CN101126181A - Polyurethaneurea elastic fiber and method for preparation thereof - Google Patents
Polyurethaneurea elastic fiber and method for preparation thereof Download PDFInfo
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- CN101126181A CN101126181A CNA2007101421900A CN200710142190A CN101126181A CN 101126181 A CN101126181 A CN 101126181A CN A2007101421900 A CNA2007101421900 A CN A2007101421900A CN 200710142190 A CN200710142190 A CN 200710142190A CN 101126181 A CN101126181 A CN 101126181A
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/72—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyureas
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
Abstract
The present invention relates to a preparation method of a polyurethaneurea elastic fiber, in which the sub-reaction and reaction speed are regulated during the prepolymer reaction by adding 1- functional monoalcohol and an organic acid in order to provide an elastic fiber exhibiting excellent uniformity during the weaving and processing of a synthetic fiber such as polyester or nylon, a static mixer having excellent stirring efficiency and a tubular reactor are used for constant even reaction to give a primary uniform polymer, the primary polymer is dissolved in a solvent using a high shear mixer, and a chain extender and chain terminator are added with regulation to give the secondary polymer having intrinsic viscosity of at least 1.0. In the present invention, a high shear mixer for the secondary polymerization exhibiting at least 80% of stirring efficiency and a cylindrical pipe shaped static mixer were used to inhibit sub-reaction and gelation to give a secondary polymer exhibiting stable spinning.
Description
Technical field
The present invention relates to a kind of polyurethaneurea elastic fiber, this fiber has excellent uniformity and spinnability, and is provided for the weaving performance (textile property) of the excellence that interweaves with synthetic fiber such as polyester and nylon.
Background technology
In order to prepare polyurethaneurea elastic fiber, obtain polymer by the prepolymer chain of using diamines to increase the isocyanates end, then carry out dry spinning and melt spinning, above-mentioned isocyanates end is synthesized by the pure and mild excessive organic diisocyanate of macromolecular multi-component.Made polyurethaneurea elastic fiber with polyamide fiber or polyester fiber interweave with natural fabric (cross-weave) become the clothes of various elasticity of demand, for example corset, socks, pantyhose, swimming suit etc.
Although polyurethaneurea elastic fiber has the excellent resilience of the hydrogen bond that comes from the hard segment of being made up of a large amount of urea groups, it has weakness aspect heat resistance, and this is because under the stimulation of high temperature, and hard segment wherein moves easily.Thereby, when polyurethaneurea elastic fiber interweaves by high-temp dyeing and synthetic fiber, when perhaps secondary dyeed for the undies that prepare the color matching of clothing such as needs, the elastomer of fabric may fluff or become single cord, causes the elasticity and the degraded appearance of product.This has been all common problems that comprise the polyurethane-base elastomer of polyurethaneurea elastic fiber.
Therefore, a lot of polyurethaneurea elastic fiber production companies have attempted various ways and have improved its heat resistance.Some companies produce the improved polyurethaneurea elastic fiber product of heat resistance, but but still are in the trouble of correspondingly sacrificing other physical property such as elastic recovery rate shape stability and elasticity and very difficult control production technology.
For preparation is keeping elasticity and stable on heating polyurethane-urea under the synthetic dyeing technology or under other secondary dyeing condition, use independently cahin extension agent of ethylenediamine conduct, because the linearity of ethylenediamine and the strong cohesion between hard segment cause heat resistance to be improved.Yet in propagation process, the very fast acceleration of its meeting reaction speed causes side reaction.In addition, the strong cohesion between hard segment causes gelation, causes because viscosity is inhomogeneous, instability causes difficulty in spinning, and the intensity of elastomer and elasticity reduce.
As a part of effort that overcomes the above problems, Japanese kokai publication sho 44-22113 describes: use a spot of 1-official to come the reaction speed of Quality Initiative growth and to prevent side reaction by single group alcohol.But for this method, other physical property of elastomer such as intensity and flexible sacrifice are that inevitably this must be improved.
In Japanese kokai publication sho 58-59213 and United States Patent (USP) 5,100,999, the stable on heating conventional method of raising polyurethaneurea elastic fiber has been described.According to these descriptions, by adopting polycaprolactone glycol and PCDL to form the soft chain segment of polyurethane-urea as polyalcohol, make the stronger heat resistance of improving of structure of crystallization crosslinking points, but this improvement effect is not very satisfactory, and decreases with the polyurethane-urea resilience in comparison response rate of using polyether polyol.
1-110520 is described according to Japanese kokai publication hei, in order to improve heat resistance, uses the diamino-diphenyl urea to improve the crosslink density of urea groups hard segment in the diamine structure as cahin extension agent.
Yet this method may be damaged stability of spinning process, and this is because formed crosslinked between the polymer in the pre-spinning solution of levels of viscosity continually varying.
Japanese kokai publication hei 4-100919 describes, with the triamine polymerization to improve heat resistance as spinning additive in advance.Since introduce this particular procedure method before spinning since, a lot of polyurethaneurea elastic fiber production company has used triamine to improve heat resistance as cahin extension agent or additive, but improvement effect still can not be satisfactory.Also used a kind of cahin extension agent altogether as the heat settability (heat settability) that reduces, viscosity and stable on heating replenishing, but effect still have problems.In addition, excessive use crosslinking agent can bring viscosity problem in technology.
Summary of the invention
Even one object of the present invention be to provide a kind of weave and the processing (comprising high-temp dyeing) of dyeing after also have excellent weaving performance polyurethaneurea elastic fiber, above-mentioned weaving performance comprises elastic recovery rate, heat settability and intensity.
Thereby another object of the present invention is to provide a kind of polyurethaneurea elastic fiber by at first preparing primary polymer to reduce gelation and side reaction and to help last spinning.
Another object of the present invention is to provide a kind of polyurethaneurea elastic fiber with uniform physical properties, its the compositions of additives by making the secondary polymerization thing and the stabilized with mixture of generation prepare, to obtain peace and easy spinnability and uniform performance.
A further object of the invention is to provide a kind of can provide excellent mixing efficiency and stable polymerization, and a kind of preparation method who adopts the polyurethaneurea elastic fiber with excellent heat resistance, elastic recovery rate, heat settability and intensity of said method is provided.
A further object of the invention is to provide a kind of high mixing efficiency and the very high polymerization unit that is used to react of stability.
Technical scheme
For realizing above purpose, the invention provides a kind of preparation method of new elastomer, this elastomer shows excellent heat resistance, heat settability, uniformity and elastic recovery rate, but does not have gelation, and this method may further comprise the steps:
(a) by under 40～50 ℃ of temperature, more preferably under 45 ℃, in static mixer, mix the polytetramethylene ether diol (PTMEG) and the diphenyl methane 4 that constitute by the pure and mild 5～20ppm organic acid of 500～2000ppm 1-official energy single group, 4 '-vulcabond (MDI), with its in cylinder tubulose continuous polymerization reaction tube under 70～95 ℃, preferably under 75～85 ℃, carry out polymerization, preparation viscosity is the polyurethane prepolymer primary polymer of 500～700 pools, and wherein terminal unreacted diisocyanate content is up to 3mol%;
(b) by under 40 ℃, stir N, primary polymer in the N-methylacetamide solvent, by ethylenediamine/1, cahin extension agent and chain terminating agent that 2-diaminopropanes/diethylamine is formed, the preparation apparent viscosity is the secondary polymerization thing solution of 2000～3500 pools (solids content 37%):;
(c) by add compositions of additives in polymer solution, preparation has the spinning solution (spinning dope) of 3500～5000 pools (40 ℃, solids content 37%); And
(d) by above-mentioned spinning solution being carried out spinning, the preparation polyurethaneurea elastic fiber.
The preparation of prepolymer is designed to monomer and keeps its performance equably and polymerization in whole continuous polymerization process among the present invention, and make last elastomer have the performance of rule thus, simultaneously, by using 1-official to come reaction speed by the pure and mild organic acid of single group as the polymerization speed conditioning agent.Usually, add 1-official and can be used for polymerization by single group alcohol, with rapid quickening and gelation or the excess stickiness increase that prevents the carbamate polymerization.In the present invention, the pure and mild organic acid of 1-official's energy single group particularly phosphoric acid uses together, is used to prevent the quick variation of reaction speed, and guarantees stable polymerisation thus.1-official of the present invention can single group alcohol n-butanol preferably, and the content of n-butanol in polytetramethylene ether diol (polytetramethyleneetherglycol) 500～2000ppm preferably.If content is lower than 500ppm, it is difficult that the control of reaction will become, yet if content, just means 1-functional group group greater than 2000ppm to overuse, will reduce the molecular weight of polymer, and the physical property of fabric will descend after the spinning.In the present invention, organic acid, especially phosphoric acid can use by single group alcohol with 1-official, and at this moment, the content of phosphoric acid in polytetramethylene ether diol is 5～20ppm.If content is in above-mentioned scope, reaction speed will suitably be controlled, and the physical property of final elastomer will keep stable.
According to the present invention, PTMEG is mixed continuously with the mixture of the organic acid that mixes by measuring pump, a 1-pure and mild MDI of sense single group in static mixer, in the cylindrical duct reactor, carry out continuous polymerization afterwards.Being blended under 40～50 ℃ in the static mixer carried out, with the polymerization that prevents from not wish to take place.If mix being lower than under the said temperature, ensuing polymerization can not be caused fully, yet if mix being higher than under the said temperature, polymerization rate will be very fast, and gelation can take place.Well-mixed polymeric compositions in the cylindrical duct reactor 70～95 ℃ of following polymerizations 100～200 minutes.The duration of polymerization is depended on the physical property of final products, but preferred 120～150 minutes.Drink favourable production technology for the required physical property of final elastomer, final polyurethane prepolymer and primary polymer contain the unreacting isocyanate of 3mo1% at the most at the prepolymer end, and preferably have the viscosity of 500～700 pools.If the content of unreacting isocyanate is higher than 3mol%, then the formation of primary polymer will can be not successful, and the molecular weight of the polyurethane-urea of secondary polymerization can be too low, and the viscosity of normal level can not be provided, and this physical property that just means the after polymerization product can be very poor.
The preparation method of secondary polymerization thing is described in detail below.The primary polymer that makes above-mentioned preparation is by the filter of 10～20 μ m, stays any composition on the gel, selective polymer afterwards with removal.With polymer and solvent N, the N dimethylacetylamide is packed in the dissolvers (dissolver) together, carries out then about 1 minute or preferred 20～30 seconds vigorous stirring, makes it be cooled to 15～45 ℃, to dissolve unreacted vulcabond fully.With cahin extension agent ethylenediamine and 1, the 2-diaminopropanes is with 70～90: the ratio of 30～10mol% is added in the above-mentioned solvent.Primary polymer solution is joined in the after polymerization reactor that blade (blade) is housed that comprises cooling system simultaneously.Be aggregated in 10 minutes and finish.The temperature of polymer reactor is below 85 ℃.
The mixing speed of blade is controlled by reponse system in the secondary polymerization reaction device, and purpose is to make the mixing efficiency in exit to be at least 80%.The cahin extension agent amido of mixing efficiency by unreacted polymer ends in the secondary polymerization thing included whole before percentage calculation in the amido (preamine group).If mixing efficiency is lower than 80%, the mixing of primary polymer and amine will be unfavorable in the second reactor so, and this causes disordered chain propagation, gelation, the uncertain adhesion of polymer in the production process, and weaving performance irregular after the spinning.By rising heat of stirring and reaction heat, caused side reaction and gelation for improving the excessive spinning speed that improves of mixing efficiency, thereby increased the viscosity unstability of spinning solution and the scrambling of weaving performance.Therefore, mixing efficiency is controlled at least 80% by high shear mixing, more preferably 80～100%, special result of the present invention.
Take out polymer from the outlet of secondary polymerization reaction device.In order to measure the amine content of spinning solution and polymer ends, each polymer dissolution in N,N-dimethylacetamide solution, is used 0.1N HCl titration afterwards.Polymer is made film, dry then.Polymer is dissolved in the N,N-dimethylacetamide solution once more, uses 0.1N HCl titration then.Measure the content of terminal amine in the polymer.The ratio calculating of amine content in the content of the mixing efficiency of reactor by terminal amine in the polymer and the spinning solution.
Control the viscosity of final polymer by the content of diethylamine in cahin extension agent solution being adjusted to 1/20 (amine equivalent ratio).The amount of amine is added in adjusting in secondary polymerization reaction, so that the amine of final polymer ends reaches 40～60meq/kg.Determine the mixing speed of reaction,, measure mixing efficiency in the exit of secondary polymerization reaction device so that the reaction efficiency between primary polymer and the amine reaches at least 80%.
Solids content by the synthetic polyurethaneurea polymer of chain growth and chain termination is approximately 32～37%, makes after polymerization thing solution have the apparent viscosities of about 2800 pools in the time of 40 ℃.The inherent viscosity of polymer is approximately 1.0 in the N,N-dimethylacetamide solution of 0.5g/100ml.
As above-mentioned explanation, in polymerization process, the preferred ratio of ethylenediamine (cahin extension agent) and 1,2 diaminopropanes is 70～90: 30～10mo1%, more preferably 80: 20mol%.Chain terminating agent is 1/15～1/30 with the ratio of the content of the amine that is used for cahin extension agent, more preferably 1/20.Most preferably, as cahin extension agent and 1, the 2-diaminopropanes is with 80 with ethylenediamine: the mixed of 20mol%.Along with the increase of ethylenediamine, the hydrogen bond force in the polymer increases, and makes viscosity become unstable.Along with 1, the increase of 2-diaminopropanes, it is stable that viscosity becomes, but heat resistance is not improved.Simultaneously, the preferred ratio of chain terminating agent diethylamine and cahin extension agent is 1/20, and this is suitable for preparing the polymer with stable viscosity and physical property.If the content of diethylamine is too little, then secondary polymerization speed can not be controlled, and the molecular weight of polymer can increase, and cause unsettled high viscosity.On the contrary, if the content of diethylamine is too high, secondary polymerization speed will reduce, and the molecular weight of polymer is less like this, causes viscosity low, and the weaving performance after the spinning is poor.
For remaining in unreacted isocyanate groups in prepolymer and the primary polymer, the content of cahin extension agent and chain terminating agent amine is 2～4mol%.At this moment, if the consumption of amine is less than 2mol%, along with the scrambling increase of polymer, the viscosity of spinning solution will increase.If it is excessive that the content of amine, just means that amine uses greater than 4mol%, the molecular weight of polymer will reduce together along with viscosity, and the yarn qualities that causes spinning to obtain descends.The viscosity of secondary polymerization thing polyurethaneurea polymer is preferably 2000～3500 pools, and (40 ℃, solids content: 37%), more preferably viscosity is 2500～3000 pools.If the viscosity of secondary polymerization thing is 2000 pools at the most, and is too low with regard to meaning for polymer and fiber production viscosity, weaving performance can be very poor, and spinning technique can not stably carry out.Therefore, in this case, for forming the stable viscosity that enough spinning are used, require to prolong the curing time, this is that economy and technical elements are undesirable.Simultaneously, if viscosity is at least 3500 pools, too high with regard to meaning for viscosity with regard to the polymer, the viscosity Control in the subsequent handling will be very difficult, thereby still be difficult to carry out stable spinning.In addition, under the high viscosity condition, variously be used to react the additive that is added and also can evenly do not disperse, produce the very low product of quality.
Compositions of additives of the present invention is described in detail later.For helping conventional elastomer to keep persistence and white, and have improved anti-discoloration (preventing flavescence) and a stainability, and the damage that prevents mechanical performance, brightening agent, waste gas stabilizing agent, antioxidant, viscosity and unwind (unwinding) performance enhancers, stainability reinforcing agent and spinning stabilizing agent are mixed, and this mixture is joined in the after polymerization thing polyurethane-urea.
Among the present invention, with respect to the various additives of the following interpolation of gross weight of elastomer, the diethylenediamine that adds 50～200ppm is as the spinning stabilizing agent, add the titanium dioxide of 0.1～5.0wt%, add 1,1 of 0.1～5.0wt%, 1 ', 1 '-tetramethyl-4,4 ' (methylene-two-right-phenylene) diaminourea [HN-150] add the 2-[4 of 0.1～3.0wt% as the waste gas stabilizing agent, 6-two (2, the 4-xylyl)-1,3,5-triazines-2-yl]-5-(octyloxy) phenol [CYASORB
UV-1164D (Cynamid, USA)] as light stabilizer, add 1 of 0.1～5.0wt%, 3,5-three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethylbenzene)-1,3,5-triazine-2,4,6-1H, 3H, 5H)-triketone (trion) CYANOX 1790 (R) (Cynamid, USA) as antioxidant, the dolomol that adds 0.1～3.0wt% improves the adhesion and the performance of unwinding, and (N, N-diethyl-2-ethylaminoethanol methacrylate is as the stainability reinforcing agent to add 0.1～3.0wt% poly-.At this, in order to improve the heat resistance of elastomer, prevent the precipitation that the inorganic additive cohesion causes, and in the even mixing of polymer and additive, play a part certain simultaneously, diethylenetriamines is not to add as cahin extension agent, but adds as forming crosslinked additive when the high temperature spinning.Even mixing between final polymer and additive is very important, for the even mixing between final polymer and additive, uses the static mixer of cylinder tubulose at this.The solid content of the polyurethane urea solutions (spinning solution) of preparation is 37%, and viscosity is 3500～5000 pools (under 40 ℃), and this is very suitable for spinning.
To also be very important with the storage temperature of the additive slurry of final mixed with polymers.If the storage temperature of this additive is higher than 60 ℃, the increase of slurry viscosity will surpass the settling rate that factor caused that is triggered by the micro Brownian motion that reduces every kind of additive component and reduce, cause the cohesion of additive slurry, and along with the reduction of additive slurry quality, settling velocity is quickened.In addition, at high temperature, the blocking period of additive filter also can shorten, and causes product quality to descend.If the storage temperature of additive slurry is lower than 40 ℃, then the relative viscosity of additive slurry will increase along with the increase of additive filter differential pressure, make the technical process instability.In addition, the micro Brownian motion of every kind of additive component weakens at low temperatures, shows that cohesion will quicken, and cause the additive quality to reduce, and the blocking period of filter shortens.Thereby the storing temperature of additive slurry is preferably in 40～50 ℃ scope.
Preparation method of the present invention describes in detail with preferred implementation hereinafter, and has provided the additional explanation explanation of concrete composition and content respectively.
The specific embodiment
Before describing preferred implementation of the present invention, explain the evaluation method of various performances in this article.
1) measurement of polymer viscosity
By the viscosity of chain growth to the polymer of chain termination, viscosity applying unit pool is represented when measuring 40 ℃ by the use Brookfield viscometer.
2) measurement of gel particles in the polymer
In 1%LiCl DMAc electrolyte, concentration is 0.5% with polymer dissolution, and the quantity of gel particles calculates by Coulter counter (Beckman) in the polymer.
3) measurement of mixed with polymers efficient
Take out polymer from the outlet of secondary polymerization reaction device.In order to measure the amine content of spinning solution and polymer ends, each polymer all is dissolved in the N,N-dimethylacetamide solution, use the 0.1NHCl titration afterwards.Polymer is made film, dry then.Polymer is dissolved in the N,N-dimethylacetamide solution once more, uses 0.1N HCl titration afterwards.Measure the content of terminal amine in the polymer.The mixing efficiency of reactor calculates by the ratio of terminal amine content in the polymer and the amine content in the spinning solution.
4) mensuration of intrinsic viscosity
In order to measure the intrinsic viscosity of polymer, at 100ml N, in the N-dimethylacetamide solution, use Ubbelohde viscometer to measure the viscosity of solution the 0.5g polymer dissolution.
5) fracture strength, elongation at break
Fracture strength (g/d) and elongation at break (%) are measured 20 ℃ the time, under the 65%RH with general tensile test machine (UTM Instrong).(sample length: 5cm, draw speed: 50cm/min)
6) elastic recovery rate
With 10cm is to mark on sample at interval, afterwards sample is elongated 300%.Sample kept 24 hours under the state of elongation, replied from elongation state then.Reply after 10 minutes, measure the length after replying.
ER(％)＝[(Ls-La)/(Ls-Lo)]×100
(wherein, Lo refers to the distance between the sample mark, and Ls refers to that sample extends 300% o'clock length, and La refers to the length after sample is replied from elongation state.)
7) damp and hot elastic recovery rate
With 10cm is to mark on sample at interval.After elongating 100%, the samples with water steam was handled 60 minutes down at 130 ℃, allowed it reply then from elongation state.Length after measure replying, and be expressed as ratio with the length of untreated samples.Elastic recovery rate is high more, and then heat resistance is high more, but but the heat shape stability is lower.
Damp and hot elastic recovery rate=[LSs-Lt)/Lo] * 100
(wherein, Lo refers to the distance between the sample mark, and Ls refers to that sample extends 100% o'clock length, and Lt refers to the length after sample is replied from elongation state.)
8) xeothermic strength retention ratio
Sample elongates 100%, handles 1 minute with hot blast under 180 ℃ then.With general tensile test machine measured intensity, the ratio of the intensity after the dry heat treatment and the intensity of untreated samples is regarded as strength retention ratio.Strength retention ratio is high more, and heat resistance is high more.
Reality of the present invention and at present preferred embodiment below embodiment and comparative example in illustrate.
Yet, should be realized that consider these disclosed technology, those skilled in the art can carry out changes and improvements in scope and spirit of the present invention.
Embodiment 1
(PTMEG, MW:1815) (n-butanol MW:74.12) with 10ppm phosphoric acid, mixes middle adding 1150ppm n-butanol afterwards at the 252.780g polytetramethylene ether diol.By measuring pump with 57.063g diphenyl methane-4,4 '-vulcabond joins in 45 ℃ the static mixer continuously, in its polymerisation tube of cylinder tubulose of 85～90 ℃ of packing into, next reacted 130 minutes, unreacted terminal vulcabond is adjusted to 2.33 ± 0.02mol%, makes primary polymer viscosity reach 700 pools.
Primary polymer 40 ℃ of coolings down, is continued 20 hours.Before primary polymer is joined second reactor, also with the 456.663g N,N-dimethylacetamide with in the high-shear mixer that was enclosed in vigorous stirring under about 2500rpm in 20 seconds continuously.Primary polymer dissolves fully and cools down under 15 ℃, makes the polyurethane prepolymer mixture have 40% solids content.
Mixture together with cahin extension agent solution (4.00g ethylenediamine/1.23g 1,2-diaminopropanes=mol ratio 80/20) and chain terminating agent solution (0.64g diethylamine) the secondary polymerization reaction device of packing into, was stirred 4 minutes under about 200rpm then, cause after polymerization.As a result, under 65～70 ℃, obtain the polyurethane-urea compound.In order to calculate the mixing efficiency of secondary polymerization reaction device, reclaim the polymer in secondary polymerization reaction device exit, and measure residual preceding amine (preamine) and terminal amine in spinning solution and the polymer.The mixing speed of polymer reactor, amine content and temperature of reactor are all regulated, to obtain at least 80% mixing efficiency.
The amount of diethylamine is defined as 1/20 (amine equivalent ratio) of cahin extension agent solution.With respect to the isocyanate groups that remains in the prepolymer, amine content is defined as 2mol%.At this, do not add chain terminating agent, when then the termination time, point was reduced to 1～5mol% for the content of unreacted amine.
The polymerization by the adding of cahin extension agent and chain terminating agent of polyurethane-urea secondary polymerization thing, the solids content of this polymer are that the apparent viscosity under 37%, 40 ℃ is 2500 pools.This polymer is 1.0 with the intrinsic viscosity that the concentration of 0.5g is dissolved in the 100ml N,N-dimethylacetamide solution.
Concerning conventional elastomer (spandex); in order when washing or use, not lose durability and white; and raising fastness (preventing flavescence) and stainability; protect its performance injury-free; in above-mentioned polymeric solution, add 0.12wt% titanium dioxide, 0.60wt%1; 1; 1 '; 1 '-tetramethyl-4; 4 ' (methylene-two-right-phenylene) diaminourea waste gas stabilizing agent [HN-150], 0.1～3.0wt%2-[4,6-two (2, the 4-xylyl)-1; 3,5-triazine-2-base-5-(octyloxy) phenol light stabilizer [CYASORB
UV-1164D (Cynamid, USA)], 1.44wt%1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethylbenzene)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone (trion) CYANOX1790 (R) (Cynamid, USA), be used to 0.50wt% dolomol (the Nippon Oil that improves viscosity and unwind performance; Fat, Japan), poly-(N, N-diethyl-2-ethylaminoethanol methacrylate) stainability reinforcing agent and the 100ppm diethylenetriamines of 0.6wt%, above-mentioned all ratios all is for the gross weight of the elastomer of spinning.At this, in order to improve the heat resistance of elastomer, and prevent that the cohesion of inorganic additive from producing precipitation, makes polymer and additive mix simultaneously, diethylenediamine is not to add as cahin extension agent, but adds as forming crosslinked additive when the high temperature spinning.At this moment, the even mixing of final polymer and additive is very important.For final polymer and additive are mixed, used cylinder tubulose static mixer.The solids content of prepared polyurethane-urea product is 37%, and viscosity is 4250 pools (40 ℃), and this viscosity is the appropriate viscosity of spinning.
To remain on the additive slurry of final mixed with polymers under 45 ℃.
Use gear pump that made spinning is slowly advanced past spin duct, solvent evaporated in this process with polymer solution under 245～255 ℃.Like this, get polyurethaneurea elastic fiber by above-mentioned dry spinning legal system, spinning speed is 900m/min, and the physical property of product is presented in the table 2.
Embodiment 2
Prepare elastomer with the same quadrat method of describing as embodiment 1, difference is: added the n-butanol with respect to polytetramethylene ether diol gross weight 1500ppm.
Comparative example 1
Prepare elastomer with the same quadrat method of describing as embodiment 1, difference is: add cahin extension agent solution (3.92g ethylenediamine/1.20g 1,2-diaminopropanes=mol ratio 80/20) and chain terminating agent solution (0.627g diethylamine) with the equivalent proportion identical with the primary polymer terminal isocyanate group (amine equivalent ratio/vulcabond equivalent proportion=1.00).
Comparative example 2
Prepare elastomer with the same quadrat method of describing as comparative example 1, difference is: by increased the amount of N,N-dimethylacetamide in the pre-polymer solution before the secondary polymerization reaction device of packing into, solids content is reduced by 2%, reduce to 35% from 37%, to reduce viscosity.
Comparative example 3
(MEG, MW:1815) (n-butanol MW:74.12) with 10ppm phosphoric acid, mixes middle adding 900ppm n-butanol afterwards to the 240.63g polytetramethylene ether diol.Use measuring pump with 57.04g diphenyl methane-4,4 '-vulcabond joins in 45 ℃ the static mixer continuously, in its cylinder tubulose polymerisation tube of 75～90 ℃ of packing into, next reacted 120 minutes, unreacted terminal vulcabond is adjusted to 2.65 ± 0.02mol%.Prepare elastomer with the same quadrat method of describing as comparative example 1, difference is: cahin extension agent solution (4.29g ethylenediamine/1.32g 1, and solids content is 35% the 2-diaminopropanes) and the reaction of the terminal isocyanate of chain terminating agent solution (0.67g diethylamine) and primary polymer.
[table 1]
| The amount of n-butanol (relative glycol, %) | The amount of amine (%) | Terminal NCO (%) | Solids content (%) | Gel particles quantity | Add the preceding viscosity of additive (40 ℃, pool) | Viscosity behind the interpolation additive (40 ℃, pool) | ||
| 24 hours | 48 hours | |||||||
| Embodiment 1 | 0.115 | 102 | 2.33 | 37 | 800-900 | 2800 | 3450 | 4250 |
| Embodiment 2 | 0.150 | 102 | 2.33 | 37 | 800-900 | 2420 | 2830 | 3550 |
| Comparative example 1 | 0.115 | 100 | 2.33 | 37 | 1000-1250 | 4800 | 5650 | 7250 |
| Comparative example 2 | 0.115 | 100 | 2.33 | 35 | 1000-1200 | 4000 | 4400 | 4830 |
| Comparative example 3 | 0.090 | 100 | 2.65 | 35 | 1200-1400 | 3800 | 4160 | 4660 |
[table 2]
| Elasticity | Heat resistance | |||||
| Fracture strength (g/d) | Elongation at break (%) | Elastic recovery rate (%) | Damp and hot elastic recovery rate (%) under 130 ℃ | Xeothermic strength retention ratio (%) under 180 ℃ | The striped rank * | |
| Embodiment 1 | 1.40 | 550 | 98.0 | 41.5 | 82.0 | B |
| Embodiment 2 | 1.32 | 565 | 97.6 | 40.5 | 80.1 | BC |
| Comparative example 1 | 1.28 | 530 | 92.4 | 39.3 | 80.5 | C |
| Comparative example 2 | 1.32 | 550 | 96.2 | 36.0 | 70.3 | C+ |
| Comparative example 3 | 1.32 | 575 | 96.5 | 38.7 | 75.0 | C |
*Fabric striped rank (vision-based detection, striped rank/sign indicating number)
A(no striped),
B ±(1-2 stria),
B(3-5 stria),
BC(5-10 stria),
C+(10-20 stria),
C(1-5 banded cord),
D(at least 5 banded cords).
As previously explained, the method according to this invention, by the even mixing in the first stage polymerization course of reaction, side reaction and gelation are inhibited, therefore, the elastomer of spinning has excellent uniformity, spinnability, elastic recovery rate, damp and hot elastic recovery rate and strength retention ratio, and this causes elastomer to have good performance, this performance comprises the striped style that keeps fabric, and keeps the exquisite part (elegance) after braiding and the dyeing.
Commercial Application
The invention provides a kind of polyurethaneurea elastic fiber, this fiber has excellent weaving performance, and for example You Yi uniformity and spinnability are even and the elastic recovery rate and the strength retention ratio that also have excellence behind dyeing.
Person of skill in the art will appreciate that, can be at an easy rate change, perhaps be designed for other embodiment of realizing the identical purpose of the present invention based on the disclosed notion of foregoing description and the specific embodiment.Those skilled in the art will recognize that also the specific embodiment of this equivalence does not deviate from the spirit and scope of the present invention as described in the appended claims.
Claims (13)
1. the preparation method of a polyurethaneurea elastic fiber, it may further comprise the steps:
A) by mixing 1-official energy single group alcohol, organic acid, polytetramethylene ether diol and diphenyl methane-4 in the static blender, 4 '-vulcabond, and in the cylinder tubular reactor, make the mixture successive reaction, the preparation primary polymer; And
B) comprise ethylenediamine/1 by in described primary polymer, adding, the amine blends of 2-diaminopropanes/diethylamine, and in stirred reactor, stir the mixture preparation secondary polymerization thing with shearing force.
2. the preparation method of polyurethaneurea elastic fiber as claimed in claim 1, wherein, in described step B, described primary polymer is dissolved in N, in the N-dimethylacetylamide, make the prepolymer mixture, described prepolymer mixture and comprise ethylenediamine/1, the amine blends of 2-diaminopropanes/diethylamine stirs under required speed, described speed setting becomes to produce at least 80% mixing efficiency, making apparent viscosity is 2000～3500 pool (solids content: 37%, 40 ℃) secondary polymerization thing solution, adds compositions of additives in described secondary polymerization thing solution, preparation viscosity is (40 ℃ of 3500～5000 pools, solids content: spinning solution 37%), with described spinning solution spinning, the preparation elastomer.
3. the described 1-official preparation method of polyurethaneurea elastic fiber as claimed in claim 1, wherein said steps A) can single group alcohol be a n-butanol, and described organic acid is a phosphoric acid.
4. the preparation method of polyurethaneurea elastic fiber as claimed in claim 3, wherein said n-butanol, be 1-official's energy single group alcohol, use with concentration with respect to polytetramethylene ether diol weight 500～2000ppm, described phosphoric acid, be organic acid, use with concentration with respect to polytetramethylene ether diol weight 5～20ppm.
5. the preparation method of polyurethaneurea elastic fiber as claimed in claim 1, wherein the content of determining described amine blends is to feed intake more, and its amount makes that amido is 2～4mol% with respect to the equivalent proportion value of isocyanate group in the described primary polymer.
6. the preparation method of polyurethaneurea elastic fiber as claimed in claim 5, wherein said amine blends comprises that ratio is the ethylenediamine and 1 of 70-90: 30-10mol%, 2-diaminopropanes cahin extension agent, with and the ratio of amount and described cahin extension agent amine equivalent be the diethylamine terminator of 1/15-1/30.
7. the preparation method of polyurethaneurea elastic fiber as claimed in claim 2, wherein said compositions of additives comprises that the gross weight with respect to the spinning solution composition is the titanium dioxide of 0.05～4.5wt%, 0.2 1 of～3.5wt%, 1,1 ', 1 '-tetramethyl-4,4 ' (methylene-two-right-phenylene) diaminourea, 0.1 the dolomol of～2wt%, 0.2 poly-(N, the N-diethyl-2-amido ethanol methacrylate) of～1.0wt%, 0.1 the 2-[4 of～3.0wt%, 6-two (2, the 4-xylyl)-1,3,5-triazine-2-yl]-5-(octyloxy) phenol, 0.5 1,3 of～3.5wt%, 5-three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethylbenzene)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-diethylenetriamines of triketone and 50～200ppm.
8. the preparation method of polyurethaneurea elastic fiber as claimed in claim 2, wherein said spinning is carried out when spinning cap temperature is reduced to 240-255 ℃, and spinning speed is 700-1200m/min.
9. the preparation method of polyurethaneurea elastic fiber as claimed in claim 2 wherein is cooled to 30-50 ℃ with described primary polymer, and packs in the high-shear mixer and dissolving with N,N-dimethylacetamide, to prepare described pre-polymer mixture.
10. the preparation method of polyurethaneurea elastic fiber as claimed in claim 2, wherein said pre-polymer mixture and described ethylenediamine/1 that comprises, the amine blends of 2-diaminopropanes/diethylamine stirs together, take out polymer from the outlet of described secondary polymerization reaction device afterwards, measure the content of end group amine and preceding amine, and at this moment regulate mixing speed, amine content and the temperature of reactor of described polymer reactor, make mixing efficiency be at least 80%.
11. the preparation method of polyurethaneurea elastic fiber as claimed in claim 1, wherein said steps A) the described primary polymer in contains the unreacted vulcabond of 3mol% at the most endways.
12. the preparation method of polyurethaneurea elastic fiber as claimed in claim 4, the temperature of wherein said static mixer is 40-50 ℃, polymerization temperature in the continuous polymerization reaction tube is 70-95 ℃, the polyurethaneurea elastic fiber that produces has the viscosity of 500-700 pool, and contains the unreacted vulcabond of 3mol% at the most endways.
13. polyurethaneurea elastic fiber by any described method preparation among the claim 1-12.
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| KR1020060064927A KR100780434B1 (en) | 2006-07-11 | 2006-07-11 | Polyurethaneurea elastic fiber and method for preparation thereof |
| KR1020060064927 | 2006-07-11 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8623950B2 (en) | 2008-10-28 | 2014-01-07 | Tae Kwang Ind. Co., Ltd. | High heat and chlorine resistant polyurethaneurea elastic fiber and preparation of thereof |
| CN104884688A (en) * | 2012-10-23 | 2015-09-02 | 路博润先进材料公司 | Dyeable and flame-retarded thermoplastic polyurethane fibers |
| CN107129686A (en) * | 2017-05-03 | 2017-09-05 | 阜南县邰氏宇崴运动器材有限公司 | Soft fibrous composite of a kind of knee-pad and preparation method thereof |
| CN111164246A (en) * | 2017-07-27 | 2020-05-15 | 纳米技术制陶株式会社 | Additive slurry for producing polyurethane urea elastic fiber |
| CN112281247A (en) * | 2020-10-30 | 2021-01-29 | 浙江华峰氨纶股份有限公司 | Method for preparing high-uniformity spandex through continuous polymerization |
| CN113089122A (en) * | 2021-04-01 | 2021-07-09 | 华峰重庆氨纶有限公司 | Preparation method of polyurethane urea spinning solution with stable and controllable viscosity and fiber |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180044532A (en) * | 2016-10-24 | 2018-05-03 | 주식회사 효성 | polyurethanurea elastic fiber and a manufacturing method having high elongation |
| KR101913354B1 (en) * | 2017-02-28 | 2018-10-30 | 태광산업주식회사 | Polyurethaneurea elastic fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR910004474B1 (en) * | 1988-06-25 | 1991-06-29 | 동양나이론 주식회사 | Manufacturing method of polyurethane elastic yarn |
| JPH07278246A (en) * | 1994-04-11 | 1995-10-24 | Toyobo Co Ltd | Production of urethane polymer and elastic thread |
| JP4378667B2 (en) | 2000-09-11 | 2009-12-09 | 東レ・オペロンテックス株式会社 | Method for producing polyurethane fiber |
| KR100514458B1 (en) * | 2003-11-25 | 2005-09-13 | 태광산업주식회사 | High heat-resistance polyurethaneurea elastic fiber and method for preparation thereof |
-
2006
- 2006-07-11 KR KR1020060064927A patent/KR100780434B1/en active IP Right Grant
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- 2007-07-09 WO PCT/KR2007/003312 patent/WO2008007879A1/en active Application Filing
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| US8623950B2 (en) | 2008-10-28 | 2014-01-07 | Tae Kwang Ind. Co., Ltd. | High heat and chlorine resistant polyurethaneurea elastic fiber and preparation of thereof |
| CN104884688A (en) * | 2012-10-23 | 2015-09-02 | 路博润先进材料公司 | Dyeable and flame-retarded thermoplastic polyurethane fibers |
| CN104884688B (en) * | 2012-10-23 | 2017-03-08 | 路博润先进材料公司 | Can dye and fire-retardant thermoplastic polyurethane fibers |
| CN107129686A (en) * | 2017-05-03 | 2017-09-05 | 阜南县邰氏宇崴运动器材有限公司 | Soft fibrous composite of a kind of knee-pad and preparation method thereof |
| CN111164246A (en) * | 2017-07-27 | 2020-05-15 | 纳米技术制陶株式会社 | Additive slurry for producing polyurethane urea elastic fiber |
| CN112281247A (en) * | 2020-10-30 | 2021-01-29 | 浙江华峰氨纶股份有限公司 | Method for preparing high-uniformity spandex through continuous polymerization |
| CN113089122A (en) * | 2021-04-01 | 2021-07-09 | 华峰重庆氨纶有限公司 | Preparation method of polyurethane urea spinning solution with stable and controllable viscosity and fiber |
| CN113089122B (en) * | 2021-04-01 | 2023-03-10 | 华峰重庆氨纶有限公司 | Preparation method of polyurethane urea spinning solution with stable and controllable viscosity and fiber |
| CN115787129A (en) * | 2022-12-15 | 2023-03-14 | 华峰重庆氨纶有限公司 | Preparation method of antibacterial and deodorant polyurethane elastic fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100780434B1 (en) | 2007-11-29 |
| WO2008007879A1 (en) | 2008-01-17 |
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