive, and wherein fatty amine accounts for 2.5% of section weight, and silicone oil accounts for 2.0% of section weight;
Example 3 is selected the melt spun spandex of octadecylamine and coupling agent KH550 for use for additive, and wherein fatty amine accounts for 2.5% of section weight, and coupling agent accounts for 0.5% of section weight;
Comparative example is not for adding the melt spun spandex of additive.
3) degree of crystallinity and crystallite dimension are recorded by X-ray diffraction method;
4) xeothermic recovery rate method of testing is: get the long sample silk of a 50mm, the sample silk is stretched, make the sample silk be stretched to 200mm, promptly stretched 300%.The sample silk that stretches is fixed on the anchor clamps at xeothermic recovery rate analyzer two ends, puts into 130 ℃ electric heating convection oven, take out behind the 30min.Cool off after 2 hours, clamper is unclamped, measure the length of this up-to-date style silk behind the 30min, unit is mm.Xeothermic recovery rate is: xeothermic recovery rate={ [50-(handling back length-50)]/50}*100%.The xeothermic recovery rate of sample is the mean value of five xeothermic recovery rates of sample silk.
Test result shows: after adding additive, comprehensive mechanical property and heat resistance increase.Provided the influence of portions additive in the table to melt spun spandex.Since various reactive functional groups can with segmented polyurethane generation physical-chemical reaction, improve the active force of the macromolecular chain of hard section phase in the spandex microphase-separated, particularly hard section phase degree of crystallinity and crystallite dimension, thereby improve the heat endurance of spandex.For example, the spinning experiment of adding percentage by weight respectively and be the 0.1-5.0% octadecylamine in section shows: degree of crystallinity and crystallite dimension can obtain the elastomer of function admirable along with the octadecylamine addition increases; Addition is then improving DeGrain more than 5%.In addition, fatty amine adds coupling agent simultaneously or silicone oil also can make performance be further enhanced adding.
Claims (10)
1. the preparation method of a thermostable meltspun urethane elastic fiber, heat-resisting crosslinking agent and Polyurethane Thermoplastic Elastomer section are added screw extruder, section is owing to be heated and fusion, melt is extruded and is delivered to spinning part with certain pressure, with Spinning pumps melt quantitative is depressed into spinnerets equably then, the melt thread is extruded from the spinnerets aperture, cools off and solidificating fiber in the path, and oiling is wound into tube; It is characterized in that: also be mixed with additive in the described Polyurethane Thermoplastic Elastomer section, described additive is one of fatty amine, nylon, benzene guanidine, thiocarbamide, epoxide modified soybean oil, coupling agent, silicone oil or its mixture, the percentage by weight that additive accounts for the Polyurethane Thermoplastic Elastomer section is 0.1～15.0%, and the alkyl length of described fatty amine is between 12-18.
2, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1 is characterized in that: the consumption of described fatty amine is to account for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
3, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1 is characterized in that: described additive is copolymer nylon or nylon 1010, and its consumption is to account for 1～15.0% of Polyurethane Thermoplastic Elastomer section weight.
4, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1 is characterized in that: described additive is the benzene guanidine, and its consumption is to account for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
5, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1 is characterized in that: described additive is a thiocarbamide, and its consumption is to account for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
The preparation method of 6 thermostable meltspun urethane elastic fibers according to claim 1 is characterized in that: described additive is epoxide modified soybean oil, and its consumption is to account for 1～15.0% of Polyurethane Thermoplastic Elastomer section weight.
7, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1, it is characterized in that: described additive is made up of fatty amine and silicone oil, wherein fatty amine accounts for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight, and it accounts for the 0.1-15.0% of Polyurethane Thermoplastic Elastomer section weight.
8, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1 is characterized in that: described silicone oil is amino or epoxy or hydroxyl modification silicone oil.
9, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1 is characterized in that: described coupling agent is amino or its mixture of one of epoxies silane coupler or titanate coupling agent.
10, the preparation method of thermostable meltspun urethane elastic fiber according to claim 1, it is characterized in that: described additive is made up of fatty amine and coupling agent, wherein fatty amine accounts for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight, and coupling agent accounts for 0.1～5.0% of Polyurethane Thermoplastic Elastomer section weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410065487 CN1291080C (en) | 2004-12-08 | 2004-12-08 | Method for preparing thermostable meltspun urethane elastic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410065487 CN1291080C (en) | 2004-12-08 | 2004-12-08 | Method for preparing thermostable meltspun urethane elastic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1635198A CN1635198A (en) | 2005-07-06 |
| CN1291080C true CN1291080C (en) | 2006-12-20 |
Family
ID=34846492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410065487 Expired - Fee Related CN1291080C (en) | 2004-12-08 | 2004-12-08 | Method for preparing thermostable meltspun urethane elastic fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1291080C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372552B (en) * | 2007-08-22 | 2010-11-10 | 中国科学院化学研究所 | High-strength temperature-resistant thermoplastic polyurethane elastomer blended modifier and preparation thereof |
| CN105330875B (en) * | 2015-11-23 | 2019-01-29 | 青岛大学 | A kind of cross-linking modified sodium alginate and preparation method thereof |
| CN106995946A (en) * | 2017-02-23 | 2017-08-01 | 南通强生石墨烯科技有限公司 | The preparation method of graphene spandex composite fibre |
| CN111575817A (en) * | 2019-02-19 | 2020-08-25 | 海宁新高纤维有限公司 | Method for manufacturing thermoplastic polyurethane fiber |
| CN109825895B (en) * | 2019-03-05 | 2021-07-20 | 华峰化学股份有限公司 | High-temperature-resistant alkali-resistant spandex and preparation method thereof |
| CN110760945B (en) * | 2019-10-28 | 2022-01-25 | 华峰化学股份有限公司 | Spandex fiber with good thermal stability and preparation method thereof |
-
2004
- 2004-12-08 CN CN 200410065487 patent/CN1291080C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1635198A (en) | 2005-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Toki et al. | New insights into structural development in natural rubber during uniaxial deformation by in situ synchrotron X-ray diffraction | |
| CN1291080C (en) | Method for preparing thermostable meltspun urethane elastic fiber | |
| US20100009204A1 (en) | Carbon nanofibers, method of producing the same, and carbon fiber composite material | |
| CN104675922B (en) | A kind of high intensity Timing Belt and preparation method thereof | |
| CN1771153A (en) | Polyester filament woven fabric for air bags | |
| CN105780178B (en) | A kind of preparation method of low melting point spandex fibre | |
| CN112695392A (en) | Method for manufacturing high-modulus low-shrinkage industrial yarn by utilizing recycled polyester | |
| CN112127006A (en) | Easy-to-dye spandex fiber and preparation method thereof | |
| KR100308739B1 (en) | High strength polyethylene fiber and its manufacturing method | |
| CN110183749A (en) | A kind of graphene enhancing rubber packing material and preparation method thereof | |
| CN1846018A (en) | Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance | |
| CN110041700B (en) | Carbon fiber reinforced nylon material, preparation raw material, preparation method and application thereof | |
| CN111394821A (en) | High-strength and high-resilience spandex fiber and preparation method thereof | |
| CN113215669B (en) | Thermoplastic polyurethane fiber and manufacturing method thereof | |
| CN117535806A (en) | Preparation method of ultra-high molecular weight polyethylene fiber and ultra-high molecular weight polyethylene fiber | |
| WO2005059212A1 (en) | Method for producing polyester fiber and spinning mouth piece for melt spinning | |
| JP5508183B2 (en) | Polyester cord for power transmission belt reinforcement | |
| CN107663670A (en) | A kind of polyurethane elastomeric fiber and preparation method thereof | |
| CN113774505B (en) | Polypropylene fiber, preparation method and sweeping brush | |
| JPH11350249A (en) | Polyester fiber for v-belt reinforcement and its production and cord for v-belt reinforcement | |
| CN115558102B (en) | Long-chain nylon elastomer and transesterification preparation method | |
| CN108641277A (en) | A kind of high-performance charging pile cable thermoplastic elastomer (TPE) and preparation method thereof | |
| RU2822642C1 (en) | Meta-aromatic polyamide fiber with high elongation, method for its production and device | |
| CN115772714B (en) | High-strength high-heat-resistance spandex and preparation method thereof | |
| CN112725929B (en) | Spinning control method for high-temperature-resistant polyurethane elastic fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061220 Termination date: 20141208 |
|
| EXPY | Termination of patent right or utility model |