CN101548036A - Melt-spun elastoester multifilament yarns - Google Patents
Melt-spun elastoester multifilament yarns Download PDFInfo
- Publication number
- CN101548036A CN101548036A CNA2007800446716A CN200780044671A CN101548036A CN 101548036 A CN101548036 A CN 101548036A CN A2007800446716 A CNA2007800446716 A CN A2007800446716A CN 200780044671 A CN200780044671 A CN 200780044671A CN 101548036 A CN101548036 A CN 101548036A
- Authority
- CN
- China
- Prior art keywords
- multifilament
- silk
- ester
- weight
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- -1 polytrimethylene Polymers 0.000 claims abstract description 62
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- 150000002148 esters Chemical class 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 55
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- 229940039696 lactobacillus Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002632 lipids Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000005418 vegetable material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
This invention relates to a method of melt-spinning a polyether ester thermoplastic elastomer under commercially viable conditions to produce an elastoester multifilament yarn, wherein the polyether ester thermoplastic elastomer is a polytrimethylene ether ester comprising a polytrimethylene ether dicarboxylate ester soft segment and hard segment selected from a trimethylene dicarboxylate ester and/or a tetramethylene dicarboxylate ester hard segment.
Description
Invention field
The present invention relates under the condition of commericially feasible the melt spinning polyether ester thermoplastic elastomer with the method for production elasticity ester (elastoester) multifilament, wherein said polyether ester thermoplastic elastomer is the polytrimethylene ether-ether, it comprises polytrimethylene ether dicarboxylic ester soft chain segment and is selected from 1,3-propylidene dicarboxylic ester and/or 1, the hard segment of 4-butylidene dicarboxylic ester hard segment.
Background of invention
In the U.S., title " elasticity ester " is the specific name in the fiber art, and it comprises by weight at least 50% aliphatic polyether and at least 35% polyester by weight.The elasticity ester can stretch as spandex, is easy to washing, and can bears high temperature when wetting.The elasticity ester it is said and can keep dyestuff better than nylon and spandex, and fugitive color or be not subject to the harmful effect of chlorine not, and fugitive color or the harmful effect that is not subject to chlorine are not the key characters of swimsuit and so on clothes.
US6562457 discloses and has comprised polytrimethylene ether-ether soft chain segment and 1, the polyether ester thermoplastic elastomer of 4-butylidene ester hard segment.US6599625 discloses and has comprised polytrimethylene ether-ether soft chain segment and 1, the polyether ester thermoplastic elastomer of 3-propylidene ester hard segment.US6905765 discloses the polyester elastomer that comprises poly-(propylidene-ethyleneether) ester soft chain segment and alkylene ester hard segment.
More than announce to show that wherein disclosed polyether ester can be used for making fiber, continuous filament yarn or staple fibre, and this fiber can be used for preparing Woven fabric, braided fabric and supatex fabric.Disclosed fiber is stretchable, has good chlorine tolerance, can be colored under common polyester dyeing condition, and have good physical characteristic, comprises excellent intensity and stretching recovery characteristics, especially unload forces of Gai Shaning and stress decay.
US6562457 and US6599625 also show described fiber the speed of the highest about 1200m/min and can be stretched about 6 times at most by disclosed polymer melt-spun.Melt spinning will be a commercial benefit that surpasses solvent spinning under these conditions, and solvent spinning is used for spandex or elastic cotton, a kind of made fiber that comprises at least 85% blocked polyurethane.
Although above-mentioned generality is open, US6562457 and US6599625 only illustration with the speed of 4 times draw ratio and about 160m/min melt spinning to monofilament.These spinning conditions are too slow for the practical commercialization of described fiber.Successful commercialization generally require spinning speed greater than about 1200m/min and draw ratio up to 5 times, and to require fiber be the form of multifilament.
Summary of the invention
Have now found that some polyether ester thermoplastic elastomer can be greater than the spinning speed melt spinning of about 1200m/min, and produces multifilament (multifilament) under the condition of other commericially feasible.Therefore, the invention provides the condition of the commericially feasible that is used for melt spinning elasticity ester fiber, described elasticity ester fiber comprises the polytrimethylene ether ester polymer, and it comprises polytrimethylene ether dicarboxylic ester soft chain segment and 1,3-propylidene dicarboxylic ester or 1,4-butylidene dicarboxylic ester hard segment.
According to the present invention, the method that is used to prepare elastoester multifilament yarns is provided, said method comprising the steps of:
(a) provide polyether ester thermoplastic elastomer, described elastomer comprises by polytrimethylene ether dicarboxylic ester soft chain segment and about 20% the hard segment to about 60% weight of the combination weight of described hard segment and soft chain segment about 80% to about 40% weight, described hard segment is selected from 1,3-propylidene dicarboxylic ester, 1,4-butylidene dicarboxylic ester and their mixture;
(b), come the described elastomer of melt spinning to form at least 2 threads by elastomer is extruded via one or more spinning heads; And
(c) described long filament is processed into multifilament,
Wherein said melt spinning is to carry out greater than about 1200 meters/minute spinning speed.
Method of the present invention also can comprise the step that multifilament is cut into staple fibre.
The invention still further relates to multifilament and the fabric that comprises the multifilament of preparation like this by above method preparation.
The multifilament of gained is an elasticity ester silk, and it preferably has about 100% to about 600% percentage elongation and about 0.5 intensity to about 2.5 gram/DENIER, and comprises about 0.5 long filament to about 20 Denier per filament (dpf).
In a preferred embodiment of the invention, described multifilament is the silk of spin-drawing, and described step comprise with about 1250 to about 5000m/minute the draw speed elongate filaments, described draw speed is measured at the roller place at stretching step end (at the end of the draw step).Preferably, the step in the spin-drawing multifilament comprises stretching, heat treatment, interweaves and winding filaments.
In a further preferred embodiment, described multifilament is the silk that partly is orientated, and spinning speed is preferably greater than about 1500 meters/minute.
Textured multifilament yarn can be by someway by the partly silk preparation of orientation, and described method comprises: (a) the partly package of the multifilament of orientation of preparation; (b) the described silk of unwinding from the package; (c) elongate filaments is to form the silk that stretches; (d) silk of the described stretching of false twist texturing is to form textured yarn; (e) silk is wound in the package.
DESCRIPTION OF THE PREFERRED
If do not point out separately, mentioned all announcements, patent application, patent and other list of references of this paper all incorporated this paper fully to be shown as purpose into way of reference.
Unless otherwise defined, the implication of all scientific and technical terminologies used herein and those skilled in the art's common sense is the same.Under situation about conflicting, the definition included with this specification is as the criterion.
Unless spell out, trade mark is represented with upper case.
Unless point out separately, all percentages, umber, ratio etc. are all by weight.
When a quantity, concentration or other numerical value or parameter provide with scope, preferable range or some row preferred upper limit numerical value and preferred lower limit numerical value, it should be understood that open particularly any a pair of all scopes that constitute by any range limit or preferred value and any scope lower limit or preferred value, and no matter whether described scope is by open individually.Allly provide a certain number range part in this article, this scope all is intended to comprise its end points, and all integers and the mark that are positioned at this scope, unless point out separately.When scope of definition, do not wish scope of the present invention is defined in cited concrete numerical value.
When term " about " was used for the end points of description value or scope, disclosure should be understood to include concrete value or related end points.
As used herein, term " comprises ", " comprising ", " having " or their any other distortion all are intended to cover comprising of nonexcludability.For example, comprise that technology, method, goods or the equipment of a series of key elements needn't only limit to those key elements, but can comprise clearly do not list or this technology, method, goods or equipment intrinsic other key element.In addition, unless specify in addition, " or " be meant inclusive or, rather than refer to exclusiveness or.For example, condition A or B satisfy following arbitrary situation: A and are false (or not existing) for the B of true (or existence), and A is true (or existence) for the B of false (or not existing), and A and B are truly (or existence).
" one " or " a kind of " are used to describe key element of the present invention or component.This only is for convenience and provides general sense of the present invention.This description should be understood to include one or at least one, and odd number also comprises negative plural number, anticipates unless clearly refer to him in addition.
Unless specifically indicate, the material of this paper, method and embodiment only are illustrative, are not to be intended to limit.Although also can be used for practice of the present invention or test with methods described herein and materials similar or the method that is equal to and material, this paper has described suitable method and material.
Polyether ester thermoplastic elastomer
Being used for polyether ester thermoplastic elastomer of the present invention preferably comprises by described hard segment and soft chain segment combination weight:
About 80% to about 40% weight, and more preferably from about 75% to about 50% weight, and the 70% polytrimethylene ether-ether soft chain segment to about 60% weight more preferably from about; With
About 20% to about 60% weight, and more preferably from about 25% to about 50% weight, and 30% hard segment to about 40% weight (polytrimethylene ester and/or poly-1,4-butylidene ester) more preferably from about.
Described polyether ester thermoplastic elastomer preferably has at least about 0.8dl/g, more preferably at least about 1.2dl/g, and preferred about 2.0dl/g at most, and the preferred inherent viscosity of about 1.6dl/g at most.
" polytrimethylene ether-ether soft chain segment " uses to be used to refer to PTMEG and " dicarboxylic acids equivalent " product by ester bond with " soft chain segment " is related with the present invention, wherein at least about 50% weight, more preferably at least about 85% weight, and more preferably from about the PTMEG that is used to form soft chain segment of 95% to 100% weight is polytrimethylene ether glycol (PO3G).
" polytrimethylene ester hard segment ", " poly-1; 4-butylidene ester hard segment " and " hard segment " related use with the present invention be used to refer to one or more 1, ammediol (1, the 3-trimethylene glycol) or 1,4-butanediol (1,4-butylidene glycol) and the product of one or more dicarboxylic acids equivalents by ester bond, wherein greater than about 50% mole, more preferably at least about 75% mole, even more preferably at least about 85% mole, and more preferably from about 95% to 100% mole the glycol that is used to form hard segment is 1, ammediol and/or 1,4-butanediol.
" dicarboxylic acids equivalent " is meant the equivalent of dicarboxylic acids and they, its be with the reaction of polymer diol and glycol in the compound that works as dicarboxylic acids basically, equally generally will be familiar with by those of ordinary skill in the related art.Except dicarboxylic acids, the dicarboxylic acids equivalent that is used for the object of the invention comprises that also for example dicarboxylic acids is monoesters and diester and forms the derivative of diester such as the halide (for example Suan chloride) and the acid anhydrides of acid.
The PTMEG that is used for soft chain segment
For purposes of the present invention, PO3G is oligomeric and/or the ether glycol of polymerization, and wherein at least 50% repetitive is the propylidene ether unit.More preferably, about 75% to 100%, also more preferably from about 90% to 100%, even more preferably from about 99% to 100% repetitive is the propylidene ether unit.
Preferably by comprising 1, the monomer polycondensation preparation of ammediol contains-(CH thereby produce PO3G
2CH
2CH
2O)-link (for example, propylidene ether repetitive) polymer or copolymer.
Except the propylidene ether unit, also can there be more a spot of other unit, as other polyalkylene ether repetitive.In the context of this disclosure, term " polytrimethylene ether glycol " has been contained by pure 1 basically, ammediol and comprise those oligomer of maximum by weight 50% comonomers and polymer and the PO3G that makes.
Be used to prepare 1 of PO3G, ammediol can obtain by any approach in the various known chemistry routes or by the biochemical transformation approach.Preferred approach for example is described among US5015789, US5276201, US5284979, US5334778, US5364984, US5364987, US5633362, US5686276, US5821092, US5962745, US6140543, US6232511, US6235948, US6277289, US6297408, US6331264, US6342646, US7038092, US20040225161A1, US20040260125A1, US20040225162A1 and the US20050069997A1.
Preferably, 1, ammediol is obtained by renewable source (" biologically-derived " 1, ammediol) in biochemical mode.
Especially preferred 1, the ammediol source is to obtain via the fermentation process that uses the recyclable organism source.As illustrative example, described and utilized the raw material that produces by biology and renewable resource (as maize raw material) to obtain 1, the biochemical route of ammediol (PDO) from the raw material of renewable source.For example, can be 1 with transformation of glycerol, the bacterial isolates of ammediol is present in bacterial classification Klebsiella pneumoniae (Klebsiella), citric acid bacillus (Citrobacter), clostridium (Clostridium) and the Bacillus acidi lactici (Lactobacillus).Described technology is disclosed in several announcements, comprises US5633362, the US5686276 and the US5821092 that incorporate into previously.US5821092 discloses a kind of use recombinant organisms especially by the biological preparation 1 of glycerine, the method for ammediol.Described method has been introduced 1, and the 2-propylene glycol has the Escherichia coli of specific allos pdu diodehydrase genetic transformation.The Escherichia coli that transformed grow in the presence of as the glycerine of carbon source, and isolate 1 from growth medium, ammediol.Because bacterium and yeast can both be converted into glycerine with syrup (as primverose) or other carbohydrate, be disclosed in that these methods in announcing provide fast, cheapness and environmental protection 1, ammediol monomer source.
Biologically-derived 1, ammediol (for example by mentioned earlier with the method preparation of reference) comprises the carbon of the atmospheric carbon dioxide that absorbs from plant, and this plant has constituted 1, the raw materials for production of ammediol.Like this, be preferred for the biologically-derived 1 of the context of the invention, ammediol only comprises reproducible carbon, and does not comprise based on fossil fuel or based on the carbon of oil.Therefore, biologically-derived 1 based on utilizing, the PO3G of ammediol and elastomer have less influence to environment, and this is because in the composition employed 1, ammediol does not have the depletion fossil fuel, and release carbon in degraded back is got back in the atmosphere to be utilized once more by plant.Therefore, composition of the present invention can be characterized by more natural, and littler than the analogous composition that comprises the petroleum base glycol to the influence of environment.
Biologically-derived 1, ammediol and PO3G and can come and distinguish mutually by two carbon isotope fingerprint analysis by the petrochemical industry source or by the similar compound that the carbon that fossil fuel is originated is produced based on their elastomer.This method can be used for distinguishing chemically identical material, and distributes the carbon in the copolymer by the growth source (may be year) that biosphere (plant) formed.Isotope
14C and
13C has brought side information for this problem.The radiocarbon dating isotope (
14C) (its nuclear half-life is 5730) can make clearly and distribute sample carbon (Currie between fossil (" dead ") and biosphere (" work ") raw material, L.A. " Source Apportionment of Atmospheric Particles; " Characteriza-tion of Environmental Particles, J.Buffle and H.P.vanLeeuwen compile, in IUPAC Environmental Analytical Chemistry Series (LewisPub-lishers, Inc) (1992) 3-74) the I volume 1.The basic assumption of radiocarbon dating is in the atmosphere
14The concentration of C is invariable, and it makes in the organism that lives
14C is invariable.When the sample that handle to separate, the age of sample can be derived like close by following:
t＝(-5730/0.693)ln(A/A
0)
Wherein the t=age, 5730 is the half-life of radioactive carbon, and A and A
0Be respectively the concrete of sample and contemporary standard thing
14C activity (Hsieh, Y., Soil Sci.Soc.Am J., 56,460, (1992)).Yet, because since the atmosphere nuclear test of nineteen fifty and the combustion of fossil fuel of beginning in 1850,
14C has obtained second geochemistry temporal characteristics.In middle 1960s, in the nuclear test peak period, it is in Atmospheric CO
2In and therefore the concentration in the biosphere of living is approximately double.After that, its return to gradually stable state (atmosphere) baseline isotope ratio that produces by cosmic ray (
14C/
12C) (about 1.2 * 10
-12), have the prolongation " half-life " of about 7-10.(the back understanding that a kind of half-life can not literally look like; But people must use detailed atmosphere nuclear input/decay function to follow the trail of in atmosphere and the biosphere
14The variation of C after the nuclear age begins.) back just a kind of biosphere
14The temporal characteristics of C presented to modern age biosphere carbon carry out the hope of dating.
14C can measure by accelerator mass spectrometry (AMS), and the result is with " umber of contemporary carbon " (f
M) provide for unit.f
MBy National Institute of Standards and Technology (NIST) standard reference materials (SRM) 4990B and 4990C (being called oxalic acid standard HOxI and HOxII) definition.Basic definition relates to 0.95 and multiply by
14C/
12C isotope ratio HOxI (with reference to AD1950).This roughly is equivalent to the preceding timber of the industrial revolution that decay correction is crossed.For current living organism circle (vegetable material), f
M≈ 1.1.
Stable carbon isotope ratio (
13C/
12C) the additional approach that provides the source to distinguish and distribute.In given biogenetic derivation material,
13C/
12The C ratio is when carbon dioxide fixation in the atmospheric carbon dioxide
13C/
12The ratio of C, and reflected accurate metabolic pathway.Regional change has also taken place.Oil, C
3Plant (broad-leaved), C
4Plant (draft), and marine carbonate all exist
13C/
12Demonstrate significant difference on C and the corresponding δ 13C value.In addition, since metabolic pathway, C
3And C
4The decomposition of the lipid material of plant is different with the material derived from the carbohydrate ingredient of identical plant.In the precision of measuring, because the isotope fractionation effect
13C demonstrates very big variation, and the most significant for the present invention is photosynthesis mechanism.In the plant in the main cause of carbon isotope rate variance and the plant difference of photosynthesis carbon metabolic pathway closely related, the especially reaction that during elementary carboxylation reaction, is taken place, i.e. Atmospheric CO
2Initial fixation.Two big class plants are to adopt " C
3" (or Calvin-Benson) photosynthetic circulation those and adopt " C
4" those of (or Hatch-Slack) photosynthetic circulation.The C of hardwood and needle and so on
3The type plant is mainly in the tierra templada.At C
3In the type plant, elementary CO
2Fixing or carboxylation reaction relates to the enzyme ribulose-1,5-bisphosphate, 5-diphosphonic acid carboxylase, and first stable product is the 3-carbon compound.On the other hand, C
4The type plant comprises the plant as tropical pasture, corn and sugarcane and so on.At C
4In the type plant, the other carboxylation reaction that relates to another kind of enzyme, phosphoric acid enol pyruvic acid carboxylase is elementary carboxylation reaction.First stable carbon compound is a 4-carbonic acid, and it is subsequently by decarboxylation.The CO of Shi Fanging thus
2By C
3Circulation is fixing once more.
C
4And C
3The type plant all shows certain limit
13C/
12The C isotope ratio, but typical value is about-10 to-14 per thousand (C
4) and-21 to-26 per thousand (C
3) (people such as Weber, J.Agric.Food Chem., 45,2942 (1997)).Coal and oil generally drop in the back scope.
13C measurement degree be at first with the South Carolina, United States Cretaceous period skin Di to organize plan belemnite fossil (PDB) limestone in the layer position serve as zero to define, wherein numerical value provides with thousand marks of the deviation of material therewith." δ
13C " be worth with thousand marks (some thousandths of) expression, be abbreviated as ‰, be calculated as follows:
Because PDB standard substance (RM) is depleted, IAEA, USGS, NIST and other selected international isotopic laboratory have developed a series of alternative RM cooperatively.Deviation thousand mark δ with PDB
13C represents.Be on 44,45 and 46 the molecular ion to CO by high-precision stable ratio mass spectrum (IRMS) in quality
2Measure.
Therefore, biologically-derived 1, ammediol and comprise biologically-derivedly 1, the composition of ammediol can and show two carbon isotope fingerprint analysis of novel substance composition and the material suitable with them of deriving with petrochemical industry differentiates fully according to 14C (fM).The ability of distinguishing these products helps following the tracks of these materials in the commerce.For example, the product that comprises " newly " and " old " two kinds of Carbon Isotope Characteristics figure can differentiate with the product of only being made by " old " material.Therefore, can promptly use material, and be used for limiting competition, determining storage life, and be particularly useful for assessing purpose the influence of environment commercial the close attention according to its unique characteristic pattern.
When measuring by gas chromatographic analysis, be used as reactant or be used as 1 of reactant composition, the purity that ammediol has is preferably greater than about 99% weight by weight, and more preferably greater than about 99.9% weight.Especially preferred is as 1 of disclosed purifying among US7038092, the US20040260125A1, US20040225161A1 and the US20050069997A1 that had before incorporated into, ammediol, and as the PO3G of disclosed preparation among the US20050020805A1.
1 of purifying, ammediol preferably have following properties:
(1) UV absorption at 220nm place is less than about 0.200, and at the 250nm place less than about 0.075, and at the 275nm place less than about 0.075; And/or
(2) L that has of composition
*a
*b
*" b
*" colour is less than about 0.15 (ASTM D6290), and in the absorption at 270nm place less than about 0.075; And/or
(3) peroxide compositions is less than about 10ppm; And/or
(4) when adopting gas chromatographic measurement, the concentration of total organic impurities (removing 1, the organic compound outside the ammediol) is more preferably less than about 300ppm, and is more preferably less than about 150ppm less than about 400ppm.
The raw material of preparation PO3G will depend on the utilizability, catalyst, equipment etc. of required PO3G, raw material, and comprise " 1, the ammediol reactant "." 1, the ammediol reactant " is meant 1, ammediol and 1, the oligomer of ammediol and prepolymer (preferably having 2 to 9 the degree of polymerization), and their mixture.In some cases, expectation use maximum 10% or more low-molecular-weight oligomer (when they can utilize).Therefore, raw material preferably comprises 1, ammediol and dimer thereof and tripolymer.Especially preferred raw material is by about 90% weight by weight or more 1, ammediol, and more preferably based on 1, and about 99% weight of the weight meter of ammediol reactant or more 1, ammediol constitutes.
PO3G can be by multiple methods known in the art preparation, as disclosed among US6977291 and the US6720459.Preferable methods such as among the US20050020805A1 that had before incorporated into proposition.
As implied above, except 1, outside the 3-propylidene ether unit, PO3G also can comprise more a spot of other polyalkylene ether repetitive.Therefore, the monomer that is used to prepare polytrimethylene ether glycol is except 1, outside the ammediol reactant, also can comprise maximum 50% weight (preferred about 20% weight or still less, 10% weight or still less more preferably from about, and 2% weight or still less more preferably from about) the comonomer polyalcohol.Suitable comonomer polyalcohol comprises aliphatic diol, ethylene glycol, 1 for example, 6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3,3,4,4,5,5-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ten hexafluoros-1,12-dodecanediol; Alicyclic diol, for example 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol and isobide; And polyol, for example glycerine, trimethylolpropane and pentaerythrite.The preferred group of comonomer diol is selected from: ethylene glycol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, 2,2-diethyl-1, ammediol, 2-ethyl-2-(methylol)-1, ammediol, C
6-C
10Glycol (as 1,6-hexylene glycol, 1,8-ethohexadiol and 1,10-decanediol) and isobide and their mixture.Remove 1, outside the ammediol, especially preferred glycol is ethylene glycol, 2-methyl isophthalic acid, ammediol and C
6-C
10Glycol.
A kind of preferred PO3G that comprises comonomer is poly-(propylidene-ethyleneether) glycol, described in US20040030095A1.Preferred poly-(propylidene-ethyleneether) glycol by under the acid catalysis greater than 50% to about 99% mole (preferred about 60% to about 98% mole, and more preferably from about 70% to about 98% mole) 1, the ethylene glycol of ammediol and maximum 50% to about 1% mole (preferably about 40% to about 2% mole, and more preferably from about 30% to about 2% mole) carries out polycondensation reaction and prepares.
Preferably, the PO3G behind the purifying is substantially free of the acid catalyst end group, but can contain the unsaturated end group of utmost point low content, mainly is the allyl end group, and scope is about 0.003 to about 0.03meq/g.Can think that this type of PO3G comprises (being made up of it basically) and has following molecular formula (II) and a compound (III):
HO-((CH
2)
3O)
m-H (II)
HO-((CH
2)
3-O)
mCH
2CH＝CH
2 (III)
Wherein m make within the specific limits Mn (number-average molecular weight) about 200 to about 5000 scope, the compound of molecular formula (III) exists with a certain amount of, makes the amount of allyl end group (preferably all unsaturated ends or end group) in about scope of 0.003 to about 0.03meq/g.A spot of allyl end group is used to control elastomer molecular weight among the PO3G, and does not excessively limit it, makes to prepare the perfect for example composition of fiber final use that is fit to.
The preferred PO3G that is used for the present invention has at least about 750, more preferably at least about 1000, and more preferably at least about 2000 Mn.Described Mn is preferably less than about 5000, is more preferably less than approximately 4000, also is more preferably less than about 3500.Also can use the blend of PO3G.For example, PO3G can comprise blend higher molecular weight and PO3G lower molecular weight, and preferably wherein the PO3G of higher molecular weight has about 1000 to about 5000 number-average molecular weight, and the PO3G of lower molecular weight has about 200 to about 950 number-average molecular weight.The Mn of the PO3G of blend is preferably still in above-mentioned scope.
The PO3G that preferably can be used for this paper is generally the polydispersion polymer, and it has preferred about 1.0 to about 2.2, and more preferably from about 1.2 to about 2.2, and 1.5 to about 2.1 polydispersity (being Mw/Mn) more preferably from about.Polydispersity can be regulated by the blend that uses PO3G.
Be used for PO3G of the present invention and preferably have, and be more preferably less than the colour of about 50APHA less than about 100APHA.
Based on 1, when the PO3G of ammediol was used to form soft chain segment, described soft chain segment can be expressed as comprising the unit by following structure representative when basically:
Wherein R representative is removed the remaining divalent group in back with carboxyl functional group from the dicarboxylic acids equivalent, and x represents among the PO3G 1, the integer of 3-propylidene ether unit number.
The PTMEG that is used to prepare the polytrimethylene ether-ether soft chain segment of polyether ester also can comprise the PTMEG of maximum 50% weight except that PO3G.Preferred this type of other PTMEG comprises for example poly-ether glycol, polytrimethylene ether glycol, polybutylene ether glycol, polyhexamethylene ether glycol, oxolane and the copolymer of 3-alkyl tetrahydro furans and their mixture.
The glycol that is used for hard segment
When 1,3-propylidene/1, when 4-butylidene glycol was used to form hard segment, described hard segment can be expressed as comprising the unit with following structure:
Wherein n is 3 (1, the 3-propylidene) or 4 (1, the 4-butylidene), and R ' representative is removed the remaining divalent group in back with carboxyl functional group from the dicarboxylic acids equivalent.In most cases, be used for preparing the dicarboxylic acids equivalent of soft chain segment and the hard segment of the polyester elastomer that is used for the present invention will be identical.
Described hard segment also available less than 50% mole (preferred about 25% mole at most, more preferably at most about 15% mole) remove 1, the glycol preparation beyond the 3-trimethylene glycol or 1,4-butylidene glycol, described glycol preferably has the molecular weight less than about 400.Other glycol is aliphatic diol preferably, and can be acyclic or ring-type.Preferably have the glycol of maximum about 15 carbon atoms such as ethylene glycol, isobutyl glycol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1, ammediol, 2-methyl isophthalic acid, ammediol, 1,6-hexylene glycol and 1,10-decanediol, dihydroxy cyclohexane, cyclohexanedimethanol, hydroquinones two (2-hydroxyethyl) ether.Especially preferred is the aliphatic diol that comprises 2 to 8 carbon atoms.Ethylene glycol most preferably.Can use two or more other glycol.
The dicarboxylic acids equivalent
The dicarboxylic acids equivalent can be aromatics, aliphatic series or alicyclic.In this, " aromatic dicarboxylic acid equivalent " is that wherein each carboxyl is connected to the dicarboxylic acids equivalent on the carbon atom in the phenyl ring system, as following those that mention." aliphatic dicarboxylic acid equivalent " is that wherein each carboxyl is connected on the saturated fully carbon atom or the dicarboxylic acids equivalent on the carbon atom of the part of olefinic double bond.If carbon atom is on ring, then described equivalent is " alicyclic ".Described dicarboxylic acids equivalent can comprise any substituting group or their combination, needs only the characteristic that this substituting group does not disturb polymerisation or has a strong impact on the polyether ester product.
Preferably be selected from the dicarboxylic acids equivalent of the group of forming by the diester of dicarboxylic acids and dicarboxylic acids.The dimethyl ester of dicarboxylic acids more preferably.
Preferably aromatic dicarboxylic acid or their diester perhaps have a spot of aliphatic series or alicyclic dicarboxylic acid or diester.Especially preferred is the dimethyl ester of aromatic dicarboxylic acid.
The representational aromatic dicarboxylic acid that is used for the present invention comprises terephthalic acids, isophathalic acid, biphenyl dicarboxylic acid, naphthalene diacid, have the dicarboxylic compounds of replacement of the benzene nucleus heart as two (to carboxyl phenyl) methane, 1; 5-naphthalene diacid, 2; 6-naphthalene diacid, 2; 7-naphthalene diacid, 4,4 '-sulfonyl biphenyl dicarboxylic acid and C1-C10 alkyl and other ring substitutive derivative such as halo, alkoxyl or aryl derivatives.As long as also there is aromatic dicarboxylic acid, just can use carboxylic acid such as right-(hydroxyl-oxethyl) benzoic acid.The representational aliphatic series and the alicyclic dicarboxylic acid that are used for the present invention are decanedioic acid, 1,3-or 1, the 4-cyclohexane diacid, adipic acid, dodecanedioic acid, glutaric acid, butanedioic acid, oxalic acid, azelaic acid, diethyl malonic acid, fumaric acid, citraconic acid, allyl malonic acid, 4-cyclohexene-1, the 2-dicarboxylic acids, pimelic acid, suberic acid, 2,5-diethyl adipic acid, 2-ethyl suberic acid, 2,2,3,3-tetramethyl butanedioic acid, the ring glutaric acid, decahydro-1,5-(or 2,6-) naphthalene diacid, 4,4 '-the dicyclohexyl diacid, 4,4 '-methylene two (cyclohexyl diacid), 3,4-furans diacid, and 1,1-encircles succinic acid.The dicarboxylic acids equivalent of the diester of above-mentioned aliphatic dicarboxylic acid, sour halide and anhydride form also can be used for providing polyether ester of the present invention.Representational aromatic diester comprises terephthalic acids dimethyl ester, biphenyl dicarboxylic acid dimethyl ester, dimethylisophthalate, repefral and naphthalene diformic acid dimethyl ester.
More than among, preferably terephthalic acids, biphenyl dicarboxylic acid, isophathalic acid and naphthalene diacid; Terephthalic acids dimethyl ester, biphenyl dicarboxylic acid dimethyl ester, dimethylisophthalate, naphthalene diformic acid dimethyl ester and repefral; And their mixture.Especially preferred dicarboxylic acids equivalent is the phenylene dicarboxylic acids equivalent, especially is selected from following those: terephthalic acids and isophathalic acid and their diester, especially dimethyl ester, terephthalic acids dimethyl ester and dimethylisophthalate.In addition, can use two or more dicarboxylic acids equivalents.For example, terephthalic acids and/or terephthalic acids dimethyl ester can use with a spot of other dicarboxylic acids equivalent.
In a preferred embodiment, the dicarboxylic acids equivalent at least about 70% mole (more preferably at least about 80% mole, also more preferably at least about 90% mole, and more preferably from about 95% to 100% mole) is terephthalic acids and/or terephthalic acids dimethyl ester.
The preparation of polyester elastomer
The polyether ester that is used for spinning technique of the present invention preferably prepares by providing and reacting following material: (a) polytrimethylene ether glycol, (b) 1,3-trimethylene glycol or 1,4-butylidene glycol or their mixture and (c) chloride or the acid anhydrides of dicarboxylic acids, ester, acid.Also can provide and react aforesaid other dihydroxylic alcohols, glycol etc.Comprise polytrimethylene ether-ether soft chain segment and 1, the preparation process of the polyester elastomer of 3-propylidene ester hard segment at length is disclosed among the US6599625.Comprise polytrimethylene ether-ether soft chain segment and 1, the preparation process of the polyester elastomer of 4-butylidene ester hard segment at length is disclosed among the US6562457.
Additive
Described polyether ester thermoplastic elastomer can be the form of mixture, described mixture also comprises one or more additives except elastomer, described additive comprises but is not limited to be selected from following those: matting agent, nucleator, heat stabilizer, tackifier, Optical Bleaching Agent, pigment and antioxidant.Titanium dioxide or other pigment for example can be added to during polymer or fiber make.
Also can use the additive described in US2003-0083441A1 and the WO01/034693 to make the polyester elastomer acid-dyeable.The additive of WO01/034693 comprises secondary amine with effective dose or secondary amine salt is acid-dyeable with lifting and the acid-dyeable of composition acid dyeing.Preferably, the secondary amine unit in the described polymeric blends is with at least about 0.5% mole, more preferably exists at least about 1% mole amount.Secondary amine unit in the described polymeric blends based on the weight meter of described mixture preferably with about 15% mole or still less, more preferably from about 10% mole or still less, and more preferably from about 5% mole or amount still less exist.The additive of US2003-0083441A1 is based on the polymeric additive of tertiary amine.Described polymeric additive comprises the triamine of secondary amine or secondary amine salt unit and (ii) one or more other monomers and/or polymer unit preparation by (i).A kind of preferred polymeric additive comprises polyamide, and described polyamide is selected from: poly--imino group-two alkylidenes-terephthalamide ,-isophthaloyl amine and-1,6-naphthalene diamides and their salt.
Also use the feasible polyether ester cationic-dyeable that is used for the present invention of stainability conditioning agent (those described in US6312805).
The preparation of long filament and silk
For spinning, polymer is heated to its temperature more than fusing point, then at about 175 ℃ to about 295 ℃, preferably at least about 200 ℃, and about 275 ℃ at most, about 270 ℃ temperature at most most preferably, it is extruded by spinning head, preferably extrude by multi-holed jet.Higher temperature is used for the short holdup time.
Can stretch or drawing of fiber not.When they were stretched, stretch rate was at least 1.01, and is preferred about at most 5, more preferably about at most 4, and most preferably at most about 3.
In a preferred embodiment of the invention, described method advantageously is used for preparing the silk of spin-drawing, is also referred to as " fullly drawn yarn (FDY) ".The preferred steps of making the silk of spin-drawing comprises spinning, stretching, randomly heat treatment, randomly interweaves and winding filaments, and it is similar with those of preparation poly-(Polyethyleneglycol Terephthalate) silk use.The silk of the spin-drawing of producing by the inventive method is multifilament preferably.
The silk that an advantage of the invention is spin-drawing can use than US6562457 that is used for the same polyether ester and the disclosed higher draw ratio of US6599625.This can be by using lower than usual spinning speed, stretches with the speed of previous use then and realize.When carrying out this method, the interruption that runs into is than in the past still less.
Draw speed (when measuring at the roller place at the stretching step end) is higher than about 1200m/m, and preferably at least about 3000m/m, more preferably at least about 3200m/m, and preferred about 8000m/m at most, more preferably about at most 7000m/m.Another advantage of the present invention is spinning on the equipment of the silk of the spin-drawing silk that can formerly be used to spin poly-(Polyethyleneglycol Terephthalate) spin-drawing.
The silk of spin-drawing usually can be by in package, and the silk that can be used to prepare fiber or further be processed into other type, as textured yarn.
Although following illustration the method that is used to prepare the silk of spin-drawing of the present invention, the present invention also can be used for preparing partially oriented silk.
The basic step of the silk of fabrication portion orientation comprises spinning, interweaves and reels and gathers (1, the 3-propylidene terephthalate) long filament, and described step is described among US6287688, US6333106 and the US2001-030378A1.Can use those steps or conventional other step that is used to prepare partially oriented Polyester Filament to implement the present invention.
Described partially oriented silk is a multifilament.Described silk (being also referred to as " tow ") preferably comprises at least about 2, and more preferably at least about 25 threads.Described silk has about 1 usually to about 500, preferably at least about 20, and more preferably at least about 50, and even total DENIER of 50 to about 300 more preferably from about.
Long filament is preferably at least about 0.5 Denier per filament (dpf), more preferably at least about 1dpf, and at most about 20 or more dpf, more preferably about at most 7dpf.Typical long filament is about 3 to 7dpf, and fine filament is about 0.5 to about 2.5dpf.
Spinning speed is greater than about 1200, and can be about 5000m/minute (" m/m ") or higher at most.They are preferably at least about 1500m/m, and more preferably at least about 3000m/m.With regard to the present invention, spinning speed generally is restricted to maximum process velocity, and is counted as the speed of draw roll.Therefore, an advantage of the invention is that described method can carry out under than the US6562457 that is used for the same polyether ester and disclosed those the higher speed of US6599625.
The partially oriented silk that an advantage of the invention is polyether ester can formerly be used to spin spinning on the equipment of partially oriented silk of poly-(Polyethyleneglycol Terephthalate), so the preferably the highest about 4000m/m of spinning speed, more preferably the highest about 3500m/m.
Partially oriented silk usually can be by in package, and the silk that can be used to prepare fiber or further be processed into other type, as textured yarn.In preparation fabric or further first being processed, also they can be stored in the jar, perhaps can directly use and do not form package or other storage.
Textured yarn can be by the silk preparation of partially oriented silk or spin-drawing.The main distinction is that partially oriented silk needs to stretch usually, and the silk of spin-drawing is a drawn.
US6287688, US6333106 and US2001-030378A1 have all described the basic step of being made textured yarn by partially oriented silk.Can use those steps or conventional other step that is used to prepare partially oriented Polyester Filament to implement the present invention.Described basic step comprises from wrapping the unwinding silk, stretches, and twisting, heat setting, untwisting, and be wound in the package.By generally being known as false twist texturized method, by twisting, heat setting and untwisting, distortion will be given curling.Careful control false twist texturing is to avoid silk and long filament excessively damaged.
Described in US6287688, US6333106 and US2001-030378A1, the method for optimizing of friction false twist comprises the temperature that partially oriented silk is heated to 140 ℃ to 220 ℃, the twisting of use twisting apparatus, make in the zone between twisting apparatus and calorifier inlets, described silk has about 46 ° to 52 ° angle of twist, and silk is wound on the up-coiler.
When the silk by spin-drawing prepared, method was identical, and different is that stretching is reduced to low-down degree (for example draw ratio can be low to moderate 1.01).
These multifilament (being also referred to as " tow ") comprise the long filament with (long filament is prepared by it) similar number of partially oriented silk and spin-drawing.Therefore, they preferably comprise at least about 2, and even more preferably at least about 25 threads.Described silk has about 1 usually to about 500, preferably at least about 20, and preferably at least about 50, and total DENIER of 50 to about 300 more preferably from about.Long filament is preferably at least about 0.1dpf, more preferably at least about 0.5dpf, and more preferably at least about 0.8dpf, and about at most 10dpf or more, more preferably about at most 5dpf, and more preferably about at most 3dpf.
Staple fibre and product can be by polyether ester preparations of the present invention.A kind of preferable methods comprises: the polytrimethylene ether-ether (a) is provided, described polytrimethylene ether-ether comprises about 80% polytrimethylene ether dicarboxylic ester soft chain segment and about 20% hard segment to about 60% weight to about 40% weight and (is selected from: 1,3-propylidene dicarboxylic ester, 1,4-butylidene dicarboxylic ester), (b) polytrimethylene ether-ether melt spinning is become long filament about 245 to about 285 ℃ temperature, (c) with the long filament quenching, (d) long filament of stretching quenching, (e) use mechanical crimper with about 8 to about 30 volume per inch (about 3 long filaments that curl and stretched to the crimpness of about 12 volumes/cm), (f) about 50 to the lax long filament that curls of about 120 ℃ temperature, (g) lax long filament is cut into staple fibre, described staple fibre preferably has about 0.2 length to about 6 inches (about 0.5 to about 15cm).In a preferred embodiment of this method, the long filament that stretched before curling about 85 to about 115 ℃ of heat treatments.The preferred roller that heated that uses is heat-treated under tension force.In another preferred embodiment, the long filament that stretched is not heat-treated before curling.
Staple fibre is used for preparation weaving yarn and textiles or supatex fabric, and can be used for the fibrefill application and make carpet.
Spinning technique of the present invention also can be used for improving the spinning feeding in the preparation of bulked continuous filament yarn (" BCF ").The manufacturing of BCF silk and they for example is described among US5645782, US6109015, US6113825, US6576340, US6723799, US6740276 and the US2003-0175522A1.The BCF silk is used to prepare various types of carpets and textiles.Composition of the present invention can be used for improving their spinning speed of preparation.
Relate to the preferred steps for preparing bulked continuous filament yarn and comprise spinning (for example pushing, cool off and apply (spinning oil) long filament); About 80 to about 200 ℃ and with about 1.1 to about 5, preferably at least about 1.5, and preferred about 4.5 draw ratio single-stage or multistage stretching (preferably with the roller that heat, the bearing pin that heated or hot fluid adminicle (for example steam or air)) at most; About 120 to about 200 ℃ heat-treated; Expanded; Twine (it can carry out in a step or in independent subsequently step with expanded); Randomly lax; And with winding filament in package to use subsequently.
Can use the technology of knowing that bulked continuous filament yarn is made carpet.Common many silk be retwist together, and device as autoclave in heat setting, restraint in primary substrate then.Use latex and secondary substrate then.
Independent long filament can be circular or have other shape, as octofoil, triangle, rising sun shape (being also referred to as " sol "), scalloped ellipse, trilobal, four flute profiles (being also referred to as " four grooves "), scalloped band shape, band shape, radial etc.They can be solid, hollow or porous.
Though the long filament that may use independent spinning head to have the varying cross-section geometry with the preparation of yarn bundle is preferred by implementing the present invention by the filament cross of one type of a spinning head spinning.
Embodiment
Following examples are to present for purpose of the present invention is described, and are not intended to limit.Except as otherwise noted, all umbers, percentage etc. are all by weight.
Inherent viscosity
Inherent viscosity (IV) is measured and is carried out according to ASTM Method 2857-70.Before weighing, with polymer sample 70 ℃ of dryings 3 hours.Use 0.5% m-cresol solution operation sample at 30 ℃.For raise the efficiency, the degree of accuracy and accuracy, use
AutomaticMeasuring System (Cannon Instrument Company, State College, Pa., U.S.A.) automation viscosity measurement system.Use high density infrared fibre optics detection system to replace the human operator, and use air bath to replace being commonly used to provide the oil bath or the water-bath of steady temperature.Described
The degree of accuracy specification that has surpassed ASTM D-445 (Standard Test Method For KinematicViscosity of Transparent and Opaque Liquids).
Number-average molecular weight
Use molecular weight to be about 44,000 poly-(Polyethyleneglycol Terephthalate) calibration reference and hexafluoroisopropanol solvent according to ASTM D 5296-97 and calculate number-average molecular weight.
Hard segment percentage
Described in US6562457, measure hard segment percentage.
Fibre strength and percentage elongation
Fracture strength T (with gram/DENIER (gpd) expression) and extension at break percentage E go up at the INSTRON.RTM.Tester that Series 2712 (002) Pneumatic Action Grips (the acrylic resin contact-making surface is housed) are housed and measure.Duplicate detection three times.Report result's mean value.
The average DENIER that is used for the fiber of intensity and elongation measurement is reported as " DENIER 1 ".
Fiber unload forces, stress decay and distortion percentage
The average DENIER of fiber that is used to measure unload forces, stress decay and distortion percentage is as " DENIER 2 " report.
Unload forces is measured with dN/texeffx1000.Each long filament that uses one 2 inches (5cm) gauge lengths of measuring.Use zero-extremely-300% cycles of elongation is carried out independent measurement.Per minute with sample loops five times, remains on for percentage elongation half a minute of 300% with 100% constant percentage elongation then after the 5th elongation, measure unload forces (being the stress of concrete percentage elongation) after this.When from last elongation unloading, with various elongation measurement stress or unload forces.This paper uses general formula " UPx/y " with effective unload forces report unload forces, and wherein x is the elongation of fiber circulation five times, and y is an elongation of measuring stress or unload forces.
When the 5th load cycle finishes, sample is being remained on 300% percentage elongation after 30 seconds, measuring stress decay is the percentage of fiber upper stress loss.
S＝((F-C)*100)/F
S=stress decay % wherein
Stress when F=extends entirely
The stress of C=30 after second
Measure distortion percentage by the stress/strain curves that is recorded on the carte paper.
Embodiment 1
Described in US6562457, this embodiment has described has polytrimethylene ether-ether soft chain segment and 1, the preparation of the polyester elastomer of 4-butylidene ester hard segment.This polymer design is become to have 72/28 the soft chain segment and the weight ratio of hard segment.Use batch methods by terephthalic acids dimethyl ester, 1,4-butanediol and polytrimethylene ether glycol prepare described polymer.
In the autoclave that agitator, evacuation and distiller are housed, also pack into 8.81kg terephthalic acids dimethyl ester, 8.94kg 1, the tetraisopropyl titanate polymerization catalyst of the polytrimethylene ether glycol of 4-butanediol, 20.2kg (number-average molecular weight is 2019), 22g and ETHANOX 330 antioxidants (Albemarle Corporation) of 37.5g.The temperature of reactor is risen to 210 ℃ gradually, and reclaim the methyl alcohol of about 2.6kg by distillation from reactor.Under 250 ℃ of decompressions, continue to react again 1.5 hours to increase molecular weight.The polymer of gained extruded from reactor and be transformed into piller, before further using with its dried overnight under 80 to 90 ℃ of decompressions.The character of described polymer is as follows:
Inherent viscosity: 1.403dL/g
Mn： 31400
Molecular weight: 61200
The glass transition temperature of soft chain segment :-67 ℃
The melt temperature of hard segment: 170 ℃
Hard segment percentage: 28%
Following fibre spinning embodiment carries out with the polymer of embodiment 1.
The spinning step
273 ℃ are extruded and remained on to the polymer of embodiment 1 by sand filter spin pack and multi-holed jet (hole of the 0.3mm diameter and the 0.56mm capillary degree of depth, the number in hole is presented in the following table 1).To leave the filament stream quenching of spinning head with 21 ℃ air, and gather into a branch of.Before (feeding) roller have the superficial velocity described in the following table, the speed described in the following table 1 is delivered to one group of draw roll, the nozzle that interweaves, one group of relax rolls and up-coiler successively with tow.The spinning condition that is used for described silk is described in table 1.The property description of gained silk is in table 2.
For the data with embodiment 2 to 9 compare, comparative example 1 and 2 has shown the character of the spandex of two kinds of different commercially available acquisitions.
Table 1
Spinning condition
Embodiment long filament number g/min feeding roller speed draw roll speed stretch rate relax rolls speed winding speed
(mpm) (mpm) (mpm) (mpm)
2 3 7.95 760 2660 3.5 2515 2500
3 3 7.95 760 2660 3.5 2515 2580
4 3 7.95 760 2660 3.5 2515 2590
5 3 7.95 760 2660 3.5 2515 2590
6 3 7.95 2000 2660 1.33 2515 2610
7 6 10.5 760 2660 3.5 2515 2590
8 6 10.5 760 2660 3.5 2515 2590
9 6 10.5 760 2660 3.5 2515 2590
Table 2
The character of silk
| Embodiment | DENIER 1 | Intensity (g/den) | Elongation | DENIER 2 | The percent stretch of 5 circulations | Intensity (g/den) | Elongation | Decay percentage | Distortion percentage | Unloading (g/den) |
| 2 | 53.5 | 1.00 | 303 | 49.1 | 300 | 0.83 | 320 | 18.8 | 52.2 | 18.9 |
| 3 | 51.6 | 1.11 | 256 | 51.8 | 300 | 1.04 | 255 | 16.0 | 21.1 | 21.4 |
| 4 | 53.0 | 1.07 | 255 | 52.0 | 200 | 1.05 | 260 | 16.0 | 21.4 | 21.4 |
| 5 | 48.1 | 1.13 | 256 | 50.0 | 200 | 0.96 | 235 | 16.0 | 20.8 | 20.7 |
| 6 | 41.1 | 1.07 | 275 | 43.0 | 200 | 1.03 | 291 | 14.1 | 20.9 | 14.9 |
| 7 | 72.5 | 1.08 | 260 | 78.0 | 200 | 0.96 | 264 | 15.5 | 18.5 | 29.4 |
| 8 | 68.3 | 1.19 | 253 | 70.9 | 200 | 1.14 | 272 | 16.1 | 19.2 | 30.4 |
| 9 | 80.3 | 1.02 | 245 | 80.0 | 200 | 1.13 | 278 | 16.7 | 19.7 | 33.9 |
| C1 | 71.2 | 0.92 | 490 | 70.8 | 300 | 1.02 | 514 | 27.6 | 16.9 | 9.7 |
| C2 | 41.9 | 1.30 | 487 | 41.3 | 300 | 1.32 | 495 | 29.0 | 13.4 | 7.3 |
Data in the table 1 clearly illustrate, employed polyester elastomer can be according to the present invention be spun into silk with the speed of commericially feasible (its than reported among US6562457 and the US6599625 those are faster).In addition, comparing data confirms, has summarized the character of elasticity ester by the silk that the inventive method obtains.
Claims (16)
1. be used to prepare the method for elastoester multifilament yarns, said method comprising the steps of:
(a) provide polyether ester thermoplastic elastomer, described elastomer comprises by polytrimethylene ether dicarboxylic ester soft chain segment and about 20% the hard segment to about 60% weight of the combination weight of described hard segment and soft chain segment about 80% to about 40% weight, described hard segment is selected from: 1,3-propylidene dicarboxylic ester, 1,4-butylidene dicarboxylic ester and their mixture;
(b), come the described elastomer of melt spinning to form at least 2 threads by elastomer is extruded via one or more spinning heads; And
(c) described long filament is processed into multifilament,
Wherein said melt spinning is to carry out greater than about 1200 meters/minute spinning speed.
2. the process of claim 1 wherein that described dicarboxylic ester comprises terephthalate.
3. the process of claim 1 wherein described polytrimethylene ether-ether comprise about 80% to the polytrimethylene ether terephthalate soft chain segment and about 20% of about 40% weight to 1 of about 60% weight, 3-propylidene terephthalate hard segment.
4. the process of claim 1 wherein described polytrimethylene ether-ether comprise about 80% to the polytrimethylene ether terephthalate soft chain segment and about 20% of about 40% weight to 1 of about 60% weight, 4-butylidene terephthalate hard segment.
5. the process of claim 1 wherein that described multifilament comprises and has about 0.5 long filament to about 20 Denier per filament.
6. the method for claim 5, wherein said method also comprise and interweave and reel described long filament.
7. the process of claim 1 wherein that described multifilament is the silk of spin-drawing, and described processing comprise with about 1250 to about 5000m/minute the draw speed described long filament that stretches, described draw speed is measured at described roller place at described stretching step end.
8. the method for claim 7, the wherein said multifilament that the is processed into spin-drawing described long filament that comprises stretching, heat treatment, interweaves and reel.
9. the process of claim 1 wherein that described multifilament is partially oriented silk.
10. the process of claim 1 wherein that described method also comprises cuts into staple fibre with described multifilament.
11. the process of claim 1 wherein that described polyether ester thermoplastic elastomer comprises at least a additive, described additive is selected from: matting agent, nucleator, heat stabilizer, tackifier, Optical Bleaching Agent, pigment and antioxidant.
12. the process of claim 1 wherein that described multifilament is the elasticity ester silk with percentage elongation of about 100% to about 600%.
13. the process of claim 1 wherein that described multifilament is to have the about 0.5 elasticity ester silk to the intensity of about 2.5 gram/DENIER.
14. be used to prepare the method for textured multifilament yarn, described textured multifilament yarn comprises the long filament of polytrimethylene ether-ether, described polytrimethylene ether-ether comprises about 80% polytrimethylene ether dicarboxylic ester soft chain segment and about 20% hard segment to about 60% weight to about 40% weight, described hard segment is selected from: 1,3-propylidene dicarboxylic ester and 1,4-butylidene dicarboxylic ester, described method comprises: the package that (a) is prepared partially oriented multifilament by the method for claim 9; (b) the described silk of unwinding from the described package; (c) stretch described long filament to form the silk that stretches; (d) silk of the described stretching of false twist texturing is to form described textured yarn; (e) described silk is wound up in the package.
15. multifilament by the preparation of the method for claim 1.
16. comprise the fabric of the multifilament of claim 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/634,646 US20080135662A1 (en) | 2006-12-06 | 2006-12-06 | Melt-spun elastoester multifilament yarns |
| US11/634,646 | 2006-12-06 |
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| Publication Number | Publication Date |
|---|---|
| CN101548036A true CN101548036A (en) | 2009-09-30 |
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| CNA2007800446716A Pending CN101548036A (en) | 2006-12-06 | 2007-12-05 | Melt-spun elastoester multifilament yarns |
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| Country | Link |
|---|---|
| US (1) | US20080135662A1 (en) |
| EP (1) | EP2089564A2 (en) |
| JP (1) | JP2010512465A (en) |
| KR (1) | KR20090087945A (en) |
| CN (1) | CN101548036A (en) |
| AU (1) | AU2007328017A1 (en) |
| BR (1) | BRPI0717905A2 (en) |
| CA (1) | CA2668872A1 (en) |
| MX (1) | MX2009006015A (en) |
| TW (1) | TW200837230A (en) |
| WO (1) | WO2008070159A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2471495B (en) * | 2009-07-01 | 2014-06-04 | Mrb Schumag Ltd | A coil winding device |
| KR101346316B1 (en) * | 2011-09-19 | 2014-01-06 | 송종복 | Method for producing high-strength staple fiber using multi-filament fiber and high-strength staple fiber made by it |
| EP2959509B1 (en) | 2013-02-14 | 2018-05-23 | Nanopareil, Llc | Electrospun hybrid nanofibre felt, method for making the same, and method for purifying biomolecules |
| CN103668736A (en) * | 2013-12-02 | 2014-03-26 | 常熟市新蕾针织有限公司 | Production method of cotton-like knitted fabric |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3023192A (en) * | 1958-05-29 | 1962-02-27 | Du Pont | Segmented copolyetherester elastomers |
| KR960014767B1 (en) * | 1987-11-17 | 1996-10-19 | 롱쁠랑 비스코쉬스 소시에떼 아노님 | Elastic bulky yarn and its manufacturing method |
| DE3926136A1 (en) * | 1989-08-08 | 1991-02-14 | Degussa | METHOD FOR PRODUCING 1,3-PROPANDIOL |
| US5128185A (en) * | 1991-08-29 | 1992-07-07 | E. I. Du Pont De Nemours And Company | Copolyetherester elastomer with poly(1,3-propylenebibenzoate) hard segment |
| DE4132663C2 (en) * | 1991-10-01 | 1993-10-14 | Degussa | Process for producing 1,3-propanediol by hydrogenating hydroxypropionaldehyde |
| DE4138981A1 (en) * | 1991-11-27 | 1993-06-03 | Degussa | METHOD FOR PRODUCING 3-HYDROXYAL CHANNELS |
| DE4138982A1 (en) * | 1991-11-27 | 1993-06-03 | Degussa | PROCESS FOR THE PREPARATION OF 3-HYDROXYAL CHANNELS |
| DE4218282A1 (en) * | 1992-06-03 | 1993-12-09 | Degussa | Process for the preparation of 1,3-propanediol |
| DE4222708A1 (en) * | 1992-07-10 | 1994-01-13 | Degussa | Process for the preparation of 1,3-propanediol |
| JPH083817A (en) * | 1994-06-13 | 1996-01-09 | Nippon Ester Co Ltd | Method of multi-strand spinning of polyether-ester elastic yarn |
| TW288052B (en) * | 1994-06-30 | 1996-10-11 | Du Pont | |
| KR960010623B1 (en) * | 1994-10-14 | 1996-08-06 | 제일합섬 주식회사 | Method of manufacturing stretch fabrics and knits |
| US5555143A (en) * | 1995-01-17 | 1996-09-10 | Western Automation Laboratories, Inc. | Data cartridge library system architecture |
| US6113825A (en) * | 1995-05-08 | 2000-09-05 | Shell Oil Company | Process for preparing poly(trimethylene terephthalate) carpet yarn |
| US5633362A (en) * | 1995-05-12 | 1997-05-27 | E. I. Du Pont De Nemours And Company | Production of 1,3-propanediol from glycerol by recombinant bacteria expressing recombinant diol dehydratase |
| DE59711445D1 (en) * | 1996-12-02 | 2004-04-29 | Barmag Barmer Maschf | Methods and devices for spinning and winding threads |
| DE19703383A1 (en) * | 1997-01-30 | 1998-08-06 | Degussa | Process for the preparation of 1,3-propanediol |
| US5962745A (en) * | 1997-02-14 | 1999-10-05 | E. I. Du Pont De Nemours And Company | Process for preparing 3-hydroxyalkanals |
| KR20010013907A (en) * | 1997-06-18 | 2001-02-26 | 메리 이. 보울러 | Process for the Production of 1,3-Propanediol by Hydrogenating 3-Hydroxypropionaldehyde |
| US6109015A (en) * | 1998-04-09 | 2000-08-29 | Prisma Fibers, Inc. | Process for making poly(trimethylene terephthalate) yarn |
| US6235948B1 (en) * | 1998-08-18 | 2001-05-22 | E. I. Du Pont De Nemours And Company | Process for the purification of 1,3-propanediol |
| KR20010073116A (en) * | 1998-09-04 | 2001-07-31 | 메리 이. 보울러 | Two-Stage Process for the Production of 1,3-Propanediol by Catalytic Hydrogenation of 3-Hydroxypropanal |
| US6331264B1 (en) * | 1999-03-31 | 2001-12-18 | E. I. Du Pont De Nemours And Company | Low emission polymer compositions |
| US6277289B1 (en) * | 1999-07-01 | 2001-08-21 | E. I. Du Pont De Nemours And Company | Treatment of aqueous aldehyde waste streams |
| US6342646B1 (en) * | 1999-07-30 | 2002-01-29 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenation of 3-hydroxypropanal to 1,3-propanediol |
| US6576340B1 (en) * | 1999-11-12 | 2003-06-10 | E. I. Du Pont De Nemours And Company | Acid dyeable polyester compositions |
| US6977291B2 (en) * | 1999-12-17 | 2005-12-20 | E.I. Du Pont De Nemours And Company | Production of polytrimethylene ether glycol and copolymers thereof |
| WO2001044150A2 (en) * | 1999-12-17 | 2001-06-21 | E.I. Du Pont De Nemours And Company | Continuous process for the preparation of polytrimethylene ether glycol |
| US6312805B1 (en) * | 2000-02-11 | 2001-11-06 | E.I. Du Pont De Nemours And Company | Cationic dyeability modifier for use with polyester and polyamide |
| US6287688B1 (en) * | 2000-03-03 | 2001-09-11 | E. I. Du Pont De Nemours And Company | Partially oriented poly(trimethylene terephthalate) yarn |
| US6740276B2 (en) * | 2001-06-29 | 2004-05-25 | E. I. Du Pont De Nemours And Company | Process for preparing pigmented shaped articles comprising poly (trimethylene terephthalate) |
| US6723799B2 (en) * | 2001-08-24 | 2004-04-20 | E I. Du Pont De Nemours And Company | Acid-dyeable polymer compositions |
| US6599625B2 (en) * | 2001-10-31 | 2003-07-29 | E. I. Du Pont De Nemours And Company | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and trimethylene ester hard segment |
| US6562457B1 (en) * | 2001-10-31 | 2003-05-13 | E. I. Du Pont De Nemours And Company | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment |
| JP4129506B2 (en) * | 2001-11-13 | 2008-08-06 | インビスタ テクノロジーズ エス エイ アール エル | Heat set method |
| US20030175522A1 (en) * | 2002-03-13 | 2003-09-18 | Kurian Joseph Varapadavil | Poly(trimethylene terephthalate) carpets |
| US6923925B2 (en) * | 2002-06-27 | 2005-08-02 | E. I. Du Pont De Nemours And Company | Process of making poly (trimethylene dicarboxylate) fibers |
| US6921803B2 (en) * | 2002-07-11 | 2005-07-26 | E.I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) fibers, their manufacture and use |
| US20050031865A1 (en) * | 2002-07-23 | 2005-02-10 | Sauer Bryan B. | Fibers, tapes and films prepared from olefinic and segmented elastomers |
| US20040030095A1 (en) * | 2002-08-09 | 2004-02-12 | Sunkara Hari B. | Poly(trimethylene-ethylene ether) glycols |
| US6905765B2 (en) * | 2002-08-09 | 2005-06-14 | E.I. Du Pont De Nemours And Company | Polyether ester elastomers comprising poly(trimethylene-ethylene ether) ester soft segment and alkylene ester hard segment |
| US6848151B2 (en) * | 2003-03-31 | 2005-02-01 | Invista Norh America S.à.r.l | Air-jet method for producing composite elastic yarns |
| US7084311B2 (en) * | 2003-05-06 | 2006-08-01 | E. I. Du Pont De Nemours And Company | Hydrogenation of chemically derived 1,3-propanediol |
| JP4814794B2 (en) * | 2003-05-06 | 2011-11-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Purification of biologically produced 1,3-propanediol |
| US7323539B2 (en) * | 2003-05-06 | 2008-01-29 | E. I. Du Pont De Nemours And Company | Polytrimethylene ether glycol and polytrimethylene ether ester with excellent quality |
| BRPI0410686A (en) * | 2003-05-06 | 2006-06-20 | Du Pont | process and composition |
| US7009082B2 (en) * | 2003-05-06 | 2006-03-07 | E.I. Du Pont De Nemours And Company | Removal of color bodies from polytrimethylene ether glycol polymers |
-
2006
- 2006-12-06 US US11/634,646 patent/US20080135662A1/en not_active Abandoned
-
2007
- 2007-12-05 WO PCT/US2007/025006 patent/WO2008070159A2/en active Application Filing
- 2007-12-05 CN CNA2007800446716A patent/CN101548036A/en active Pending
- 2007-12-05 CA CA002668872A patent/CA2668872A1/en not_active Abandoned
- 2007-12-05 BR BRPI0717905-7A patent/BRPI0717905A2/en not_active IP Right Cessation
- 2007-12-05 JP JP2009540297A patent/JP2010512465A/en active Pending
- 2007-12-05 KR KR1020097013843A patent/KR20090087945A/en not_active Withdrawn
- 2007-12-05 AU AU2007328017A patent/AU2007328017A1/en not_active Abandoned
- 2007-12-05 EP EP07862598A patent/EP2089564A2/en not_active Ceased
- 2007-12-05 MX MX2009006015A patent/MX2009006015A/en unknown
- 2007-12-06 TW TW096146558A patent/TW200837230A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US20080135662A1 (en) | 2008-06-12 |
| KR20090087945A (en) | 2009-08-18 |
| MX2009006015A (en) | 2009-06-16 |
| WO2008070159A2 (en) | 2008-06-12 |
| CA2668872A1 (en) | 2008-06-12 |
| WO2008070159A3 (en) | 2008-12-31 |
| AU2007328017A1 (en) | 2008-06-12 |
| TW200837230A (en) | 2008-09-16 |
| JP2010512465A (en) | 2010-04-22 |
| EP2089564A2 (en) | 2009-08-19 |
| BRPI0717905A2 (en) | 2013-11-05 |
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