CN105399920A - Water-soluble and spinnable polyurethane elastomer prepared based on RIM technology - Google Patents
Water-soluble and spinnable polyurethane elastomer prepared based on RIM technology Download PDFInfo
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- CN105399920A CN105399920A CN201510783576.4A CN201510783576A CN105399920A CN 105399920 A CN105399920 A CN 105399920A CN 201510783576 A CN201510783576 A CN 201510783576A CN 105399920 A CN105399920 A CN 105399920A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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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
- C08G2120/00—Compositions for reaction injection moulding processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a water-soluble and spinnable polyurethane elastomer prepared based on the RIM technology. A linear polymer is prepared from potential hydrophilic group-containing dibasic alcohol components and diisocyanate components through the RIM technology. Because the elastomer contains a potential hydrophilic group, water-soluble and water-insoluble mutual conversion can be realized on the premise that main chains of molecules are not damaged; before being released, the hydrophilic group is a non-hydrophilic elastomer which can be used for spinning of island fiber sea components; after being released, the hydrophilic group is a water-soluble high molecular compound which can be subjected to reduced fibrillation under mild conditions; and after being sealed, the hydrophilic group is water-insoluble, so that recovery can be realized under mild conditions. Organic solvents or waste water containing organic matters are not generated in the processes, thereby being favorable for environmental protection.
Description
Technical field
The present invention relates to Polyurethane Thermoplastic Elastomer field, refer to especially a kind of prepare based on RIM technology water soluble, can polyurethane elastomer be spun.
Background technology
Sea-island fibre is the profile fibre two kinds of incompatible polymers being carried out co-blended spinning or conjugate spinning manufacture, island component polymer is scattered in another kind of sea component polymer with the form of maintaining fiber, after sea component is removed, just obtain the ultra-fine fibre of island component stroke; Ultra-fine fibre has fiber number thin, soft, has large specific surface sum capillary effect, has good moisture absorption to fall apart the feature such as moist.
Ultra-fine fibre occupies an important position in national economy, only nearly 100,000,000 meters of the output of domestic superfine fiber chemical leather in 2014.Domestic superfine fiber chemical leather mainly uses sea-island fibre to prepare, benzene decrement or Alkali reduction mode is adopted to carry out: benzene decrement uses toluene to make solvent to be dissolved by the extra large component in fiber-polyethylene, remove, although benzene decrement is carried out in relatively airtight environment, but decrement and polyethylene removal process still have a large amount of toluene (85-150g/1kg fiber) volatilization, cause severe contamination and the wasting of resources; Alkali reduction is by extra large component-terylene hydrolysis, removal in the sodium hydroxide lye of 10%, terylene hydrolysis becomes terephthalate and ethylene glycol, produce a large amount of waste water containing phthalate and ethylene glycol simultaneously, both not easily reclaimed and high value added utilization, cause again COD content in waste water high, not easily degrade, direct discharge also causes serious environmental pollution and the wasting of resources.
The major cause that sea-island fibre decrement pollutes be be not applicable to melt-spinning polymer elastomer as sea component, if this polymer elastomer can spinning, again can decrement recycling in a mild condition, then would not produce organic pollutant and contain organic waste water in a large number in decrement and removal process, its problem of environmental pollution just can be readily solved.
Summary of the invention
Main purpose of the present invention is the shortcoming overcoming prior art, and provide a kind of water soluble, the spinnable polyurethane elastomer prepared based on RIM technology, this elastomerics can prepare the ultra-fine fibre with island structure as extra large component and nylon (PA) conjugate spinning.This elastomerics itself is containing potential hydrophilic radical, water-soluble and not water-soluble mutual conversion can be realized under the prerequisite of not saboteur's main chain, can be dissolved in the water urethane recycling in a mild condition that realize decrement, can will be dissolved in the water after decrement, in decrement and removal process, do not produce organic waste, the waste water after decrement also can recycled for multiple times.
The present invention adopts following technical scheme:
Adopt RIM technology to prepare water soluble, can polyurethane elastomer be spun, prepare especially by following steps:
A. diol component mixed and preserved by the storage tank of insulation 40-60 DEG C, being labeled as A material, diisocyanate component is preserved by the storage tank being incubated 40-60 DEG C, being labeled as B material;
B. in measuring apparatus is expected with B in A material, the ratio of active group 1:1-1.05 mol ratio delivers to high-speed mixing head mixing 3-15 second, after extruding, material is placed in curing mold;
C. the mould filling material is taken out material, granulation after slaking 2-10 hour under the condition of 80-110 DEG C, obtain water soluble, can polyurethane elastomer be spun.
A material is made up of (1) oligomeric diols, (2) hydrophilic chain extender, (3) catalyzer and optional (4) small molecule chain extender:
(1) oligomeric diols be hydrolysis, a kind or its combination in the polytetrahydrofuran dibasic alcohol of relative molecular mass 100-4000;
(2) hydrophilic chain extender is
n,N-dihydroxy ethyl maleinamic acid or
n,N-dihydroxy ethyl maleinamic acid and fusing point lower than 60 DEG C, relative molecular mass is the combination containing sulfonic dibasic alcohol of 500-1500;
(3) catalyzer is: the one in organo-bismuth, organic silver and/or organotin;
(4) small molecule chain extender is a kind or its combination in ethylene glycol, BDO, hexylene glycol, quadrol, hexanediamine.
Diisocyanate component is the one in MDI100, MDI50 or liquefied mdi.
Water soluble, can to spin in polyurethane elastomer containing sulfonic dibasic alcohol and
n,Nthe content of-dihydroxy ethyl maleinamic acid is the 15-23% of elastomerics gross weight, and is no more than 3% of elastomerics gross weight containing the content of sulfonic dibasic alcohol.
The active group of A material is hydroxyl and amino, and the active group of B material is isocyanate groups.
From the above-mentioned description of this invention, compared with prior art, the present invention has following beneficial effect:
1, water soluble, polyurethane elastomer can be spun containing potential hydrophilic radical, when hydrophilic radical does not discharge, polyurethane elastomer is not hydrophilic, thus its applicable melt-spinning technology; The acid-basicity of adjustment environment discharges and the hydrophilic radical in occlusive polyurethane, can change the water-soluble of polyurethane elastomer, thus can as the sea component of sea-island fibre; During as sea-island fibre sea component, fiber decrement process, sea component removal process do not damage water soluble, the molecular backbone chain that can spin polyurethane elastomer, again can utilize, do not cause the wasting of resources after recovery; Without organic emission in process, do not cause environmental pollution.
2, adopt reaction injection moulding technology to prepare water soluble, can spin polyurethane elastomer, have speed of response fast, course of processing energy consumption is low, low cost and other advantages.
3, as the spinning of sea-island fibre sea component, time, existing island conjugate spinning equipment can be used to produce, can be ultra-fine fibre industry value chain and scheme is provided.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are just for being further detailed the present invention; limiting the scope of the invention can not be interpreted as; the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above, still belongs to protection scope of the present invention.
Embodiment one:
A material is 110 weight part PTMG1000,40 weight part dihydroxy ethyl maleinamic acids, the organotin catalysts of 0.1 weight part, the mixture of 8 weight part BDO compositions; B material is MDI50.A, B expect 40 DEG C of insulations in storage tank respectively.Through measuring apparatus with B, A material is expected that delivering to high-speed mixing head by the mol ratio of active group 1:1.01 mixes 10 seconds, after extruding, material is placed in curing mold, then under material and curing mold being put in the condition of 110 DEG C, slaking took out material after 6 hours, granulation obtains water soluble, can spin polyurethane elastomer, and hydrophilic radical content is 15.5%.
Embodiment two:
A material is the organic silver catalyzer of 110 weight part PTMG1000,6 weight part hundred source 3306,56 weight part dihydroxy ethyl maleinamic acids, 0.2 weight part; B material is MDI100.A, B expect 46 DEG C of insulations in storage tank respectively.Through measuring apparatus with B, A material is expected that delivering to high-speed mixing head by the mol ratio of active group 1:1.01 mixes 5 seconds, after extruding, material is placed in curing mold, then under material and curing mold being put in the condition of 90 DEG C, slaking took out material after 10 hours, granulation obtains water soluble, can spin polyurethane elastomer, hydrophilic radical content is 22.79%, wherein containing sulfonic glycol content 2.21%.
Embodiment three:
A material is the organic bismuth catalyst of 220 weight part PTMG2000,58.5 weight part dihydroxy ethyl maleinamic acids, 0.2 weight part; B material is MDI100.A, B expect 46 DEG C of insulations in storage tank respectively.Through measuring apparatus with B, A material is expected that delivering to high-speed mixing head by the mol ratio of active group 1:1.01 mixes 10 seconds, after extruding, material is placed in curing mold, then under material and curing mold being put in the condition of 100 DEG C, slaking took out compound after 10 hours, obtain water soluble, can spin polyurethane elastomer, hydrophilic radical content is 15.46%.
Claims (5)
1. the water soluble prepared based on RIM technology, can a polyurethane elastomer be spun, it is characterized in that: adopt RIM technology to prepare water soluble, can polyurethane elastomer be spun, prepare especially by following steps:
A. diol component mixed and preserved by the storage tank of insulation 40-60 DEG C, being labeled as A material, diisocyanate component is preserved by the storage tank being incubated 40-60 DEG C, being labeled as B material;
B. in measuring apparatus is expected with B in A material, the ratio of active group 1:1-1.05 mol ratio delivers to high-speed mixing head mixing 3-15 second, after extruding, material is placed in curing mold;
C. the mould filling material is taken out material, granulation after slaking 2-10 hour under the condition of 80-110 DEG C, obtain water soluble, can polyurethane elastomer be spun.
2. as claimed in claim 1 a kind of prepare based on RIM technology water soluble, can polyurethane elastomer be spun, it is characterized in that: described A material is made up of (1) oligomeric diols, (2) hydrophilic chain extender, (3) catalyzer and optional (4) small molecule chain extender:
(1) oligomeric diols be hydrolysis, a kind or its combination in the polytetrahydrofuran dibasic alcohol of relative molecular mass 100-4000;
(2) hydrophilic chain extender is
n,N-dihydroxy ethyl maleinamic acid or
n,N-dihydroxy ethyl maleinamic acid and fusing point lower than 60 DEG C, relative molecular mass is the combination containing sulfonic dibasic alcohol of 500-1500;
(3) catalyzer is: the one in organo-bismuth, organic silver and/or organotin;
(4) small molecule chain extender is a kind or its combination in ethylene glycol, BDO, hexylene glycol, quadrol, hexanediamine.
3. as claimed in claim 1 a kind of prepare based on RIM technology water soluble, can polyurethane elastomer be spun, it is characterized in that described diisocyanate component is the one in MDI100, MDI50 or liquefied mdi.
4. as claimed in claim 1 a kind of prepare based on RIM technology water soluble, can polyurethane elastomer be spun, it is characterized in that: described water soluble, can to spin in polyurethane elastomer containing sulfonic dibasic alcohol and
n,Nthe content of-dihydroxy ethyl maleinamic acid is the 15-23% of elastomerics gross weight, and is no more than 3% of elastomerics gross weight containing the content of sulfonic dibasic alcohol.
5. as claimed in claim 1 a kind of prepare based on RIM technology water soluble, can polyurethane elastomer be spun, it is characterized in that: the active group of described A material is hydroxyl and amino, and the active group of B material is isocyanate groups.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107604533A (en) * | 2017-09-19 | 2018-01-19 | 四川大学 | A kind of elastic force superfine fiber chemical leather and its environment-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 |
CN109295533A (en) * | 2018-09-18 | 2019-02-01 | 广东山石微量元素研究院(普通合伙) | A kind of spandex fibre of the micro mist containing Khotan jade and preparation method thereof |
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CN1242385A (en) * | 1998-07-06 | 2000-01-26 | 可乐丽股份有限公司 | Thermoplastic polyurethanes, polyurethane elastic fibers therefrom, and method for producing the fibers |
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2015
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CN1242385A (en) * | 1998-07-06 | 2000-01-26 | 可乐丽股份有限公司 | Thermoplastic polyurethanes, polyurethane elastic fibers therefrom, and method for producing the fibers |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107604533A (en) * | 2017-09-19 | 2018-01-19 | 四川大学 | A kind of elastic force superfine fiber chemical leather and its environment-friendly preparation method |
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 |
CN109295533A (en) * | 2018-09-18 | 2019-02-01 | 广东山石微量元素研究院(普通合伙) | A kind of spandex fibre of the micro mist containing Khotan jade and preparation method thereof |
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