CN1509352A - Polyurethane type elastic fiber and process of preparing for the same - Google Patents
Polyurethane type elastic fiber and process of preparing for the same Download PDFInfo
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- CN1509352A CN1509352A CNA028084802A CN02808480A CN1509352A CN 1509352 A CN1509352 A CN 1509352A CN A028084802 A CNA028084802 A CN A028084802A CN 02808480 A CN02808480 A CN 02808480A CN 1509352 A CN1509352 A CN 1509352A
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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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- 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
- C08G18/0895—Manufacture of polymers by continuous processes
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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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- 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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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Artificial Filaments (AREA)
Abstract
Disclosed a polyurethane elastic fiber and a method of producing the polyurethane elastic fiber. The method of producing the polyurethane elastic fiber is characterized in that polyol with high molecular weight and diisocyanate with excessive amount are mixed in a condition of a designated shear rate and prepolymerized to produce a prepolymer, the prepolymer is reacted with the chain extender and the chain terminator to produce a polymer, and an additive is added to the polymer and the final polymer is spun. The method of producing the polyurethane elastic fiber according to the present invention improves the stability of the polymer, has an excellent spinnability even in high-speed spinning, and remarkably reduces the generation of wave yarns. The polyurethane elastic fiber of the present invention is excellent in heat resistance, thermosetting efficiency and coherence strength between the monofilaments.
Description
Invention field
The present invention relates to a kind of polyurethane elastomeric fiber and preparation method thereof.More particularly, the present invention relates to prepare the method for polyurethane elastomeric fiber, described method can improve the stability of polymer, and has the high speed spinnability, has significantly reduced the formation of onde yarn thus.And, the present invention relates to have excellent heat resistance, the polyurethane elastomeric fiber of cohesive force between heat-set efficiency and monofilament.
Polyurethane can prepare by a stage polymerisation, in described polymerisation, incites somebody to action very high molecular 1,600-2, and the polyalcohol of 000g/mol, excessive vulcabond and cahin extension agent such as glycol or diamine compound react simultaneously.Perhaps, prepare polyurethane by the two stage polymerisations that comprise following two steps: the first step is a polymerizable molecular amount 1,600-2, the polyalcohol of 000g/mol and excessive di-isocyanate reaction make prepolymer, and second step reacted simultaneously for the described prepolymer that adds and cahin extension agent and chain terminating agent such as glycol or diamine compound.
A more described stage polymerisation, described two stage polymerisations can produce the structure of rule more, and the possibility of formation bridged bond is lower, therefore control the degree of polymerisation easily.Now, most polyurethane elastomeric fiber prepares by two stage polymerisations.
The phase I of described two stage polymerisations, it is the prepolymerization stage of reaction, be that high polyalcohol of molecular weight such as diol compound and excessive di-isocyanate reaction form amino-formate bond, prepare prepolymer thus, form isocyanate group at the two ends of polyalcohol this moment.
Usually, the molecular weight of polyalcohol is about 1,800g/mol, and the ratio of NCO/OH is about 1.5-1.8.Above-mentioned prepolymerization is reflected under the bulk polymerization conditions that does not have solvent, carries out 1-2 hour about 60-90 ℃ temperature.When described reaction temperature was higher, reaction speed was also higher.If use solvent such as dimethylacetylamide (hereinafter referred to as " DMA ") or dimethyl formamide (hereinafter referred to as " DMF "), reaction temperature is owing to the catalytic action of solvent raises.Therefore, under 30-60 ℃, just finish in the described 10-20 of being reflected at minute.
The second stage of described two stage polymerisations, i.e. the chain growth stage is the reaction prepolymer and low-molecular-weightly have compound bearing active hydrogen such as ethylenediamine, a propane diamine, 1, the 4-butanediol reacts, and improves the degree of polymerization thus.In this article, this compound is as cahin extension agent.
If described prepolymer and diamine reactant then form the urea key.If described prepolymer and glycol reaction then form amino-formate bond.Described chain growth step is faster than described first step, is exothermic reaction.Therefore, in order to carry out described reaction equably, should use polar solvent such as DMAc or DMF.
Background technology
The open No.196651 of Korean Patent has disclosed method for producing polyurethanes, wherein, (the reaction mol ratio: 1.5-1.64) and react, preparation has first polymer of 4 moles of % unreacted vulcabond thus to mix ethylene glycol and vulcabond under 40-50 ℃ temperature in static mixer.Afterwards, with described first polymer and cahin extension agent reaction, prepare polyurethane thus; Described cahin extension agent comprises 74-80 mole % ethylenediamine, 19-25 mole %1, the Diethylenetriamine of 2-diaminopropanes and 0.2-0.8 mole %.
But there are many problems in above-mentioned prior art, and is as described below.
40-50 ℃ temperature is too wide, can not evenly mix ethylene glycol and vulcabond.For example, the reaction of ethylene glycol and vulcabond is very violent.Therefore, under greater than 45 ℃ temperature, a large amount of ethylene glycol and vulcabond reacts before evenly mixing.Like this, just be difficult to evenly mix ethylene glycol and vulcabond, and before evenly mixing, reacted a large amount of ethylene glycol and vulcabond, thus, increased the possibility that forms gel because of reaction.
For reaction temperature being remained below 42 ℃, before being placed on described static mixer, the material temperature of ethylene glycol and vulcabond is set in advance in is lower than 42 ℃.But, in the time of temperature departure 43-44 ℃, can increase impurity such as diamines in the s vulcabond rapidly.Therefore, for reaction temperature being remained below 42 ℃, before static mixer, heat exchanger must be installed, perhaps external jacket be attached on the static mixer, this this control temperature.Relatively mix the method for ethylene glycol and vulcabond under the temperature identical with vulcabond storage temperature (43-44 ℃), this method is more suitable.
And in cahin extension agent, above-mentioned prior art is used Diethylenetriamine (0.2-0.8 mole %), is improving heat resistance and heat-set efficiency in the technology subsequently thus.But, in polymer, introduce excessive bridged bond, can reduce the linearity of polymer and in the phase transformation of spinning prepolymer.Therefore, be difficult to make polymer stabilizing, therefore reduced spinnability.Therefore, this prior art can not be brought up to spinning speed more than 650 meter per seconds.
And a day disclosure communique No.4-100919 has disclosed and has wherein only used 0.18 weight % ethylenediamine as cahin extension agent, and goes to the method that adds triamine, tetramine etc. in the described polymer in the spinning step.But the problem of this method is very unstable in the viscosity of spinning prepolymer, and spinnability is low.And this method has improved heat resistance, but has reduced heat-set efficiency.
In U.S. Patent No. 5,362, in 432, use to comprise 83-92 mole % ethylenediamine and 8-17 mole %1, the mixture of 2-diaminopropanes is as cahin extension agent.But in this method, more be to use to have the good ethylenediamine that enriches (filling) performance, therefore reduced the viscosity stability of described polymer before spinning.Therefore, process is difficult to control.And this method makes the heat setting performance variation of gained elastomer.
And, in U.S. Patent No. 5,981, in 686, using to comprise 10-65 mole % ethylenediamine and 35-90 mole %1, the mixture of 3-diaminourea pentane is as cahin extension agent.In this patent, provide some bridged bonds in order to give described polymer, the amine of selectivity use trifunctional such as Diethylenetriamine are as cahin extension agent or chain terminating agent.But above-mentioned patent does not spell out the amount of used Diethylenetriamine.And, U.S. Patent No. 5,000,899 have disclosed wherein, and use comprises the method for the compound of 50-80 mole % ethylenediamine and 20-50 mole %2-methyl pentamethylene diamine as cahin extension agent.
In U.S. Patent No. 5,981,686 and 5,000, in 899 the cahin extension agent, 2-methyl pentamethylene diamine and 1,3-diaminourea pentane has than ethylenediamine and 1, the chain that the 2-diaminopropanes is longer is characterized as the odd number chain with 5 carbon atoms, and has loose side chain such as methyl or ethyl.By these characteristics, above-mentioned United States Patent (USP) prevents the internal crystallization of polymer or elastomer, promptly causes hard fragment and soft segment to rearrange the crystallization that causes owing to be separated, and has reduced its heat resistance thus.Described lower heat resistance has reduced the hold facility of physical property in procedure of processing subsequently, and has lost some particular characteristics of described elastomer.
Summary of the invention
Therefore, made the present invention based on above-mentioned problem.The purpose of this invention is to provide a kind of method for preparing polyurethane elastomeric fiber, described method can improve the stability of polymer viscosity, even and also have a good spinnability, the formation of significantly lowering onde yarn thus under the high-speed spinning condition.And, the invention provides have excellent heat resistance, the polyurethane elastomeric fiber of cohesive force between heat-set efficiency and monofilament.
One aspect of the present invention is to reach above-mentioned and other purpose by the method for preparing polyurethane elastomeric fiber, it is characterized by use and prepare prepolymer at the continuous polymerization pipe of cylindrical tube shape, described continuous polymerization pipe comprises static mixer, heater, reactor and cooler, and described prepolymer and cahin extension agent/chain terminating agent prepared in reaction polymer, and in described polymer, add additive.
As described below:
[method for preparing prepolymer]
(i) under without the internal mix component condition, in static mixer, with greater than 20 seconds
-1Shear rate the polyalcohol of high molecular and excessive vulcabond are mixed,
(ii) under, in heater, with greater than 3 seconds without the internal mix component condition
-1Shear rate at first react the polyalcohol of high molecular and excessive vulcabond,
(iii) under, in reactor, with greater than 0.1 second without the internal mix component condition
-1Shear rate again secondary response described at first the reaction mixture, prepare described first prepolymer thus.
The present invention provides between monofilament cohesive strength on the other hand greater than the polyurethane elastomeric fiber of 145mgf.
In order to provide shear rate in preparation prepolymer process, the present invention uses the continuous polymerization pipe that has at Kenics type or the inner hydrid component that forms of Sulzer type.Described continuous polymerization pipe be shaped as cylindrical tube.Described continuous polymerization pipe comprises static mixer, heater, reactor and cooler.Described static mixer designs becomes without the internal mix parts, and its shear rate is promptly greater than 20 seconds
-1Described heater design becomes without the internal mix parts, and its shear rate is promptly greater than 3 seconds
-1Described reactor is designed to without the internal mix parts, and its shear rate is promptly greater than 0.1 second
-1
At first, under without the internal mix component condition, in static mixer, with greater than 20 seconds
-1Shear rate the polyalcohol of high molecular and excessive vulcabond are mixed, and under, with greater than 3 seconds without the internal mix component condition
-1Shear rate in heater, react, and under, with greater than 0.1 second without the internal mix component condition
-1Shear rate in reactor, react, prepare first prepolymer thus.
Herein, using number-average molecular weight is 1,700-3, and 000 polytetramethylene ether glycol and 4,4 '-methylenediphenyl diisocyanates, they are to be commonly used to prepare polymer that polyurethane elastomeric fiber uses.Herein, vulcabond should be about 1.5-1.75 to the molar ratio of ethylene glycol.In the process of preparation prepolymer, form three-dimensional bridged bond easily by this heterogeneous body mixture and reaction.Therefore, the shear rate of suitably controlling in static mixer, heater and the reactor is very important.
Under without the internal mix component condition, the shear rate of the mixture that prepolymer is used in the static mixer was greater than 20 seconds
-1If shear rate is lower than 20 seconds
-1, then can not evenly mix described monomer, form a large amount of gels thus, and reduce the spinnability and the quality of described prepolymer.
The mixing temperature of static mixer is preferably 43-44 ℃.If mixing temperature is greater than 45 ℃, described reaction will be carried out before evenly mixing largely, formed the gel that three-dimensional bridged bond connects thus.Gel component can accumulate in the static mixer, perhaps transfers in the next step.Therefore, make the replacing circulation of static mixer shorten, perhaps make the degradation of described prepolymer.
And gel can influence final spinning step, reduce spinnability thus, formed onde yarn, and unfavorable to the physical property of gained elastomer.If mixing temperature is lower than 43 ℃, because mixing temperature is lower than the storage temperature of vulcabond, equipment that will be extra.
And, under without the internal mix component condition, the shear rate in the heater was set at greater than 3 seconds
-1Very important.If shear rate is lower than 3 seconds
-1, then the heterogeneous body reaction increases, and gel increases in prepolymer.
The temperature that heater raises and the final temperature of described intensification prepolymer also are important factors.Should prevent from promptly to heat up, and the final elevated temperature of heater is set in is lower than 90 ℃.When the reaction temperature of prepolymer during greater than 90 ℃, can side reaction take place rapidly, improved the possibility that forms gel thus.And, because the reaction of ethylene glycol and vulcabond is exothermic reaction, so must control described exothermic reaction by regulating the heating-up time well.
If the heating-up time is too fast, owing to be difficult to control the heat that produces in the course of reaction, the final elevated temperature of described prepolymer can be greater than 90 ℃.On the other hand, if the heating-up time is too slow, heater device is the same long with the raw material supply amount, therefore heater must be installed additionally.
And, under without the internal mix component condition, the shear rate in the reactor was set at greater than 0.1 second
-1Very important.If shear rate is lower than 0.1 second
-1, described heterogeneous body reaction can form gel.Herein, the reaction temperature of reactor should be controlled at and be lower than 80-90 ℃.If reaction temperature is higher than 90 ℃, side reaction can take place rapidly, increase the possibility that forms gel thus.
The prepolymer that makes by said method is a diameter less than 20 microns gel.Herein, the quantity of these gels is 600/g.Described gel has improved the processing characteristics and the quality of end product.In the prepolymer gel quantity measure by the Coulter counter.
Then, in prepolymer, add cahin extension agent and chain terminating agent, carry out prepared in reaction polyurethane with it.More particularly, use N, N '-dimethylacetylamide (hereinafter referred to as " DMAc ") the described prepolymer of dissolution with solvents forms the solution of described prepolymer.Described solution with comprise the N of diamines and triamine, N '-dimethylacetamide solution (cahin extension agent) and comprise the N of monoamine, N '-dimethylacetamide solution (chain terminating agent) reacts.Herein, the diamines as for as cahin extension agent can use ethylenediamine or 1, the 2-diaminopropanes.As for triamine, can use diethyl triamine.
As for cahin extension agent solution, for example can use to comprise 60-75 mole % ethylenediamine, 24.9-39 mole %1,2-diaminopropanes and the solution that is less than 0.1 mole of % diethyl triamine.Monoamine as for as chain terminating agent can use diethylamine.Should use the cahin extension agent of 96-98.5 equivalent % and the chain terminating agent of 4.5-7.0 equivalent %.Described cahin extension agent and chain terminating agent solution can provide respectively, also can provide simultaneously.
According to the N that is used to dissolve prepolymer, the amount of N '-dimethylacetamide solution, the concentration of prepared polyurethane (hereinafter referred to as " final polymer ") is 36-38.5 weight %, number-average molecular weight is 30,000-50,000.Described number-average molecular weight can be measured by gel permeation chromatography (GPC).
In shear rate greater than 0.13 second
-1Condition under, in without the static mixer of internal mix parts, mix described polyurethane and additive, form the spinning solution before the spinning thus.Described additive is preferably the compound that comprises triamine group.
More particularly, described additive can be selected from the compound with triamine group, conventional antioxidant, resisting etiolation agent, ultra-violet stabilizer, dyeing promoter, delustering agent or spinning promoter.More particularly, can use diethylenetriamines as compound with triamine group.
When not using diethylenetriamines as cahin extension agent, but during as additive, in high-speed spinning, can form bridged bond, improve the heat resistance of described elastomer thus, prevent that inorganic additive from precipitating owing to reuniting again, and evenly mix described additive and polymer.
At this moment, evenly mix described additive and final polymer is very important.If described additive and final mixture of polymers undercompounding, the uneven additive component that disperses and mix can produce onde yarn from spun elastomer, break yarn thus.And cohesive force can reduce between silk thread, cause thus breaking silk thread in the procedure of processing subsequently, and the processing characteristics and the degradation of fiber that makes described final processing.
In order evenly to mix described final polymer and additive, use the static mixer that is shaped as cylindrical tube.Shear rate in the static mixer that does not have the internal mix parts was greater than 0.13 second
-1
The storage temperature of sneaking into the additive slurries in the final polymer is very important.If the storage temperature of additive slurries is greater than 60 ℃, because small Brownian movement, slurry viscosity rises and these factors of discontinuity can be greater than the factor of settling velocity reduction, promote the reunion again and the settling velocity of described additive slurries thus, make the degradation of additive slurries, and improved the blocking period of the filter that is used for additive.Therefore, the quality of shadow final polymerization thing and output are subjected to ringing institute.
And if the storage temperature of additive slurries is lower than 40 ℃, then the additive slurries rise with respect to the relative viscosity of temperature, increase the formation of pressure reduction thus, and become factors of instability in the described method.And small Brownian movement is very weak, thereby promotes to reunite once more, has improved the quality of additive and has shortened the blocking period of filter.Therefore, the storage temperature of described additive slurries should be remained in 40-60 ℃ the scope.
Use gear pump under 180-280 ℃, the formation spinning solution of specified amount to be squeezed into spin duct) in, evaporate the solvent that is contained in the spinning solution, prepare described polyurethane elastomeric fiber thus.Described method is called dry-spinning method.
In the dry-spinning process because the final polymer (spinning solution) that comprises various additives becomes the form of yarn, by transamidation or ammonolysis chemical modification described polymer.By this chemical change, spinning solution changes yarn shape into, and improves its molecular weight.
The number-average molecular weight of the elastomer of the present invention's preparation is about 40,000-70,000.The number-average molecular weight of elastomer also can be measured by gel permeation chromatography (GPC).Spinning speed of the present invention should be set in 800-1,200 meter per seconds.
The gel content of the spinning solution of the present invention's preparation is low.Additive evenly mixes/is dispersed in the described spinning solution.Therefore, described spinning solution has good spinnability, and has significantly reduced the formation of onde yarn.State in the use in the polyurethane elastomeric fiber of spinning solution preparation, use an amount of triamine, form three-dimensional bridged bond thus, and improve the cohesive force between heat resistance, heat-set efficiency and monofilament as cahin extension agent and additive.According to the heat resistance test, strength retention is greater than 54%, and cohesive force is greater than 145mgf between monofilament.
The stability of the gel particle number of measurement prepolymer as described below, final polymer and the molecular weight of elastomer, final polymer viscosity, the heat resistance and the heat-set efficiency of final polymer.
The gel particle number of prepolymer
Prepolymer is dissolved in the 1%LiCl DMAc electrolyte concentration to 0.5%.Then, Coulter counter (manufacturing of Britain Coulter ' company) is measured the gel particle number of prepolymer.
The stability of end product viscosity
End product is stored in 50 ℃ the baking oven.Simultaneously, in 3 days, measured the viscosity of end product, thereby measure the rate of climb of end product viscosity every 2 hours.Herein, the viscosity of end product is measured by the Brook Fliter RV viscosimeter that uses the No.7 hammer body, and its rotary speed is 10rpm.
The molecular weight of final polymer and elastomer
With described sample dissolution in 0.05M LiCl DMF solution, to concentration be 0.05%, measure the molecular weight of final polymer and elastomer by gel permeation chromatography (GPC)., use poly(ethylene oxide) herein, and the product of use Waters is as GPC as the calibration criterion material.
The judgement of onde yarn
Elongating length with 500%/30 second speed is 10 centimetres sample to 500%, leaves standstill then 1 minute.And make described sample lax.If formed yarn has the joint of 2 bendings or winding at least in 10 centimetres length, this yarns is judged to be onde yarn so.The percentage of waveform number of threads is represented in judgement 5,000 cheeses of this onde yarn.
Heat resistance and heat-set efficiency
Elongate to 15cm at the sample that with described length is 10cm, be placed in 195 ℃ the hot blast baking oven.Then, under normal temperature and damp condition, allow it lax and cooled off 2 hours, in 100 ℃ boiling water, handled 30 minutes then.Measure the intensity before handling, intensity and the length variations after the processing.Characterize heat resistance by strength retention, and characterize heat-set efficiency by sample length change rate.Sample with high strength conservation rate has good heat resistance, and the sample with high length change rate has good heat-set efficiency.
Strength retention (%)=(handling the intensity of the preceding sample of intensity/processing of back sample) * 100
Length change rate (%)=[(handling the length of the preceding sample of length-processing of back sample) * 200]/length of sample before handling
Cohesive force between monofilament
Tell one monofilament that length is 5cm from the polyurethane elastomeric fiber that comprises many silk threads.One end of telling monofilament and other end that mixes monofilament are tied up on the Instrung less than the rod-type dynamometer that has 1kg, the center that the monofilament told and the contact point between unsegregated many monofilament are placed 5cm grid (cage), then, with 1000%/minute speed stretch, measure thus the monofilament of telling and the shear strength of not separating many monofilament.Be used as the result by the cohesive force mean value that in drawing process, records.Each sample carries out the measurement more than three times.
Implement best mode of the present invention
Embodiment 1
With 1 mole is 1,800 polytetramethylene ether glycol and 1.65 mole 4, and 4 '-diphenyl diisocyanate places the continuous polymerization pipe, and this tube shape is cylindrical.Described continuous polymerization pipe comprises without its shear rate of internal mix parts and reaches 20 seconds
-1Static mixer, reach 3 seconds without its shear rate of internal mix parts
-1Heater, reach 0.1 second without its shear rate of internal mix parts
-1Reactor and cooler.When static mixer remained on 43.5 ℃, the heater end remained on 89 ℃, and reactor remains on 88 ℃.Make polytetramethylene ether glycol and 4,4 '-diphenyl diisocyanate reaction 110 minutes makes the prepolymer that two ends have isocyanates thus.Described prepolymer is cooled to 40 ℃, and adds 4,4 '-dimethylacetylamide makes the solution that comprises 45% prepolymer thus.Then, when being cooled to 5 ℃ of also violent mixing along with polymer solution, described polymer solution and 98.5 equivalent % are as cahin extension agent and comprise the ethylenediamine of 59.5 moles of %, 40 moles of %1, the N of 2-diaminopropanes and 0.1 mole of % diethylenetriamines, N '-dimethylacetamide solution and 6.5 equivalent % are as chain terminating agent and comprise the N of diethylamine, N '-dimethylacetamide solution reaction prepares final polymer thus.The number-average molecular weight of the final polymer of gained is 31,000, and the viscosity under 40 ℃ is 2,200 pools, comprises 38.5% solid.Described final polymer and additive slurries evenly mix, and are stored in 45 ℃, and shear rate is 0.13 second
-1The static mixer without the internal mix parts in, make thus the spinning before spinning solution; Described additive slurries comprise 1.2 weight %1,3,5-three (the 4-tert-butyl group-3-hydroxyl-2, the 6-dimethyl benzene)-1,3,5 triazines 2,4,6-(1H, 3H, 5H) triketone (trion) antioxidant, 1.0 weight %1,1,1 ', 1 '-tetramethyl-4,4 '-(methylene-to diphenylene (phethylene)) diaminourea waste gas stabilizing agent, 1.5 weight %N-(4-ethoxy carbonyl phenyl)-N-methyl-N-phenyl formamide ultra-violet stabilizer, 2 weight % titanium oxide, 0.01 weight % blue pigment (superbright ocean blue) and 0.2 weight % diethylenetriamines.The spin duct that is distributed between 260-200 ℃ by dry-spinning method serviceability temperature carries out spinning to described spinning solution, makes 40 deniers' polyurethane elastomeric fiber thus.Table 1 has shown prepolymer gel granule number, the rate of climb of end product viscosity, the production rate of onde yarn, the heat resistance and the heat-set efficiency of gained elastomer, and the result of cohesive force between monofilament.
Embodiment 2
Except using wherein ethylenediamine, 1, the mol ratio of 2-diaminopropanes and diethylenetriamines is 75: 24.9: 0.1 a chain extender compound, and use outside 96.0 equivalent % cahin extension agents and the 7.0 equivalent % chain terminating agents, use to prepare polyurethane elastomeric fiber with embodiment 1 identical method.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Embodiment 3
Except using 0.1 weight % diethylenetriamines, use to prepare polyurethane elastomeric fiber with embodiment 1 identical method as the additive.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Embodiment 4
Except using 0.3 weight % diethylenetriamines, use to prepare polyurethane elastomeric fiber with embodiment 1 identical method as the additive.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of institute's prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Comparative Examples 1
Use to prepare polyurethane elastomeric fiber with embodiment 1 identical method, different being to use comprises that shear rate is 19 seconds
-1Static mixer, shear rate be 2.8 seconds
-1Heater, it is 0.09 second without the shear rate of internal mix parts
-1Reactor and be 0.1 second without the shear rate of internal mix parts
-1The continuous polymerization pipe of extra static mixer; The temperature of static mixer is 49 ℃, and the temperature of the prepolymer of intensification is 95 ℃, and the temperature of reactor is 93 ℃, and the storage temperature of additive slurries is 65 ℃.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Comparative Examples 2
Except use comprises the cahin extension agent of 70 moles of % ethylenediamines and 30 moles of %2-methyl pentamethylene diamines, and use and do not contain outside the additive of diethylenetriamines, use to prepare polyurethane elastomeric fiber with embodiment 1 identical method.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Comparative Examples 3
Use continuous polymerization pipe identical and extra static mixer with Comparative Examples 1.And, prepare the spinning solution except using ethylenediamine to add 0.18 weight % diethylenetriamines as cahin extension agent and in described polymer solids, use to prepare polyurethane elastomeric fiber with embodiment 1 identical method.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Comparative Examples 4
Use continuous polymerization pipe identical and extra static mixer with Comparative Examples 1.And, except use comprises 80 moles of % ethylenediamines, 19.8 moles of %1, outside the cahin extension agent of 2-diaminopropanes and 0.2 mole of % diethylenetriamines, use to prepare polyurethane elastomeric fiber with embodiment 1 identical method.The results are shown in Table 1 for cohesive force between the production rate of the gel particle number of prepolymer, the rate of climb of end product viscosity, onde yarn, the heat resistance of gained elastomer and heat-set efficiency and monofilament.
Table 1 result of the test
| Prepolymer gel (grain number) | The speed that viscosity rises (pool/hour) | The production rate of onde yarn (%) | Strength retention (%) | Heat-set efficiency (%) | Cohesive strength (mgf) | |
| Embodiment 1 | ?500-600 | ????25 | ????0.1 | ????59 | ????39 | ????145 |
| Embodiment 2 | ?500-600 | ????29 | ????0.1 | ????62 | ????35 | ????150 |
| Embodiment 3 | ?500-600 | ????27 | ????0.13 | ????54 | ????41 | ????148 |
| Embodiment 4 | ?500-600 | ????26 | ????0.08 | ????65 | ????33 | ????152 |
| Comparative Examples 1 | ?800-1200 | ????31 | ????0.25 | ????54 | ????40 | ????105 |
| Comparative Examples 2 | ?800-1200 | ????26 | ????0.24 | ????42 | ????42 | ????120 |
| Comparative Examples 3 | ?800-1200 | ????48 | ????0.31 | ????68 | ????17 | ????124 |
| Comparative Examples 4 | ?800-1200 | ????36 | ????0.28 | ????55 | ????39 | ????119 |
Industrial use
Elastomer of the present invention has the cohesive force between good heat resistance (strength retention), heat setting performance and monofilament, can be used as the clothes yarn effectively thus.The present invention has improved the stability of used polymer, even and under the high speed spinning condition, also have good spinnability, and significantly reduced the formation of onde yarn.
Though for the purpose of example has illustrated preferred implementations more of the present invention, but those skilled in the art should know, under the condition that does not deviate from scope described in the appended claims of the present invention and principle, can carry out various modifications, add to replace.
Claims (11)
1. method for preparing polyurethane elastomeric fiber, it is characterized in that, the continuous polymerization pipe that use is shaped as cylindrical tube prepares prepolymer, described continuous polymerization pipe comprises static mixer, heater, reactor and cooler, and described prepolymer and cahin extension agent/chain terminating agent carry out the prepared in reaction polymer, and add additive in described polymer;
As described below:
[method for preparing prepolymer]
(i) under without the internal mix component condition, in static mixer, with greater than 20 seconds
-1Shear rate the polyalcohol of high molecular and excessive vulcabond are mixed,
(ii) under, in heater, with greater than 3 seconds without the internal mix component condition
-1Shear rate at first make the polyalcohol of high molecular and excessive di-isocyanate reaction,
(iii) under, in reactor, with greater than 0.1 second without the internal mix component condition
-1The shear rate mixture that reacted of the described elder generation of secondary response again, prepare first prepolymer thus.
2. the described method for preparing polyurethane elastomeric fiber of claim 1 is characterized in that, the temperature of described static mixer is 43-44 ℃.
3. the described method for preparing polyurethane elastomeric fiber of claim 1 is characterized in that, the temperature of described heater is lower than 90 ℃.
4. the described method for preparing polyurethane elastomeric fiber of claim 1 is characterized in that, the temperature of described reactor is 80-90 ℃.
5. the described method for preparing polyurethane elastomeric fiber of claim 1 is characterized in that, in described chain growth/chain termination reaction, adds 96-98.5 equivalent % cahin extension agent and 4.5-7.0 equivalent % chain terminating agent.
6. the described method for preparing polyurethane elastomeric fiber of claim 1 is characterized in that, in without the static mixer of internal mix parts with greater than 0.13 second
-1Shear rate mix the polyurethane and the additive of described polymerization.
7. the described method for preparing polyurethane elastomeric fiber of claim 1, it is characterized in that, described cahin extension agent is to comprise 60-75 mole % ethylenediamine, 24.9-39 mole %1, the N of 2-diaminopropanes and 0.1-1 mole % diethylenetriamines, N '-dimethylacetamide solution.
8. the described method for preparing polyurethane elastomeric fiber of claim 1 is characterized in that, described additive is the compound with triamine group.
9. the described method for preparing polyurethane elastomeric fiber of claim 8 is characterized in that, the 0.1-0.3 weight % that described content with compound of triamine group is described polymer solids.
10. the described method for preparing polyurethane elastomeric fiber of claim 8 is characterized in that, described compound with triamine group is a diethylenetriamines.
11. a polyurethane elastomeric fiber is characterized in that the cohesive strength that monofilament is asked is greater than 145mgf.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR2001/20975 | 2001-04-19 | ||
| KR1020010020975A KR100719044B1 (en) | 2001-04-19 | 2001-04-19 | A polyurethane type elastic fiber, and a process of preparing for the same |
| KR2001/20976 | 2001-04-19 | ||
| KR1020010020976A KR100646647B1 (en) | 2001-04-19 | 2001-04-19 | A process of preparing polyurethane type elastic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1509352A true CN1509352A (en) | 2004-06-30 |
| CN1270006C CN1270006C (en) | 2006-08-16 |
Family
ID=26638999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028084802A Expired - Fee Related CN1270006C (en) | 2001-04-19 | 2002-04-19 | Polyurethane type elastic fiber and process of preparing for the same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20040121149A1 (en) |
| EP (1) | EP1392898A4 (en) |
| JP (1) | JP2004526069A (en) |
| CN (1) | CN1270006C (en) |
| WO (1) | WO2002086208A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422398C (en) * | 2006-05-15 | 2008-10-01 | 连云港杜钟氨纶有限公司 | New technology of spandex fiber |
| CN101809209B (en) * | 2007-06-22 | 2012-08-29 | 因维斯塔技术有限公司 | Elastic polyurethane yarn and process for production thereof |
| TWI506050B (en) * | 2010-01-14 | 2015-11-01 | Invista Tech Sarl | Spandex with high uniformity |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6916896B2 (en) | 2003-05-05 | 2005-07-12 | Invista North America S.A.R.L. | High productivity spandex fiber process and product |
| US7838617B2 (en) | 2003-05-05 | 2010-11-23 | Invista North America S.àr.l. | Dyeable spandex |
| CN107289806A (en) * | 2017-06-22 | 2017-10-24 | 兰州蓝星纤维有限公司 | The temperature controlled devices and methods therefor of stoste before a kind of carbon fibre precursor is spun |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL136659C (en) * | 1968-03-18 | |||
| US5000899A (en) * | 1988-05-26 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Spandex fiber with copolymer soft segment |
| CA2089069A1 (en) * | 1991-06-13 | 1992-12-14 | Hiroyuki Hanahata | Linear segmented polyurethaneurea and process for production thereof |
| US5362432A (en) * | 1993-04-02 | 1994-11-08 | E. I. Du Pont De Nemours And Company | Process for dry spinning spandex |
| DE19520732A1 (en) * | 1995-06-07 | 1996-12-12 | Bayer Ag | Thermoplastic polyurethane elastomers |
| EP0872581B1 (en) * | 1995-06-23 | 2003-03-19 | Asahi Kasei Kabushiki Kaisha | Elastic polyurethane fibers and process for the production thereof |
| EP0907771B1 (en) * | 1996-06-24 | 2003-02-12 | E.I. Du Pont De Nemours And Company | Polyurethane fibers and films |
| JPH10226921A (en) * | 1996-12-13 | 1998-08-25 | Du Pont Toray Co Ltd | Polyurethane fiber and its production |
| US6096252A (en) * | 1998-01-29 | 2000-08-01 | Dupont Toray Co., Ltd. | Process of making polyurethane fiber |
| DE19924090C1 (en) * | 1999-05-26 | 2001-01-25 | Bayer Ag | Process for the continuous production of thermoplastically processable polyurethanes with improved softening behavior |
| DE19924089C1 (en) * | 1999-05-26 | 2001-01-25 | Bayer Ag | Process for the continuous production of thermoplastically processable polyurethanes with improved softening behavior |
| WO2001014441A1 (en) * | 1999-08-26 | 2001-03-01 | Henkel Corporation | Process for preparing polyurethane polymers |
-
2002
- 2002-04-19 CN CNB028084802A patent/CN1270006C/en not_active Expired - Fee Related
- 2002-04-19 JP JP2002583718A patent/JP2004526069A/en active Pending
- 2002-04-19 WO PCT/KR2002/000714 patent/WO2002086208A1/en active Application Filing
- 2002-04-19 EP EP02718687A patent/EP1392898A4/en not_active Withdrawn
- 2002-04-19 US US10/475,011 patent/US20040121149A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422398C (en) * | 2006-05-15 | 2008-10-01 | 连云港杜钟氨纶有限公司 | New technology of spandex fiber |
| CN101809209B (en) * | 2007-06-22 | 2012-08-29 | 因维斯塔技术有限公司 | Elastic polyurethane yarn and process for production thereof |
| TWI506050B (en) * | 2010-01-14 | 2015-11-01 | Invista Tech Sarl | Spandex with high uniformity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004526069A (en) | 2004-08-26 |
| WO2002086208A1 (en) | 2002-10-31 |
| EP1392898A4 (en) | 2007-08-29 |
| EP1392898A1 (en) | 2004-03-03 |
| CN1270006C (en) | 2006-08-16 |
| US20040121149A1 (en) | 2004-06-24 |
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