CN105297161B - It is a kind of using water soluble polyurethane elastomer as the sea-island fibre decrement method in a mild condition in sea - Google Patents
It is a kind of using water soluble polyurethane elastomer as the sea-island fibre decrement method in a mild condition in sea Download PDFInfo
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- CN105297161B CN105297161B CN201510604060.9A CN201510604060A CN105297161B CN 105297161 B CN105297161 B CN 105297161B CN 201510604060 A CN201510604060 A CN 201510604060A CN 105297161 B CN105297161 B CN 105297161B
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- sea
- island
- polyurethane elastomer
- water soluble
- decrement
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- 239000000835 fiber Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 claims abstract description 22
- 239000004814 polyurethane Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 7
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims 2
- 239000000806 elastomer Substances 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000009940 knitting Methods 0.000 abstract description 3
- 239000002649 leather substitute Substances 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 230000009467 reduction Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920004933 Terylene® Polymers 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 239000010985 leather Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 102000002151 Microfilament Proteins Human genes 0.000 description 1
- 108010040897 Microfilament Proteins Proteins 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000003632 microfilament Anatomy 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Multicomponent Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
It is a kind of using water soluble polyurethane elastomer as the sea-island fibre decrement method in a mild condition in sea, sea-island fibre is made by soluble polyurethane elastomer in water under given conditions and island component melts composite spinning；Using the water dissolvable of the polyurethane containing potential hydrophilic radical, decrement and the recycling of extra large component are realized in a mild condition.Obtained sea-island fibre can be widely used for the industries such as synthetic leather, knitting, compared with prior art, the present invention can overcome current sea-island fibre be reduced during caused by environmental pollution and the wasting of resources caused by organic emission.
Description
Technical field
The present invention relates to fibre in differentiation fields, particularly relate to a kind of fine using water soluble polyurethane elastomer as the island in sea
Dimension.
Background technology
Superfine fibre is often referred to the fiber of 0.3 denier of fiber number (0.5 micron of diameter) below, saturating with cold-proof comfort, waterproof
Gas, filterability, deoil soil release performance the features such as, extensively using knitting, synthetic leather, electronic device process etc. industries.Wherein 2014
Nearly 100,000,000 meters of the yield of year domestic superfine fiber chemical leather, occupies an important position in national economy.
There are many ways to processing superfine fibre, island method is one kind particularly important at present.
Patent ZL200480020657.9, ZL01123513.6, ZL201110047108.2, ZL201019063013.2 make
It is sea with or it is preferable to use polyethylene, is mainly reduced using benzene, benzene decrement is to make solvent by the polyethylene in fiber using toluene
Dissolving, removal, although benzene decrement carries out in relatively closed environment, decrement and polyethylene removal process still suffer from largely
Toluene (85-150g/1kg fibers) volatilizees, and causes seriously pollution and the wasting of resources；Patent ZL200610085552.2,
ZL02109799.2, ZL200680036177.0, ZL201010532868.8, ZL201310042086.X use terylene or modification
Terylene is sea, and mainly using Alkali reduction, Alkali reduction is to hydrolyze terylene in lye, remove, and terylene is hydrolyzed and become after Alkali reduction
Terephthalate and ethylene glycol, are not easily recycled and high value added utilization, direct emission also result in serious environmental pollution and money
Source wastes.The production of Sea-island Composite Fiber Synthetic Leather at present is all using benzene decrement or Alkali reduction mode.Patent
ZL03121512.2, ZL201010554602.3, ZL200410013813.0 proposition use polylactic acid or polyvinyl alcohol as sea
Component, polylactic acid are polylactic acid hydrolysis, degradation when being reduced as sea component, and effect on environment is little, but causes the wasting of resources；It is poly-
Vinyl alcohol is hygroscopic, and contact wetting can be tacky, is unfavorable for spinning technique, and the melting temperature of polyvinyl alcohol and decomposition temperature are very
It is close, therefore polyvinyl alcohol is not particularly well-suited for melt spinning.
Therefore, sea-island composite fiber technology at present, can there are poisonous and hazardous organic emissions to make during decrement
Into environmental pollution or (and) wasting of resources, be unfavorable for the sustainable development of superfine fibre industry.
Invention content
The shortcomings that it is a primary object of the present invention to overcome the prior art, provides a kind of sea-island fibre, in temperate condition
The decrement method of lower no organic emission and the method for recycling sea component in a mild condition.The sea-island fibre can be widely used for closing
The industries such as finished leather, knitting.
The present invention adopts the following technical scheme that：
By the way that prepared by water soluble polyurethane elastomer and island component composite spinning sea-island fibre, the sea-island fibre is in alkalinity
Fiber decrement is carried out in aqueous solution, the aqueous polyurethane after decrement is adjusted to the recycling of acid condition progress sea component.
Water soluble polyurethane elastomer reacts the pre- of preparation for polyether Glycols and aliphatic or aromatic diisocyanate
Aggressiveness, then the linear polymer formed after hydrophilic chain extender chain extension, melting temperature are 170-210 DEG C, hydrophilic radical
For carboxyl or carboxyl, sulfonic group combination, and potential hydrophilic radical are before spinning and spinning process is closing.
Water soluble polyurethane elastomer can dissolve in the alkaline aqueous solution of pH 10-12.
Routinely technique carries out composite spinning, i.e., respectively squeezes, melts through screw extruder after sea component and the drying of island component
Melt, measure after through filament spinning component spinning, oil after cooling and shaping, coiling, then boundling, drawing-off, sizing obtain long filament or boundling, lead
It stretches, crimp, shaping, severing obtains staple fiber.
The quantity on sea-island fibre island is 7-64, and sea-island fibre sea component is (25-60) with island components by weight:(75-
40), island component is nylon 6.
A kind of or combination of the alkali for sodium hydroxide and potassium hydroxide used in fiber decrement.
Aqueous polyurethane after decrement is adjusted to the recycling that the acid condition that pH value is 2.0-4.0 carries out sea component, makes
PH value is adjusted with a kind of or combination in hydrochloric acid and sulfuric acid.
By the above-mentioned description of this invention it is found that compared with prior art, the present invention has the advantages that：
1st, the potential hydrophilic radical in water soluble polyurethane elastomer before spinning, spinning process be closing, polyurethane
Elastomer is not hydrophilic, so as to which it is applicable in melt-spinning technology.
2nd, by adjusting the acid-base property of environment come discharge and occlusive polyurethane in hydrophilic radical, gather so as to change sea component
The water solubility of urethane elastomer reaches the decrement of sea-island fibre, the recycling of sea component, in the process without organic emission, does not cause
Environmental pollution.
3rd, fiber decrement process, sea component removal process are not made the molecular backbone of sea component water soluble polyurethane elastomer
Into destruction, it can be reused after recycling, not cause the wasting of resources.
4th, the present invention is produced using water soluble polyurethane elastomer as sea using existing island composite spinning equipment, can
Scheme is provided for superfine fibre industry value chain.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, which is skilled in technique
Personnel can make some nonessential modifications and adaptations according to the content of the invention described above, still fall within the protection model of the present invention
It encloses.
Embodiment one：
(1) raw material prepares：Extra large component is carboxylic prepared by polyether Glycols and aromatic diisocyanate reaction
Polyurethane elastomer, melting temperature are 210 DEG C；Island component is nylon 6, and the mass ratio of extra large component and island component is 50：50.
(2) spinning：Routinely 37 island melt composite spinning techniques carry out, i.e., respectively through spiral shell after sea component and the drying of island component
Bar extruder squeezes, melting, after metering through filament spinning component spinning, oil after cooling and shaping, coiling, then boundling, drawing-off, curling,
Sizing, severing obtain staple fiber.
(3) it is reduced：Sea-island staple fiber is put into the sodium hydrate aqueous solution that pH is 12 and is reduced, the fiber washing after decrement
Obtain micro staple fiber.
(4) polyurethane recycles：Aqueous solution after decrement is 3.0-3.5 with sulphur acid for adjusting pH value, polyurethane Precipitation, mistake
Filter recycling polyurethane.
Sea-island fibre fiber number 4.9dtex, intensity 4.3cN/dtex prepared by the embodiment；Sea-island fibre reduction rate is
99.7%, the polyurethane rate of recovery is 99.5%.
Embodiment two：
(1) raw material prepares：Extra large component is contains carboxyl, sulphur prepared by polyether Glycols and aliphatic diisocyanate reaction
The polyurethane elastomer of acidic group, melting temperature are 170 DEG C；Island component is nylon 6, and the mass ratio of extra large component and island component is
25：75.
(2) spinning：Routinely 7 island melt composite spinning techniques carry out, i.e., respectively through spiral shell after sea component and the drying of island component
Bar extruder squeezes, melting, after metering through filament spinning component spinning, oil after cooling and shaping, coiling, then boundling, drawing-off, shape
To long filament.
(3) it is reduced：Sea island filament is put into the sodium hydrate aqueous solution that pH is 10-10.5 and is reduced, the long filament after decrement
Washing obtains microfilament.
(4) polyurethane recycles：Aqueous solution after decrement is 2-2.5 with sulphur acid for adjusting pH value, polyurethane Precipitation, filtering
Recycle polyurethane.
Sea island filament fiber number 5.1dtex, intensity 3.8cN/dtex prepared by the embodiment；Sea-island fibre reduction rate is
98.9%, the polyurethane rate of recovery is 99.3%.
Embodiment three：
(1) raw material prepares：Extra large component is carboxylic prepared by polyether Glycols and aromatic diisocyanate reaction
Polyurethane elastomer, melting temperature are 195 DEG C；Island component is nylon 6, and the mass ratio of extra large component and island component is 60：40.
(2) spinning：Routinely 37 island melt composite spinning techniques carry out, i.e., respectively through spiral shell after sea component and the drying of island component
Bar extruder squeezes, melting, after metering through filament spinning component spinning, oil after cooling and shaping, coiling, then boundling, drawing-off, curling,
Sizing, severing obtain staple fiber.
(3) it is reduced：Sea-island staple fiber is put into the potassium hydroxide aqueous solution that pH is 10.5-11 and is reduced, the fibre after decrement
Dimension washing obtains micro staple fiber.
(4) polyurethane recycles：Aqueous solution after decrement is 3.5-4 with sulphur acid for adjusting pH value, polyurethane Precipitation, filtering
Recycle polyurethane.
Sea-island fibre fiber number 5.5dtex, intensity 4.1cN/dtex prepared by the embodiment；Sea-island fibre reduction rate is
98.9%, the polyurethane rate of recovery is 99.6%.
Example IV：
(1) raw material prepares：Extra large component is carboxylic prepared by polyether Glycols and aromatic diisocyanate reaction
Polyurethane elastomer, melting temperature are 200 DEG C；Island component is nylon 6, and the mass ratio of extra large component and island component is 40：60.
(2) spinning：Routinely 64 island melt composite spinning techniques carry out, i.e., respectively through spiral shell after sea component and the drying of island component
Bar extruder squeezes, melting, after metering through filament spinning component spinning, oil after cooling and shaping, coiling, then boundling, drawing-off, curling,
Sizing, severing obtain staple fiber.
(3) it is reduced：Sea-island staple fiber is put into the sodium hydrate aqueous solution that pH is 11-11.5 and is reduced, the fibre after decrement
Dimension washing obtains micro staple fiber.
(4) polyurethane recycles：Aqueous solution after decrement is 3-3.5 with sulphur acid for adjusting pH value, polyurethane Precipitation, filtering
Recycle polyurethane.
Sea-island fibre fiber number 4.5dtex, intensity 5.1cN/dtex prepared by the embodiment；Sea-island fibre reduction rate is
99.2%, the polyurethane rate of recovery is 99.1%.
Claims (8)
1. a kind of using decrement method of the water soluble polyurethane elastomer as extra large sea-island fibre in a mild condition, feature exists
In：By the way that prepared by water soluble polyurethane elastomer and island component composite spinning sea-island fibre, the sea-island fibre is water-soluble in alkalinity
Fiber decrement is carried out in liquid, the aqueous polyurethane after decrement is adjusted to the recycling of acid condition progress sea component；The water
Solvable polyurethane elastomer be its hydrophilic radical be carboxyl or carboxyl, sulfonic group combination, and potential hydrophilic radical before spinning and
Spinning process is the elastomer of closing, and the elastomer is soluble in the alkaline aqueous solution that pH is 10-12, is in pH value
2.0-4.0 acidic aqueous solution in be undissolved.
2. a kind of subtracting in a mild condition using water soluble polyurethane elastomer for extra large sea-island fibre as described in claim 1
Amount method, it is characterised in that：The water soluble polyurethane elastomer is polyether Glycols and aliphatic or aromatic diisocyanates
Performed polymer prepared by ester reaction, then the linear polymer formed after hydrophilic chain extender chain extension, melting temperature 170-210
℃。
3. a kind of subtracting in a mild condition using water soluble polyurethane elastomer for extra large sea-island fibre as described in claim 1
Amount method, it is characterised in that：Routinely technique carries out the composite spinning, i.e., respectively through screw rod after sea component and the drying of island component
Extruder squeezes, melting, after metering through filament spinning component spinning, oil after cooling and shaping, coiling, then boundling, drawing-off, sizing obtain
Long filament or boundling, drawing-off, curling, sizing, severing obtain staple fiber.
4. as described in claim 1 or 3 it is a kind of using water soluble polyurethane elastomer as sea sea-island fibre in a mild condition
Decrement method, it is characterised in that：The quantity on the sea-island fibre island is 7-64.
5. as described in claim 1 or 3 it is a kind of using water soluble polyurethane elastomer as sea sea-island fibre in a mild condition
Decrement method, it is characterised in that：The sea-island fibre sea component is (25-60) with island components by weight:(75-40).
6. as described in claim 1 or 3 it is a kind of using water soluble polyurethane elastomer as sea sea-island fibre in a mild condition
Decrement method, it is characterised in that：The island component is nylon 6.
7. a kind of subtracting in a mild condition using water soluble polyurethane elastomer for extra large sea-island fibre as described in claim 1
Amount method, it is characterised in that：A kind of or combination of the alkali for sodium hydroxide and potassium hydroxide used in the fiber decrement.
8. a kind of subtracting in a mild condition using water soluble polyurethane elastomer for extra large sea-island fibre as described in claim 1
Amount method, it is characterised in that：Aqueous polyurethane after the decrement is adjusted to the acid condition that pH value is 2.0-4.0 and carries out sea
The recycling of component adjusts pH value using a kind of or combination in hydrochloric acid and sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510604060.9A CN105297161B (en) | 2015-09-22 | 2015-09-22 | It is a kind of using water soluble polyurethane elastomer as the sea-island fibre decrement method in a mild condition in sea |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510604060.9A CN105297161B (en) | 2015-09-22 | 2015-09-22 | It is a kind of using water soluble polyurethane elastomer as the sea-island fibre decrement method in a mild condition in sea |
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| CN105297161A CN105297161A (en) | 2016-02-03 |
| CN105297161B true CN105297161B (en) | 2018-06-29 |
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| CN201510604060.9A Expired - Fee Related CN105297161B (en) | 2015-09-22 | 2015-09-22 | It is a kind of using water soluble polyurethane elastomer as the sea-island fibre decrement method in a mild condition in sea |
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| CN107604533B (en) * | 2017-09-19 | 2019-10-18 | 四川大学 | A kind of elastic force superfine fiber chemical leather and its environmental-friendly preparation method |
| CN107629187A (en) * | 2017-09-20 | 2018-01-26 | 四川大学 | A kind of insoluble controllable method for preparing polyurethane elastic body of water-soluble water |
| CN108048922A (en) * | 2017-12-25 | 2018-05-18 | 四川大学 | A kind of environmental-friendly preparation method of not figured type polypropylene superfine fiber |
| CN111704417B (en) * | 2020-07-21 | 2022-06-07 | 恩平市建安混凝土搅拌有限公司 | Preparation method of ultrahigh-strength concrete |
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| CN101273168B (en) * | 2005-09-30 | 2011-04-20 | 可乐丽股份有限公司 | Leather-like sheet and method of manufacturing the same |
| WO2008093850A1 (en) * | 2007-02-01 | 2008-08-07 | Kuraray Co., Ltd. | Polishing pad and process for production of polishing pad |
| CN102119069B (en) * | 2008-08-08 | 2015-04-15 | 可乐丽股份有限公司 | Polishing pad and method for manufacturing the polishing pad |
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