CN1389602A - Modified melt spun spandex and its prepn. process - Google Patents
Modified melt spun spandex and its prepn. process Download PDFInfo
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- CN1389602A CN1389602A CN 01115739 CN01115739A CN1389602A CN 1389602 A CN1389602 A CN 1389602A CN 01115739 CN01115739 CN 01115739 CN 01115739 A CN01115739 A CN 01115739A CN 1389602 A CN1389602 A CN 1389602A
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Abstract
A modifying polyurethane elastic fibre melt-spinning and its preparation property is opened, which belongs to the modifying field of chemistry fibre. By adding the nanometer flour in the synthesis process of prepolymer, mixing equably the additive which is the propolymer containing nanometer flour with heat plastic polyurethane elastic slice in the blender and extruding the filature, the modifying polyurethane elastic fibre melt-spinning is attained. Due to adding the nanoemter flour, the elasticity reversion and synthetical mechanics performance of the polyurethane elastic fibre melt-spinning is improved largely, and quality of the product such as rupture elongation, module quantity, reversion character and uniformity is as much as the dry spinning's.
Description
The invention belongs to the method for modifying field of chemical fibre, particularly melt spun spandex of modification and preparation method thereof.
Spandex is the high-grade textile fiber that a kind of existing fibre property has rubber performance again, and is increasingly extensive in the application of aspects such as various sweat shirts, swimsuit, gym wear, high stretch hosiery.The method of producing spandex has four kinds of dry method, wet method, chemical method and fusion methods.In four kinds of spandex production methods, dry spinning output maximum, account for 80% of Gross World Product, the spandex function admirable that this method is produced, but production cost height, and owing to need in the production process to use a large amount of organic solvents, as DMF and DMAc, these solvents are very big to environment and human health damage.Melt spinning method is produced spandex and is had that technological process is simple, equipment investment is low, the production efficiency advantages of higher, and be easy to realize the thin dawnization of spandex, need not to use solvent in process of production, be the spandex production technology of economy and environmental pollution minimum the most, extensively be subject to people's attention in recent years.
Spandex is a kind of fiber of being made by the block copolymer that contains soft chain segment and hard segment, soft chain segment is formed by not having crystalline low-molecular-weight polyester or polyether polyol, its vitrification point is very low, is in elastomeric state under the normal temperature, is subjected to being easy to take place deformation behind the stress; Hard segment is formed with the hydroxyl groups reaction by diisocyanate resin, and having crystallinity also can be laterally crosslinked, and deformation can not take place under the stress effect, and the high rebound characteristics of spandex derives from the physical crosslinking effect of hard segment microcell.Dry spinning adopts diamines to make chain extender usually, can in hard section, form the very high urea groups of cohesive energy, thereby make hard section to combine more closely, for increasing the intensity of resin and spandex, being used to make molten TPU (thermoplastic polyurethane spring shape body) the employing glycol that spins spandex is that the chain extender resultant effect is better, but the adhesion between hard segment molecule is lower, causes the low and less stable of hard section aggregation extent.From present development, melt spun spandex is being better than dry spinning spandex aspect fracture strength, the extension modulus, but it would be better dry spinning spandex at aspects such as elastic recovery rate, heat resistances.For improving the deficiency of melt spun spandex aspect above-mentioned two, elder generation is with granular spandex section drying when the spandex melt spinning, remove moisture, extrude through the screw extruder that has heater then, rotation along with screw rod, section is forced to push ahead, the while melted by heating, melt is extruded and is transported to spinning part with certain pressure, with Spinning pumps melt quantitative is depressed into spinnerets equably then, melt is extruded the formation thread in the pore of spinnerets, attenuate through elongation, cooling forming in the path becomes tube after reach the coiling position after oiling.Add additive in process of production mostly, before entering casing, be provided with mixing device, melt and additive spinning technique after blender mixes.
The objective of the invention is to improve the deficiency of melt spun spandex, melt spun spandex of a kind of modification and preparation method thereof is provided, in order to improve the spandex comprehensive mechanical property at aspects such as elastic recovery rate, heat resistances.
The melt spun spandex of modification of the present invention is by polytetrahydrofuran diol (PTMG), nano-powder, 4, and 4 '-diphenylmethane diisocyanate fat (MDI) and Polyurethane Thermoplastic Elastomer (TPU) section are formed, and the fiber number of the melt spun spandex of modification is 40-100dtex; Wherein by nano-powder, polytetrahydrofuran diol and 4, the performed polymer that 4 '-diphenylmethane diisocyanate fat is formed: the percentage by weight of Polyurethane Thermoplastic Elastomer is 5%-25%: 75%-95%, polytetrahydrofuran diol: 4,4 '-diphenylmethane diisocyanate fat: the ratio of weight and number of nano-powder is 20-45: 10-15: 1-11.
The relative molecular weight of described polytetrahydrofuran diol (PTMG) is 1000-2000.
Described nano-powder comprises hydrotalcite, zinc oxide, imvite, calcium carbonate, silica, magnesium hydroxide etc.
Described particle diameter of nanometer powder is 30-100nm; Preferred 60-70nm.
The preparation method of the melt spun spandex of modification of the present invention:
Add nano-powder in the performed polymer building-up process, the performed polymer that will contain nano-powder evenly mixes the back extruding spinning as additive with Polyurethane Thermoplastic Elastomer section melt in blender, obtain melt spun spandex.
1. the preparation of performed polymer: nano-powder is joined in the polytetrahydrofuran diol (PTMG), under 35-45 ℃ temperature, and at N
2Protection is stirred down; add 4; 4 '-diphenylmethane diisocyanate fat (MDI); stir, continue to heat, stir to 65-75 ℃; promptly obtain performed polymer after stirring; wherein, polytetrahydrofuran diol: 4,4 '-diphenylmethane diisocyanate fat: the ratio of weight and number of nano-powder is=20-45: 10-15: 1-11.
2. the performed polymer that obtains with step 1 behind the Polyurethane Thermoplastic Elastomer chip drying is joined and carry out melting mixing in the screw extruder, melt evenly mixes the back extruding spinning in blender, obtain the melt spun spandex that fiber number is the modification of 40-100dtex, wherein, performed polymer: the percentage by weight of Polyurethane Thermoplastic Elastomer is=5%-25%: 75%-95%.
Described mixing time is 1.5-3 hour.
Described chip drying temperature is preferably 95-100 ℃, and spinning temperature is 180 ℃-250 ℃, and melt pressure is 8-15MPa, and spinning speed is 200-1000m/min.
During spinning, at first will join in the screw extruder behind the granular Polyurethane Thermoplastic Elastomer chip drying, the performed polymer that step 1 obtains joins in the screw extruder melt mixed with Polyurethane Thermoplastic Elastomer by the prepolymer storage tank that links to each other with screw rod, fully extrudes, oils, is wound into tube behind the mixing in blender.In the melt spinning process, when the viscosity of melt excessive, Reynolds (Reynold's) criterion is very little, when the energy that the interior elastic energy of storing of unit volume increases to viscous loss is suitable, in spinning process, can show " melt fracture ", therefore, elastomer melt spinning process typical additives shielding viscoplasticity, the present invention uses the performed polymer that has added nano-powder as additive, because the performed polymer relative molecular weight is low, can reduce the viscoplasticity of melt, improve the mobile performance of melt, spinning is carried out smoothly, in spinning process, the pre-polymerization physical efficiency forms crosslinked in existing polyurethane molecular structure, makes fiber have higher intensity and better elastic.
The present invention shows, after bringing up to a certain degree with the increase of nano material addition, the comprehensive mechanical property of polyurethane descends to some extent on the contrary, and be not The more the better.The spinning experiment of adding mass percent respectively be in performed polymer behind the 1%-10% nano-powder shows, increase prepolymer solution viscosity with the nano material addition increases gradually, and solution viscosity is excessive to be unfavorable for the performance of performed polymer effect and carrying out smoothly of spinning process.Suitably regulating under the prerequisite of spinning technology parameter, addition is 4% when following, can be under the prerequisite that guarantees spinnability the very good polyurethane elastomeric fiber of acquisition mechanical property.
The spandex that elastic spandex fiber of the present invention and overseas utilization dry method and fusion method obtain has carried out performance relatively, related data as shown in Table 1:
Table one 44dtex elastomer partial properties
Annotate: A. is through 1 time 300% stretching; B. stretch repeatedly through 5 times 300%.
| Product | Fracture strength (cN/dtex) | Extension at break (%) | Extension modulus (cN/dtex) | Permanent residual elongation (%) | ||
| ??300％ | ??100％ | ????A | ????B | |||
| Lycra (dry method) Dorlastan (dry method) Fourne (molten method) Japanese (molten method) sample of the present invention | ??0.80 ??0.70 ??1.40 ??1.30 ??1.80 | ??＞600 ??＞600 ?450-550 ?450-550 ??＞700 | ??0.34 ??0.30 ??0.65 ??0.47 ??0.66 | ??0.13 ??0.13 ??0.31 ??0.16 ??0.35 | ????19 ????18 ????23 ????38 ????9 | ????25 ????25 ????33 ????48 ????15 |
Contrast by table one can illustrate, the interpolation of nano-powder has improved the elastic recovery and the comprehensive mechanical property of melt spun spandex greatly, and product quality such as extension at break, modulus, recovery characteristic and the uniformity all can be compared with the dry-spinning product.
Below in conjunction with embodiment technical scheme of the present invention is further described.Embodiment 1
In reactor, add polytetrahydrofuran diol (PTMG) 48.4Kg; nano-calcium carbonate 1% (calculating according to the performed polymer gross mass) is added among the PTMG; under nitrogen protection, stirring 1.5 hours about 40 ℃; add 15.8Kg4; 4 '-methyl diphenylene diisocyanate (MDI); to temperature-resistant, continue to heat and reacted 1.5 hours down to 70 ℃ of stirrings, it is standby to make performed polymer.
Add the performed polymer that accounts for finished product total amount 25% (quality) in spinning process, spinning temperature is 180 ℃-220 ℃, and melt pressure is 9-10MPa, and spinning speed is 700m/min.Obtain the melt spun spandex that fibre number is the modification of 44dtex.
The improvement of gained elastomer on comprehensive mechanical property is fairly obvious, especially aspect extension at break and recovery characteristic.
Embodiment 2.
Reactions steps and spinning step are with embodiment 1.Add PTMG 52.2Kg in reactor, it is zinc oxide that institute adds the nano powder body, and addition is 2.5% of a performed polymer gross mass, stirs 2 hours about 50 ℃, adds 14.4Kg MDI.
The performed polymer that adds in spinning process accounts for finished product total amount 15% (quality), and spinning temperature is 160 ℃-200 ℃, obtains the melt spun spandex that fibre number is the modification of 44dtex.The gained elastomer not only increases on mechanical property, and has sterilization and uvioresistant characteristic.
Embodiment 3.
PTMG 53.6Kg, it is nano hydrotalcite that institute adds the nano powder body, adding method such as embodiment 1, addition are that 2%, 50 ℃ of performed polymer gross mass stirred 1 hour down, add 16.8Kg MDI.
The performed polymer that adds in spinning process accounts for finished product total amount 20% (quality), and spinning temperature is 190 ℃-220 ℃, obtains the melt spun spandex that fibre number is the modification of 44dtex.The gained elastomer has good chlorine resistance.
Embodiment 4.
PTMG 50Kg, it is nano imvite that institute adds the nano powder body, adding method such as embodiment 1, addition are that 3%, 45 ℃ of performed polymer gross mass stirred 2 hours, add 12.5Kg MDI.
The performed polymer that adds in spinning process accounts for finished product total amount 10% (quality), and spinning temperature is 210 ℃-250 ℃, obtains the melt spun spandex that fibre number is the modification of 44dtex.
Claims (11)
1. the melt spun spandex of a modification is characterized in that: this melt spun spandex is by polytetrahydrofuran diol, nano-powder, 4, and 4 '-diphenylmethane diisocyanate fat and Polyurethane Thermoplastic Elastomer section are formed; Wherein by nano-powder, polytetrahydrofuran diol and 4, the performed polymer that 4 '-diphenylmethane diisocyanate fat is formed: the percentage by weight of Polyurethane Thermoplastic Elastomer is 5%-25%: 75%-95%, polytetrahydrofuran diol: 4,4 '-diphenylmethane diisocyanate fat: the ratio of weight and number of nano-powder is 20-45: 10-15: 1-11.
2. the melt spun spandex of modification as claimed in claim 1, it is characterized in that: the relative molecular weight of described polytetrahydrofuran diol is 1000-2000.
3. the melt spun spandex of modification as claimed in claim 1, it is characterized in that: described nano-powder comprises hydrotalcite, zinc oxide, imvite, calcium carbonate, silica, magnesium hydroxide.
4. as the melt spun spandex of claim 1 or 3 described modifications, it is characterized in that: described particle diameter of nanometer powder is 30-100nm.
5. the melt spun spandex of modification as claimed in claim 4, it is characterized in that: described particle diameter of nanometer powder is 60-70nm.
6. as the preparation method of the melt spun spandex of each described modification of claim 1-5: it is characterized in that: described method is:
(1). the preparation of performed polymer: nano-powder is joined in the polytetrahydrofuran diol, under 35-45 ℃ temperature, and at N
2Protection is stirred down, add 4,4 '-diphenylmethane diisocyanate fat, stir, continue to heat, stir to 65-75 ℃, promptly obtain performed polymer after stirring, wherein, polytetrahydrofuran diol: 4,4 '-diphenylmethane diisocyanate fat: the ratio of weight and number of nano-powder is 20-45: 10-15: 1-11;
(2). the performed polymer that obtains with step (1) behind the Polyurethane Thermoplastic Elastomer chip drying joined carry out melting mixing in the screw extruder, melt evenly mixes the back extruding spinning in blender, obtain the melt spun spandex of modification, wherein, performed polymer: the percentage by weight of Polyurethane Thermoplastic Elastomer is 5%-25%: 75%-95%.
7. the preparation method of the melt spun spandex of modification as claimed in claim 6: it is characterized in that: described mixing time is 1.5-3 hour.
8. the preparation method of the melt spun spandex of modification as claimed in claim 6: it is characterized in that: described chip drying temperature is 95-100 ℃, and spinning temperature is 180 ℃-250 ℃, and melt pressure is 8-15MPa, and spinning speed is 200-1000m/min.
9. the preparation method of the melt spun spandex of modification as claimed in claim 6: it is characterized in that: the relative molecular weight of described polytetrahydrofuran diol is 1000-2000.
10. the melt spun spandex of modification as claimed in claim 1, it is characterized in that: described nano-powder comprises hydrotalcite, zinc oxide, imvite, calcium carbonate, silica, magnesium hydroxide.
11. the melt spun spandex of modification as claimed in claim 6 is characterized in that: described particle diameter of nanometer powder is 30-100nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255619B (en) * | 2008-04-09 | 2010-09-01 | 南通华盛高聚物科技发展有限公司 | Preparation method of melt-spun spandex containing nano-powder |
| CN102154729A (en) * | 2011-05-18 | 2011-08-17 | 浙江开普特氨纶有限公司 | Preparation method of high-elongation and high-draft polyurethane fibers |
| CN102127827B (en) * | 2010-01-18 | 2012-10-31 | 浙江华峰氨纶股份有限公司 | Method for preparing nano-attapulgite modified polyurethane elastic fiber |
| CN104088109A (en) * | 2014-07-15 | 2014-10-08 | 浙江理工大学 | Machining shaping method capable of arbitrarily clipping shell fabrics |
| 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 |
| CN108560076A (en) * | 2018-05-15 | 2018-09-21 | 浙江华峰氨纶股份有限公司 | A kind of medical Polyurethane Elastomer and preparation method thereof with biocompatibility |
| CN114574997A (en) * | 2022-02-08 | 2022-06-03 | 南通华盛高聚物科技股份有限公司 | Sea-island composite monofilament made of TPU functional composite fiber |
-
2001
- 2001-06-04 CN CNB011157399A patent/CN1180137C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255619B (en) * | 2008-04-09 | 2010-09-01 | 南通华盛高聚物科技发展有限公司 | Preparation method of melt-spun spandex containing nano-powder |
| CN102127827B (en) * | 2010-01-18 | 2012-10-31 | 浙江华峰氨纶股份有限公司 | Method for preparing nano-attapulgite modified polyurethane elastic fiber |
| CN102154729A (en) * | 2011-05-18 | 2011-08-17 | 浙江开普特氨纶有限公司 | Preparation method of high-elongation and high-draft polyurethane fibers |
| CN104088109A (en) * | 2014-07-15 | 2014-10-08 | 浙江理工大学 | Machining shaping method capable of arbitrarily clipping shell fabrics |
| 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 |
| CN108560076A (en) * | 2018-05-15 | 2018-09-21 | 浙江华峰氨纶股份有限公司 | A kind of medical Polyurethane Elastomer and preparation method thereof with biocompatibility |
| CN108560076B (en) * | 2018-05-15 | 2020-09-25 | 浙江华峰氨纶股份有限公司 | Medical polyurethane elastomer with biocompatibility and preparation method thereof |
| CN114574997A (en) * | 2022-02-08 | 2022-06-03 | 南通华盛高聚物科技股份有限公司 | Sea-island composite monofilament made of TPU functional composite fiber |
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