CN104471119B - Produce method, fine amorphous polymer fiber and the spinning head for producing this fiber of fine amorphous polymer fiber - Google Patents

Produce method, fine amorphous polymer fiber and the spinning head for producing this fiber of fine amorphous polymer fiber Download PDF

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Publication number
CN104471119B
CN104471119B CN201380037820.1A CN201380037820A CN104471119B CN 104471119 B CN104471119 B CN 104471119B CN 201380037820 A CN201380037820 A CN 201380037820A CN 104471119 B CN104471119 B CN 104471119B
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fiber
spinning
melt
spinning head
amorphous polymer
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CN104471119A (en
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理查德·彼得斯
戴维·沃伦
迈克尔·林赛
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D01D4/025—Melt-blowing or solution-blowing dies
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/09—Control of pressure, temperature or feeding rate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/06—Distributing spinning solution or melt to spinning nozzles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/14—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • 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
    • Y10T428/298—Physical dimension

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Artificial Filaments (AREA)

Abstract

A kind of method, is included under 400 to 1500psi pressure and extrudes the melt comprising amorphous polymer composition to produce spinning fibre by spinning head；Spinning fibre is collected on feed roller in the case of no extraction spinning fibre；The fiber of solidification is produced by spinning fibre.The fiber of the solidification can have the dpf more than 0 to 2.5dpf, and the shrinkage factor less than or equal to 2%.In the case that this method can also be included in the fiber experience extraction step for not making the solidification, the fiber of the solidification is collected to bobbin.A kind of spinning head, for by the at most 2.5dpf fiber of the composition production comprising amorphous PEI, the spinning head to include having multiple circular melt canals but the die head without distribution grid.Also disclose by methods described and by the fiber of the spinnerette.

Description

Produce the method for fine amorphous polymer fiber, fine amorphous polymer fiber And for producing the spinning head of this fiber
Technical field
Present invention relates in general to fiber and for producing system, the method and apparatus of fiber.More specifically, the present invention is related to And fine danier amorphous polymer fiber (such as fine danier polyether-imide fiber), and spun in no extract out In the case of silk fiber, system, the method and apparatus for producing such fiber are used for by melt spinning polymer.
Background technology
Use the melt and physical characteristic for hemihedral crystal material, i.e. low melt viscosity, excellent heat endurance and crystallization The optimized method completely set up of property and process equipment have produced synthetic fibers many years.Traditionally, using hemihedral crystal Material produces synthetic fibers, and these hemihedral crystal materials have very low viscosity in the molten state, and need processing method Or die design method is to produce the uniform melt distribution on spinneret hole pattern.Spinning head (spinneret) is designed to have Help being uniformly distributed for melt.But these are designed without advantageously using amorphous polymer, including thermoplastic is such as PEI.It is in traditional melt spinning line using melt spinning method by amorphous thermoplastics processing into fiber The new method of upper trial, with limited success.Some designs that can be attributed to process equipment in these problems are not suitable for In amorphous material.Although needing, again without in the case of without the fiber for extracting synthesis out, by being melted spinning Amorphous thermoplastic is produced into fine fiber with the melt spinning line for the special design for reducing their danier by silk (melt spinning line) or spinning head.
Traditionally, using hemihedral crystal material production synthetic fibers, these hemihedral crystal materials from spinning head after extracting out Crystallization, and easily melt spinning into every danier of fine rule 2 (dpf) and following fine denier fiber.Noncrystal material Material does not form crystal after extraction, and therefore in the melt spinning method using routine, by the extraction section of the process 2dpf and following period are stretched to, and without sufficient elongation percentage and intensity.Traditional processing scheme is not suitable for some non- Crystalline form engineered thermoplastic composition (such as PEI (PEI) spherolite) is converted to fine denier fiber, because traditional Method causes for that can realize the limitation of how fine fiber.Deposited for the polyether-imide fiber of the dpf with 2 or lower In demand.Need development approach and process technology, its will allow produced by amorphous engineering thermoplasties such as PEI 2dpf and Lower fiber.Current trial carries out the production of fine denier fiber with conventional method, and is prolonged in rear transfer process Stretch in operation and extract out, or as little as 2dpf can not be extracted out and lower.
The content of the invention
A kind of embodiment is related to a kind of method, comprises the following steps：Pass through spinneret under 400 to 1500psi pressure Head extruded polymer melt is promoting roller (forwarding roll) to produce spinning fibre, otherwise referred to as on feed roller, Spinning fibre is collected, the fiber of solidification is produced by spinning fibre, and the fiber of solidification is undergone the feelings of extraction step Under condition, the fiber of solidification is collected to bobbin (spool).Melt can include amorphous polymer composition, such as polyethers acyl Imines.The fiber of solidification can have the dpf being more than in the range of 0 to 2.5dpf, and the shrinkage factor less than or equal to 2%.
Other embodiment is related to the danier less than 2.5 and more than 0 to the shrinkage factor less than or equal to 2% Unpumped amorphous polymer fiber.
Still there is other embodiment to be related to for raw by composition (including amorphous PEI, such as PEI) Produce the spinning head of at most 2.5dpf amorphous unpumped polyether-imide fiber.The spinning head can avoid making for distribution grid With, and can be operated under low at least 40% pressure of the operating pressure than the spinning head including distribution grid.The spinning head can So that composition is distributed to die head including the screen modules filter combined with die head (screen pack filter).Should Die head can have multiple circular melt canals, wherein, each circle melt canal has length and diameter, and wherein, often The length of individual circular melt canal：The ratio of diameter is 2:1 to 6:1.
Brief description of the drawings
These and other feature, aspect are better understood with reference to following description and appended claims, and accompanying drawing And advantage, wherein：
Fig. 1 is included in the prior art spray of non-existent two kinds of distribution grids in the design of the various embodiments of the present invention The schematic diagram of silk head design；
Fig. 2 is the various embodiments according to the present invention, the central core point of three concentric rings with charging capillary The schematic diagram of 72 hole nozzle designs of cloth；
Fig. 3 is the various embodiments according to the present invention, is used for what is be distributed with six concentric rings for feeding capillary The schematic diagram of 144 hole nozzle designs of screen modules filter；
Fig. 4 is the schematic diagram of prior art fiber production method, can be changed with using according to the various of the present invention The spinning head of embodiment.
It should be appreciated that various embodiments are not limited to the arrangement shown in the accompanying drawings and means.
Embodiment
In following detailed description and appended claims, many terms are referred to, they are defined with following Implication：
" danier " is the units of measurement of the linear mass density for fiber.In the application and claim, by it Be defined to every 9000 meters by gram based on quality.
As used in the application and claim, " spinning head " is multi-orifice devices, passes through its extrusion plastic polymer Melt is to form fiber.
Regardless of whether being unequivocally demonstrated that, all numerical value all assumes to be modified by term " about " herein.Term " about " is led to Refer to those skilled in the art and thought to be equal to the quantitative range of described value (for example, with same function or knot Really).In many cases, term " about " can include the quantity for being rounding to nearest effective digital.
Embodiments of the present invention are related to for producing fine denier Buddhist nun by engineering thermoplasties' (such as PEI) The method of your fiber.
In the conventional process by melt extrusion formation fiber, high pressure (1000 to 2000psi) is for maintaining across spray The melt of silk head bore is uniformly distributed, and wherein uses chilling apparatus to control cooling velocity, and therefore when it is from spinneret The crystallinity of material is critical when head is extracted out.The various embodiments of the present invention avoid these conditions, and they are for will be non- It is not desirable that crystalline form engineering thermoplasties, which are processed into fine denier fiber,.According to the embodiment party of the present invention Formula, can reduce pressure (400 to 2000psi) to reduce the shearing under melt state on material, and therefore reduce that The drippage of the negative effect of drawback, i.e. fibre bundle (fiber strand) is broken.It has been found that in melt state amorphous The higher viscosity of shape thermoplastic, can provide enough back pressures to be uniformly distributed melt across spinning head in systems. After spinning head is left, the not coolant in quenching cabinet (quench cabinet), and in fact, unexpectedly benefiting In the cooling rate for slowing down amorphous material using heat in this space, and reduce to being spun into the quenching that material is caused Influence.Using method described above, the method according to the invention can be successfully used to polyether-imide fiber being melt-spun into 2dpf and lower.
A kind of embodiment is related to the method including series of steps.These steps can be continuous or discrete. The step of this method can be included by spinning head melt extrusion to produce spinning fibre.
Under the pressure in the range of with lower limit and/or the upper limit, spinning head melt extrusion can be passed through.The scope can be with Including or include lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 100,150,200,250,300,350,400, 450,500,550,600,650,700,750,800,850,900,950,1000,1050,1100,1150,1200,1250, 1300,1350,1400,1450,1500,1550,1600,1650,1700,1750,1800,1850,1900,1950 Hes 2000psi.For example, according to it is some preferred embodiment, can be extruded under 400 to 1500psi pressure by spinning head Melt.
Melt can include amorphous polymer composition.Amorphous polymer composition can have with lower limit And/or the melt flow in the range of the upper limit.The scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26 can be selected from, 27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51, It is any in 52,53,54,55,56,57,58,59 and 60g/10min.For example, according to it is some preferred embodiment, amorphous Shape polymer composition can have the melt flow per 4 to 18 grams of 10min (g/10min).
Melt can include one or more crystalline materials.Amorphous polymer composition can include polyimides.It is poly- Acid imide includes PEI and polyether imide copolymer.PEI can be selected from (i) polyetherimide homopolymer, For example, PEI, (ii) polyether imide copolymer, for example, polyetherimide sulfone, and (iii) combinations thereof.It is poly- Etherimide is known polymer, andWith SILTEM* trade marks (SABIC Innovative Plastics IP B.V. trade marks) under by SABIC Innovative Plastics sell.
In one embodiment, PEI has formula (1)：
Wherein, a is greater than 1, for example, 10 to 1,000 or more, or more specifically, 10 to 500.
Group V in formula (1) be comprising ether group (as used in this article " PEI ") or ether group and The tetravalent linker of the combination (" polyetherimide sulfone ") of arlydene sulfone group.Such connector including but not limited to：(a) Substituted or unsubstituted, saturation, undersaturated or aromatic monocyclic and polycyclic base with 5 to 50 carbon atoms Group, is alternatively replaced with the combination of ether group, arlydene sulfone group or ether group and arlydene sulfone group；(b) there is 1 to 30 The substituted or unsubstituted, linear or branch of carbon atom, saturated or unsaturated alkyl group and alternatively use The combination substitution of ether group or ether group, arlydene sulfone group and arlydene sulfone group；Or include above-mentioned at least one combination. Suitable other substitution is included, but is not limited to, and ether, acid amides, ester and includes above-mentioned at least one combination.
R group in formula (1) is including but not limited to substituted or unsubstituted divalent organic group, such as：(a) have 6 to The aromatic hydrocarbon group and their halide derivative of 20 carbon atoms；(b) there is the straight or branched alkylene of 2 to 20 carbon atoms Base group；(c) there is the cycloalkylidene group of 3 to 20 carbon atoms, or (d) formula (2) divalent group：
Wherein, Q1Including but not limited to divalent moiety, such as-O- ,-S- ,-C (O)-,-SO2- ,-SO- ,-CyH2y- (y is 1 Integer to 5), and their halide derivative, include perfluoroalkylene group.
In one embodiment, tetravalence aromatic groups of the connector V including but not limited to formula (3)：
Wherein, W is divalent moiety, includes-O- ,-SO2-, or formula-O-Z-O- group, wherein ,-O- or-O-Z-O- bases Two valence links of group are that, in 3,3 ', 3,4 ', 4,3 ', or 4,4 ' positions, and wherein, Z is included, but are not limited to, the divalence of formula (4) Group：
Wherein, Q is included, but is not limited to divalent moiety, includes-O- ,-S- ,-C (O) ,-SO2- ,-SO- ,-CyH2y- (y is 1 to 5 integer), and their halide derivative, include perfluoroalkylene group.
In a kind of specific embodiment, PEI, which is included, is more than 1, specifically, and 10 to 1000, or more specifically Ground, the construction unit of 10 to 500 formulas (5)：
Wherein, T is-O- or formula-O-Z-O- group, wherein, two valence links of-O- or-O-Z-O- groups be 3,3 ', 3, 4 ', 4,3 ', or 4,4 ' positions；As defined above, Z is the divalent group of formula (3)；And as defined above, R It is the divalent group of formula (2).
In another specific embodiment, polyetherimide sulfone is the polyetherimide comprising ether group and sulfone group Amine, wherein, at least 50mol% connector V and group R includes the arlydene sulfone group of divalence in formula (1).For example, all Connector V, but there is no group R, arlydene sulfone group can be included；Or all group R, but no connector V can be with Include arlydene sulfone group；Or if the total moles of the V comprising aryl sulfone group and R group are partially larger than or are equal to 50mole%, arlydene sulfone can exist with connector V and some parts of R group.
Even more specifically, polyetherimide sulfone, which can be included, is more than 1, specifically, 10 to 1000, or more specifically, 10 To the construction unit of 500 formulas (6)：
Wherein, Y is-O- ,-SO2-, or formula-O-Z-O- group, wherein ,-O-, SO2-, or-O-Z-O- groups divalence Key be in 3,3 ', 3,4 ', 4,3 ', or 4,4 ' positions, wherein, Z is the divalent group of formula (3) as defined above, and if The 50mole% that is more than of the summation of Y molal quantitys+R molal quantitys includes-SO in formula (2)2- group, R is formula as defined above (2) divalent group.
It should be appreciated that PEI and polyetherimide sulfone can alternatively include and not include ether or ether and sulfuryl The connector V, such as formula (7) of group connector：
Acid imide unit including such connector is generally with 0 to 10mol%, and specifically, 0 to 5mol% unit is total Several amounts is present.In one embodiment, it is present in PEI and polyetherimide sulfone without other connector V.
In another specific embodiment, PEI includes the construction unit of 10 to 500 formulas (5), and Polyetherimide sulfone includes the construction unit of 10 to 500 formulas (6).
PEI and polyetherimide sulfone can be prepared by any suitable method.In one embodiment, PEI and polyether imide copolymer include polycondensation polymerization (polycondensation polymerization ) and halogen displacement polymerization (halo-displacement polymerization process) process.
Polycondensation method can include the method for being used to prepare the PEI with structure (1), referred to as nitration Method (nitro-displacement process) (in formula (8), X is nitro).In a kind of example of nitration method In, with 99% nitric acid nitrating N-Methyl-o-phthalimide to produce N- methyl -4- nitrophthalimides (4-NPI) With the mixture of N- methyl-3-nitros phthalimide (3-NPI).After purification, when there is phase transfer catalyst, Disodium reactant salt of the mixture comprising about 95 parts of 4-NPI and 5 part of 3-NPI in toluene with bisphenol-A (BPA).It is this Reaction produces BPA- double imides and NaNO in referred to as nitration step2.After purification, in acid imide exchange reaction BPA- double imides and phthalic anhydride, to provide BPA dianhydrides (BPADA), itself so with diamines (e.g., in sub- acid amides The m-phenylenediamine (MPD) being in change-polymerization procedure in o-dichlorohenzene) react to provide product polyether acid imide.
Other diamines are also possible.The example of suitable diamines is included：M-phenylene diamine (MPD)；P-phenylenediamine；2,4- diaminourea Toluene；2,6- diaminotoluenes；MXDP；Terephthaldehyde's base diamines；Benzidine；3,3 '-dimethylbenzidine；3, 3 '-dimethoxy benzidine；1,5- diaminonaphthalenes；Double (4- aminophenyls) methane；Double (4- aminophenyls) propane；Double (4- ammonia Base phenyl) thioether；Double (4- aminophenyls) sulfones；Double (4- aminophenyls) ethers；4,4 '-diamino-diphenyl propane；4,4 '-amino Diphenyl methane (4,4 '-methylene dianiline (MDA))；4,4 '-diamino diphenyl sulfide；4,4 '-diamino diphenyl sulfone；4,4’- Diamino-diphenyl ether (4,4 '-oxygen dianil)；1,5- diaminonaphthalenes；3,3 '-dimethylbenzidine；3- methyl heptamethylene two Amine；4,4- dimethyl heptamethylene diamines；2,2 ', 3,3 '-tetrahydrochysene -3,3,3 ', 3 '-tetramethyl -1,1 '-spiral shell two [1H- indenes] -6, 6 '-diamines；3,3 ', 4,4 '-tetrahydrochysene -4,4,4 ', 4 '-tetramethyl -2,2 '-spiral shell two [2H-1- benzos-pyrans] -7,7 '-diamines； 1,1 '-bis- [1- amino-2-methyl -4- phenyl] hexamethylenes, and they isomers and include above-mentioned at least one mixing Thing and blend.In one embodiment, diamines is specific aromatic diamine, especially, m-phenylene diamine (MPD) and p-phenylenediamine, With include above-mentioned at least one mixture.
The suitable dianhydride that can be used together with diamines, comprising and be not limited to double [4- (3, the 4- dicarboxyl benzene of 2,2- Epoxide) phenyl] propane dianhydride；4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides；4,4 '-bis- (3,4- dicarboxyl benzene oxygen Base) diphenylsulfide dianhydride；4,4 '-bis- (3,4- di carboxyl phenyloxies) benzophenone dianhydrides；4,4 '-bis- (3,4- dicarboxyl benzene Epoxide) diphenyl sulfone dianhydride；Double [4- (2,3- di carboxyl phenyloxies) phenyl] propane dianhydrides of 2,2-；4,4 '-bis- (2,3- dicarboxyls Phenoxy group) diphenyl ether dianhydride；4,4 '-bis- (2,3- di carboxyl phenyloxies) diphenylsulfide dianhydrides；4,4 '-bis- (2,3- dicarboxyls Phenoxy group) benzophenone dianhydride；4,4 '-bis- (2,3- di carboxyl phenyloxies) diphenyl sulfone dianhydrides；4- (2,3- dicarboxyl benzene oxygen Base) -4 '-(3,4- di carboxyl phenyloxies) diphenyl -2,2- propane dianhydrides；4- (2,3- di carboxyl phenyloxies) -4 '-(3,4- bis- Carboxyphenoxy) diphenyl ether dianhydride；4- (2,3- di carboxyl phenyloxies) -4 '-(3,4- di carboxyl phenyloxies) diphenylsulfide two Acid anhydride；4- (2,3- di carboxyl phenyloxies) -4 '-(3,4- di carboxyl phenyloxies) benzophenone dianhydride；4- (2,3- dicarboxyl benzene oxygen Base) -4 '-(3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides；Double (2,3- di carboxyl phenyloxies) benzene dianhydrides of 1,3-；Isosorbide-5-Nitrae-bis- (2, 3- di carboxyl phenyloxies) benzene dianhydride；Double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,3-；1,4- is double (3,4- di carboxyl phenyloxies) Benzene dianhydride；3,3 ', 4,4 '-biphenyltetracaboxylic dianhydride；3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride；Naphthalenedicarboxylic acid dianhydride, Such as 2,3,6,7- naphthalenedicarboxylic acid dianhydrides, etc.；3,3 ', 4,4 '-diphenyl sulfonic acid tetracarboxylic dianhydride；3,3 ', 4,4 '-diphenyl ether Tetracarboxylic dianhydride；3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride；4,4 '-bis- (3,4 di carboxyl phenyloxy) hexichol Base thioether dianhydride；4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides；4,4 '-bis- (3,4- di carboxyl phenyloxies) hexichol Base propane dianhydride；3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；Double (phthalic acid) phenyl sulfonium compound oxide dianhydride (bis (phthalic)phenylsulphineoxide dianhydride)；To phenylene-bis- (triphenyl phthalic acids) dianhydride； Metaphenylene-bis- (triphenyl phthalic acid) dianhydride；Double (triphenyl phthalic acids) -4,4 '-diphenyl ether dianhydride；Double (three Phenyl phthalic acid) -4,4 '-diphenyl methane dianhydride；2,2 '-bis- (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides；4,4’- Oxydiphthalic acid dianhydride；Pyromellitic acid anhydride；3,3 ', 4,4 '-diphenylsulfone acid dianhydride；4,4 '-bisphenol-A two Acid anhydride；The O-phthalic acid dianhydride of quinhydrones two；6,6 '-bis- (3,4- di carboxyl phenyloxies) -2,2 ', 3,3 '-tetrahydrochysene -3,3 ', 3,3 '-four Methyl -- 1,1 '-spiral shell two [1H- indenes] dianhydride；7,7 '-bis- (3,4- di carboxyl phenyloxies) -3,3 ', 4,4 '-tetrahydrochysene -4,4,4 ', 4 '-tetramethyl -- 2,2 '-spiral shell two [2H-1- chromenes] dianhydride；1,1 '-bis- [1- (3,4- di carboxyl phenyloxies) -2- methyl - 4- phenyl] hexamethylene dianhydride；3,3 ', 4,4 '-diphenylsulfone acid dianhydride；3,3 ', 4,4 '-diphenylsulfide tetracarboxylic dianhydride； 3,3 ', 4,4 '-diphenyl sulfoxide tetracarboxylic dianhydride；4,4 '-oxydiphthalic acid dianhydride；The O-phthalic of 3,4 '-oxo two Acid dianhydride；3,3 '-oxydiphthalic acid dianhydride；3,3 '-benzophenone tetracarboxylic dianhydride；The O-phthalic of 4,4 '-carbonyl two Acid dianhydride；3,3 ', 4,4 '-diphenyl methane tetracarboxylic dianhydride；Double (4- (3,3- dicarboxyphenyis) propane dianhydrides of 2,2-；2,2- Double (4- (3,3- dicarboxyphenyis) hexafluoropropane dianhydrides；(3,3 ', 4,4 '-diphenyl) Phenylphosphine tetracarboxylic dianhydride；(3,3’,4, 4 '-diphenyl) phenylphosphine oxide tetracarboxylic dianhydride；2,2 '-two chloro- 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides；2,2 '-two Methyl -3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；2,2 '-dicyano -3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；2,2’- Two bromo- 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides；2,2 '-two iodo- 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides；2,2 '-two Trifluoromethyl -3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；2,2 '-bis- (1- methyl 4-phenyls) -3,3 ', 4,4 '-xenyl four Carboxylic acid dianhydride；2,2 '-bis- (1- trifluoromethyl -2- phenyl) -3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；2,2 '-bis- (1- trifluoros Methyl -3- phenyl) -3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；2,2 '-bis- (1- trifluoromethyl -4- phenyl) -3,3 ', 4,4 ' - Biphenyl tetracarboxylic dianhydride；2,2 '-bis- (1- phenyl -4- phenyl) -3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride；4,4 '-bisphenol-A Dianhydride；3,4 '-bisphenol A dianhydride；3,3 '-bisphenol A dianhydride；3,3 ', 4,4 '-diphenyl sulfoxide tetracarboxylic dianhydride；4,4 '-carbonyl two O-phthalic acid dianhydride；3,3 ', 4,4 '-diphenyl methane tetracarboxylic dianhydride；2,2 '-bis- (1,3- trifluoromethyl -4- phenyl) -3, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, and their all isomers, and above-mentioned substance combination.
Halogen displacement polymerization for manufacturing PEI and polyetherimide sulfone includes but is not limited to, formula (8) reaction of double (phthalimides)：
Wherein, R is as described above, and X is nitryl group or halogen.For example, passing through the corresponding acid anhydrides of formula (9) Can form double-phthalimide (8) with the condensation of the organic diamine of formula (10)：
Wherein, X is nitryl group or halogen,
H2N-R-NH2(10),
Wherein, R is as described above.
The illustration of the amines of formula (10) is included：Ethylenediamine, propane diamine, trimethylene diamine, Diethylenetriamine, three second four Amine, hexamethylene diamine, heptamethylene diamines, eight methylene diamines, nine methylene diamines, decamethylene diamine, 1,12- 12 Alkane diamines, 1,18- octadecamethylene diamines, 3- methyl heptamethylenes diamines, 4,4- dimethyl heptamethylenes diamines, the methylene of 4- methyl nine Base diamines, the methylene diamine of 5- methyl nine, 2,5- dimethyl hexamethylene diamine, 2,5- dimethyl heptamethylenes diamines, 2,2- Double (the 3- aminopropan oxygen of dimethylated propyl diethylenetriamine, N- methyl-bis- (3- aminopropyls) amine, 3- methoxyl groups hexamethylene diamine, 1,2- Base) ethane, double (3- aminopropyls) thioethers, 1,4- cyclohexane diamines, double-(4- aminocyclohexyls) methane, m-phenylene diamine (MPD), to benzene Diamines, 2,4 di amino toluene, 2,6- diaminotoluenes, MXDP, terephthaldehyde's base diamines, 2- methyl -4,6- Diethyl -1,3- phenylenediamines, 5- methyl -4,6- diethyl -1,3- phenylenediamines, benzidine, 3,3 '-dimethyl diphenyl Amine, 3,3 '-dimethoxy benzidine, 1,5-diaminonaphthalene, double (4- aminophenyls) methane, double (chloro- 4- amino -3,5- bis- of 2- Ethylphenyl) methane, double (4- aminophenyls) propane, 2,4- double (b- amino-tert-butyl) toluene, double (p- b- amino-tert-s Butyl phenyl) ether, double (p- b- methyl-o-amino-phenyl) benzene, double (p- b- methyl-o- Aminopentyl) benzene, 1,3- diaminos Double (3- aminopropyls) tetramethyl disiloxanes of base -4- cumenes, double (4- aminophenyls) ethers and 1,3-.These can be used The mixture of amine.The illustration of the amines of formula (10) comprising sulfone group is including but not limited to diaminodiphenylsulfone (DDS) And double (aminophenoxy phenyl) sulfones (BAPS).Any combination comprising above-mentioned amine can be used.
, can be by double (phthalimides) (8) with formula HO-V-OH's when existing or lacking phase transfer catalyst The reaction synthesizing polyether acid imide of the alkali metal salt of the aromatic hydrocarbons of dihydroxy substitution, wherein, V is as described above.Suitable Phase transfer catalyst is disclosed in U.S. Patent number 5,229,482.Specifically, the aromatic hydrocarbons that dihydroxy can be used to replace, bis-phenol, The combination of the alkali metal salt for the aromatic hydrocarbons that alkali metal salt and other dihydroxy such as bisphenol-A, or bis-phenol replace.
In one embodiment, PEI includes the construction unit of formula (5), wherein, each R is independently to Asia Phenyl or metaphenylene include above-mentioned at least one mixture；And T is formula-O-Z-O- group, wherein ,-O-Z-O- Two valence links of group are that, in 3,3 ' positions, and Z is 2,2- diphenylenepropane radicals group (bisphenol-A group).Moreover, polyetherimide Amine sulfone includes the construction unit of formula (6), and wherein at least 50mole% R group has formula (4), and wherein Q is-SO2- and it is remaining R group be independently to phenylene or metaphenylene or comprising above-mentioned at least one combination；T is formula-O-Z-O- group, Wherein, two valence links of-O-Z-O- groups are that, in 3,3 ' positions, and Z is 2,2- diphenylenepropane radicals group.
, can be individually or in combination with each other or public with others in the polymeric component that manufacture is described herein The polymeric material opened is used together PEI and polyetherimide sulfone.In one embodiment, polyetherimide is only used Amine.In another embodiment, PEI：The weight ratio of polyetherimide sulfone can be 99:1 to 50:50.
PEI can have as 5000 to 100,000 grams every mole measured by gel permeation chromatography (GPC) The weight average molecular weight (Mw) of (g/ moles).In some embodiments, Mw can be 10,000 to 80,000.As made herein Molecular weight refers to absolute weight average molecular (Mw).
As measured by 25 DEG C in metacresol, PEI, which can have, is more than or equal to 0.2 deciliter/gram (dl/g) intrinsic viscosity.Within the scope of this, as measured by 25 DEG C in metacresol, intrinsic viscosity can be 0.35 to 1.0dl/g.
As used according to measured by ASTM tests D3418 differential scanning calorimetry (DSC), PEI can have There are the glass transition temperature more than 180 DEG C, specifically, 200 DEG C to 500 DEG C.In some embodiments, PEI, especially It is that PEI has 240 to 350 DEG C of glass transition temperature.
As using 6.7 kilograms of (kg) weight, at 340 to 370 DEG C, passing through American Society For Testing Materials (American Society for Testing Materials) measured by (ASTM) DI 238, PEI can have 0.1 to 10 The melt index (MI) of Grams Per Minute (g/min).
Alternative halogen displacement for manufacturing PEI (for example, PEI with structure (1)) gathers Conjunction method is the method for referred to as chlorine method of replacing (in formula (8), X is chlorine).Illustrate chlorine method of replacing below：When there is catalytic amount Phenyl-phosphonite sodium catalyst when, 4- chloro-phthalic anhydrides and m-phenylenediamine react to produce m-phenylenediamine Double chlorophthalimides (CAS 148935-94-8).Then there is urging in o-dichlorohenzene or fennel ether solvents During agent, double chlorophthalimides with the chlorine replacement reaction of BPA disodium salts by carrying out polymerisation.Alternately, may be used To use that 3- is chloro- and the mixture of 4- chloro-phthalic anhydrides is to provide the mixing of isomeric pair of chlorophthalimide Thing, it can be by being polymerize with the displacement of the chlorine of BPA disodium salts as described above.
Siloxane polyetherimide can include polysiloxanes/polyetherimide blocks' copolymer, based on block copolymer Gross weight, its have be more than 0 and the content of siloxane less than 40 percetages by weight (wt%).Block copolymer includes formula (I) Siloxane blocks：
Wherein, R at each occurrence1-6Independently selected from the group being made up of the following：With 5 to 30 carbon atoms It is substituted or unsubstituted, saturation, it is undersaturated, or aromatic monocyclic group, substituted with 5 to 30 carbon atoms or It is unsubstituted, saturation, it is undersaturated, or aromatic series polycyclic moiety, it is substituted or unsubstituted with 1 to 30 carbon atom Alkyl group, the substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, V is tetravalent linker, its be selected from by with The group of lower every composition：It is substituted or unsubstituted with 5 to 50 carbon atoms, saturation, it is undersaturated, or aromatic series list Ring and polycyclic moiety, with the substituted or unsubstituted alkyl group of 1 to 30 carbon atom, with 2 to 30 carbon atom substitutions Or unsubstituted alkenyl group, and include the combination of at least one of above-mentioned connector, g is equal to 1 to 30, and d be 2 to 20.Commercially available siloxane polyetherimide can be in trade name SILTEM* (* SABIC Innovative Plastics IP B.V. trade mark) under, obtained from SABIC Innovative Plastics.
PEI can have the weight average molecular weight (Mw) in the range of with lower limit and/or the upper limit.Scope can To include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 5000,6000,7000,8000,9000, 10000,11000,12000,13000,14000,15000,16000,17000,18000,19000,20000,21000, 22000,23000,24000,25000,26000,27000,28000,29000,30000,31000,32000,33000, 34000,35000,36000,37000,38000,39000,40000,41000,42000,43000,44000,45000, 46000,47000,48000,49000,50000,51000,52000,53000,54000,55000,56000,57000, 58000,59000,60000,61000,62000,63000,64000,65000,66000,67000,68000,69000, 70000,71000,72000,73000,74000,75000,76000,77000,78000,79000,80000,81000, 82000,83000,84000,85000,86000,87000,88000,89000,90000,91000,92000,93000, 94000,95000,96000,97000,98000,99000,100000,101000,102000,103000,104000, 105000,106000,107000,108000,109000, and 110000 dalton.For example, PEI can have 5, 000 to 10,000 dalton, 5,000 to 80,000 dalton, or 5000 to 70, the weight average molecular weight (Mw) of 000 dalton.It is main The PEI that the alkylamine wanted is modified is by with the lower molecular weight of the unmodified PEI compared with the beginning and more High melt flows.
PEI can be selected from and is made up of the following in group：PEI (such as in United States Patent (USP) 3, 875,116；Described in 6,919,422 and 6,355,723)；Silicone polyetherimide (such as in United States Patent (USP) 4, Described in 690,997 and 4,808,686)；Polyetherimide sulfone is (as described in United States Patent (USP) 7,041,773 ), and combinations thereof, each entirety of these patents is hereby incorporated by.
PEI can have the glass transition temperature in the range of with lower limit and/or the upper limit.Scope can be with Including or include lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 100,110,120,130,140,150,160, 170,180,190,200,210,220,230,240,250,260,270,280,290,300, and 310 degrees Celsius.For example, polyethers Acid imide can have greater than about 200 degrees Celsius of glass transition temperature (Tg).
PEI can be substantially free of benzylic proton (benzylic proton) (being less than 100ppm).Polyetherimide Amine can be free of benzylic proton.PEI can have the benzylic proton of the amount less than 100ppm.In a kind of embodiment In, the amount of benzylic proton between more than 0 to less than between 100ppm.In another embodiment, the amount of benzylic proton is nothing Method detection.
PEI can be substantially free of halogen atom (being less than 100ppm).PEI can be former without halogen Son.PEI can have the halogen atom of the amount less than 100ppm.In one embodiment, the amount of halogen atom is situated between In more than 0 to less than between 100ppm.In another embodiment, the amount of halogen atom is undetectable.
In one embodiment, PEI includes PEI thermoplastic compounds, comprising：(a) polyethers acyl Imines, (b) phosphorous stabilizer is effectively measured comprising the stabilizer of phosphorus for the Melt Stability for increasing PEI Show relatively low volatility to cause, as measured by the thermogravimetry of the initial amount of the sample as the stabilizer comprising phosphorus , under an inert atmosphere, with 20 DEG C per minute of the rate of heat addition, sample is heated to after 300 DEG C from room temperature, by weight greatly Still do not evaporate in or equal to percent 10 sample of initial amount.In one embodiment, phosphorous stabilizer has formula P-Ra, wherein, R ' is independently H, alkyl, alkoxy, aryl, aryloxy group or oxygen substituent, and a is 3 or 4.So it is adapted to The example of PEI of stabilization can find that it is hereby incorporated by as overall in U.S. Patent number 6,001,957.
This method can be included in do not extract spinning fibre out in the case of collect spinning fibre in propulsion or feed roller The step of.In the typical art methods described in as Fig. 4, when a series of extraction godet (being referred to as 409) is (logical Often with high speed operation) when extract danier of the fiber to reduce them, assemble guide plate (convergence guide) 406 Collect spinning fibre and apply pulling force (pull) on fiber.Can be in the form of kiss roll (kiss roll) 408 by upper The fiber 407 that oily device (finishapplicator) extremely solidifies oil supply materials application.In a device in accordance with the invention, give Oil and kiss roll 408 use be it is optional, and it is a series of extraction godet 409, can be complete in some embodiments Exempt.Therefore, the apparatus according to the invention includes the spinning head according to Fig. 2 or 3, propulsion or charging for collecting spinning fibre Roller (forwarding or feeding roll) and the fine danier collected thereon for further using are not extracted out At least one bobbin (spool) or reel (bobbin) of fiber.This method can be included from the life of melt spinning polymer The step of producing cured fiber.The embodiment of this method can be included in do not make cured fiber experience extract out step in the case of, The step of cured fiber being collected on bobbin.The embodiment of this method can be in the situation without air blast cooling cooling step Under, produce cured fiber.In the case that this method can be included in without any quenching (annealing, quenching) step, online The step of fiber being collected on axle.This method can be included in spinning fibre and leave after spinning head, the step of heating spinning fibre.
Cured fiber can have the dpf in the range of with lower limit and/or the upper limit.Scope can include or not include Lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3, 3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 Hes 5dpf.For example, according to it is some preferred embodiment, cured fiber can have be more than 0 to 2.5dpf in the range of dpf.
Cured fiber can have the shrinkage factor in the range of with lower limit and/or the upper limit.Scope can be included or not Including lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9, 1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9, 3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 Hes 5%.For example, according to it is some preferred embodiment, cured fiber can have less than or equal to 2% shrinkage factor.
A kind of embodiment further relates to new nozzle design, and these designs are adapted to use the amorphous engineering thermoplastic of high viscosity Property plastics are to manufacture the fiber with low denier and low-shrinkage.With need to use condition of high voltage (for example, 1500 to 2000psi) the known processing of the equally distributed polyether-imide fiber to maintain the melt across spinneret hole is different, if Count according to the spinning heads of various embodiments can as little as 400psi (for example, in the range of 400 to 1500psi, it is preferable that In the range of 400 to 1200psi, most preferably, in the range of 400-1000psi) pressure under be uniformly distributed.Die design and Corresponding spinning head allows amorphous thermoplastic, and such as PEI melt spinnings are into fine denier fiber.These embodiment party Formula can in whole die head wholecircle shape melt canal, dead space minimizes, or pause (hang up) amorphous material It will collect or be vortexed and not runny region, and suspend (hang up) and degrade, and then intermittently discharge degraded Material is into melt flow stock.The L/D ratio rate of melt canal can be optimization for amorphous material, and can be with Design distribution channel is to reduce the shearing on material, and using the more high viscosity of the amorphous material of melt state to obtain Across being uniformly distributed for spinning head melt.By similar designed in proposed things, regardless of the how previous root of danier Originally the material of fiber can not be spun into, with spinning and can be wrapped on bobbin, and optimize this method to realize finer denier Fiber.
A kind of specific embodiment is related to spinning head and/or the filament spinning component including spinning head, and it is used for by comprising non- The composition production of crystalline form PEI at most 2.5dpf amorphous unpumped polyether-imide fiber.Spinning head is not required to There is distribution grid.
Spinning head can include the die head with multiple circular melt canals, wherein, each circle melt canal has length Degree and diameter.The length of each circle melt canal：The ratio of diameter can be 1:1,2:1,3:Isosorbide-5-Nitrae:1,5:1,6:1,7:1, 8:1,9:1,10:1,11:1, or 12:1.For example, according to it is some preferred embodiment, the length of each circle melt canal： The ratio of diameter can be 2:1 to 6:1.
According to a kind of embodiment, compared with the identical spinning head including distribution grid, the spinning head can be in reduction Operated under pressure.According to various embodiments, the operating pressure of the spinning head without distribution grid is relative to the phase including distribution grid Same spinning head, can decline certain percentage.The percentage can be in the range of with lower limit and/or the upper limit.Scope can To include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 1,2,3,4,5,6,7,8,9,10,11,12, 13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37, 38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59 and 60%.For example, According to it is some preferred embodiment, according to various embodiments, the operating pressure of the spinning head without distribution grid is relative to bag The identical spinning head of distribution grid is included, at least 40% percentage can be reduced.
Spinning head may further include at least one screen modules filter (the screen pack combined with die head Filter), composition is distributed to die head.Screen modules filter can have in the model with lower limit and/or the upper limit Enclose interior screen size (screen size).Scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit can With selected from 100,110,120,130,140,150,160,170,180,190,200,210,220,230,240,250,260, 270,280,290,300,310,320,330,340,350,360,370,380,390,400,410,420,430,440,450, 460,470,480,490 and 500 mesh.For example, according to it is some preferred embodiment, screen modules filter can have The US screen sizes of 200 to 400 mesh.
Other embodiment is related to amorphous polymer fiber.Fiber can be extracted out, but even in unpumped state, Fiber can have excellent performance.
According to various embodiments, unpumped amorphous polymer fiber can have with lower limit and/or the upper limit In the range of danier.Scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 0, 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2, 2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9, and 3.For example, according to it is some preferred embodiment, it is unpumped Amorphous polymer fiber can have the danier less than 2.5.
According to various embodiments, unpumped amorphous polymer fiber can have with lower limit and/or the upper limit In the range of shrinkage factor.Scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0, 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2, 2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9 Hes 4%.For example, according to it is some preferred embodiment, unpumped amorphous polymer fiber can have be more than 0 to being less than or Shrinkage factor equal to 2%.
According to various embodiments, unpumped amorphous polymer fiber can have with lower limit and/or the upper limit In the range of polydispersity (Mw/Mn).Scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit, can With selected from 1,1.25,1.5,1.75,2,2.25,2.5,2.75,3,3.25,3.5,3.75,4,4.25,4.5,4.75,5,10, 15,20,25,30,35,40,45,50, and 100.For example, according to it is some preferred embodiment, according to various embodiments, not The amorphous polymer fiber of extraction can have the polydispersity (Mw/Mn) more than or equal to 2.5.
According to various embodiments, unpumped amorphous polymer fiber can have with lower limit and/or the upper limit In the range of danier.Scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0, 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2, 2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9 and 4. For example, according to it is some preferred embodiment, according to various embodiments, unpumped amorphous polymer fiber can have Danier less than 2.2.
According to various embodiments, unpumped amorphous polymer fiber can have with lower limit and/or the upper limit In the range of intensity.Scope can include or not include lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 1,1.1, 1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1, 3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9,5,10, 15,20,25,30,35,40,45 and 50cN/dtex.For example, according to it is some preferred embodiment, according to various embodiments, Unpumped amorphous polymer fiber can have at least 2.6cN/dtex intensity.
According to various embodiments, unpumped amorphous polymer fiber can have the performance being identified above, simultaneously It is also (unanneled is unannealed) not being quenched.
Other embodiment, which is related to, includes the article of unpumped amorphous polyether-imide fiber.Article can be included But it is not limited to by polyether-imide fiber that (including i.e., one or more unannealed amorphous polyether-imide fibers, optional Ground is wound, and is woven, knitting, spinning, or is additionally combined with different types of fiber) yarn that is made, by unpumped amorphous The fabric that shape fiber and/or yarn are made, and including or based on the compound of fabric that is made up of unpumped amorphous fiber. The example of suitable compound includes but is not limited to：Paper, for example, electrical paper (electrical paper), honeycomb paper has Spin speciality paper (woven specialty paper), nonwoven speciality paper (non-woven specialty paper)；Structure is answered Compound；Half structure compound.
In a word, including for the method for manufacturing unpumped amorphous polymer fiber include, 400 to 1500psi's Under pressure (for example, from 400 to 1000psi), by spinning head melt extrusion to produce spinning fibre, wherein, melt is comprising non- Crystalline form polymer composition, for example, PEI, can appoint ground, wherein, amorphous polymer composition can have 4 to 18g/10min melt flow；In the case of no extraction spinning fibre, spinning fibre is collected on feed roller, from spinning Fiber produce cured fiber, wherein, cured fiber have more than 0 to 2.5dpf dpf, and cured fiber have be less than or wait In 2% shrinkage factor；And in the case where not making cured fiber experience extract step out, cured fiber is wound to bobbin On.In any of above embodiment, one or more following conditions can be applied：This method can be wrapped still optionally further Include, collect fiber to bobbin in the case of no annealing steps；This method may further include, spinning fibre from Open after spinning head, heat spinning fibre, in the case of no air blast cooling cooling step, produce cured fiber；Melt includes One or more crystalline materials (crystalline material).
Amorphous polymer fiber, the fiber for example manufactured by the above method, with less than 2.5, less than 2.2, or is less than 2.0 danier, and more than 0 to the shrinkage factor less than or equal to 2%；Fiber may furthermore is that polyether-imide fiber, example Such as, polyimide alternatively have 4 to 18g/10min melt flow, still optionally further, wherein, fiber have be more than or Equal to 2.5 polydispersity (Mw/Mn), and alternatively at least 2.6cN/dtex intensity.Fiber can be unannealed.Including upper Stating the article of fiber includes yarn, fabric and compound.
For producing at most 2.5dpf amorphous unpumped polyether-imide fiber (for example, with 4 to 18g/ 10min melt flows) the above method in useful spinning head do not have distribution grid；And with multiple circular melt canals Die head, wherein, each circle melt canal has length and diameter, and wherein, the length of each circle melt canal：Diameter Ratio be 2:1 to 6:1, alternatively, wherein, spinning head in the operating pressure than the identical spinning head including distribution grid at least Run under low 40% pressure, still optionally further, wherein, spinning head further comprises at least one filtering combined with die head Screen component filter is so that composition is distributed to the filter of die head, such as the US screen sizes with 200 to 400 mesh.
The present invention is further described in following exemplary embodiment, wherein, all parts and percentages are by weight Gauge, unless otherwise indicated.
Embodiment
Table 1 is listed in the material used in embodiment.
Using two kinds of nozzle designs in embodiment.First, using α nozzle designs (Alpha Spinneret Design) (referring to Fig. 1).The nozzle design of these types will be described in more detail now.Secondly, using according to each of the present invention Plant the β components nozzle design (Beta Pack Spinneret Design) (referring to Fig. 2 and 3) of embodiment.
1. the description of α nozzle designs
As shown in figure 1, according to prior art, filament spinning component (spin pack) 100 includes capillary spinneret plate 102, its The rectangular block in the heater jacket region of extruder is to fit into, there are about 0.25 inch gaps around it.Prior art is spun Silk component 100 is between bottom plate 101 and capillary spinneret plate 102, it is necessary to install a series of distribution grids 103.Design distribution grid 103 are used to provide pressure block (pressure block) for both melt is evenly distributed to the rectangle battle array of 144 capillaries Row.Depending on the extruder of use, these plates can be different sizes and shapes.
Distribution grid 103 is very thin, the thickness only with about 0.02 inch, and the melt canal of the material is only 0.01 inch diameter and 3/16 inchage.The restricted size of melt canal is amorphous material and higher inside group Part pressure (interal pack pressure) creates strict flox condition.Intraware pressure causes adding for limited material Work window.It also causes to separate out (plate out) in production period material or built up on the face of capillary spinneret plate 102. This residue constantly accumulates and has to scrape off from face over time.This causes undesirable in this process Interrupt.
The temperature control of filament spinning component 100 is by installing the convection current of the air gap space around component in an extruder Heat to realize.The change of service condition, such as temperature and pressure are more slowly responded using the system of filament spinning component 100.In addition, The significant temperature loss from set point to filament spinning component is generally observed, it is necessary to which set point temperatures are adjusted paramount by operating personnel In about 20 degrees Celsius of desired temperature.
2. the description (" design of β components ") of new nozzle design
According to various embodiments, the capillary spinneret for producing melt-spinning fiber by PEI can be with class Shower head design is similar to, because around circular components face, capillary spinneret there can be equally distributed capillary array.
According to various embodiments, Fig. 2 is the schematic diagram of filament spinning component 200 of the explanation with capillary spinneret 201. Special capillary spinneret 201 illustrated in fig. 2 has 72 capillaries 202, but can use any suitable number of Capillary.Capillary spinneret 201 can be arranged with interlayer together with distribution block 203 between bottom plate 204 and end cap 205. Distribution block 203, which can have, to be used to melted material being distributed to multiple distribution holes 206 of capillary spinneret 201.End cap 205 Can have with corresponding hole 208 can be aligned on bottom plate 204 multiple through holes 207 with tight via bolt or others fastener Gu and compress filament spinning component 200.
According to various embodiments, Fig. 3 is the schematic diagram of filament spinning component 300 of the explanation with capillary spinneret 301. Special capillary spinneret 301 illustrated in fig. 3 has 144 capillaries 315, but can use any suitable number of Capillary 315., can be together with screen modules filter (screen pack between end cap 305 and one or more bottom plates Filter) 302, interlayer arranges capillary spinneret 301 together for the first packing ring (gasket) 303 and second packing ring 304.Such as Fig. 3 It is shown, the first bottom plate 306 and the second bottom plate 307 can be used.
Multiple through holes 308 that end cap 305 can have with corresponding hole 309 can be aligned on the first bottom plate 306 are with via spiral shell Bolt or other fasteners, part that is fixed and compressing multiple filament spinning components 200.First bottom plate 306 can via bolt or Other fasteners are fastened to the second bottom plate 307, and (bolt or other fasteners are inserted through logical on the first bottom plate 306 The receiver hole 311 that hole 310 enters on the second bottom plate 307).
Second bottom plate 307 can include injection port 312, and melted material can be injected into filament spinning component 300, example by it Such as, from via bolt or other fasteners, by the extruder fastened thereto of filament spinning component 300, (bolt or other fastenings are filled Put the fastener hole 313 being inserted through on the second bottom plate 307).First bottom plate 306 can include it is one or more distribution mouths 314 with Melted material is allowed to continue to flow through filament spinning component 300.
The embodiments described below uses filament spinning component 300 as shown in Figure 3, because the capillary with 144 capillaries Pipe spinning head 301 causes the throughput similar with old " α " component design.
In this design, melt is delivered to component face and has been simplified and has improved (streamline, pipelining). Through eliminating distribution grid, and only by the distribution of the completion melt of net-filter assembly filter 302.It is distributed mouth 314 and wholecircle shape is provided Work wheel system (full round runner system) so that melt flow is introduced into screen modules mistake from machine exit The center of filter dorsal part.Packing ring 303 and 304 can be behind filter 302 (that is, in the side closest to the first bottom plate 306 On) enough cavitys are provided, to allow the uniform flow that material is formed behind silk screen.Once the shape after screen modules filter Into enough pressure, melt is through and into spinning head.Then as shown in figure 4, passing through pressure of the capillary 315 via formation Power extrudes it, and is drawn in take-up roll (take up roll) and is wound to one or more reels by it (bobbin) on 410.
Fig. 4 is the schematic diagram of fiber process 400.Melt flow 401 from extruder can be fed to measuring pump 402, By filter 403, and pass through spinning head 404.After spinning head 404 is left, melt flow 401 can be made to be moved back through air Fire 405.Convergence guiding piece (convergence guide) 406 can guide fiber 407 to feeding means (finish Applicator) 408, and by a series of extraction godet (drawing godet) 409 be wound to it is one or more around In spool 410.
Various spinning heads are designed and construct to allow to study length and diameter (L/D) ratio (1 different in capilar bore To 6), and 0.2mm to 1.0mm diameter.In addition, the use of screen size scope being 200 to 400 purposes depending on viscosity of material Screen modules filter.
In Hills GHP bi-component melt spinning extrusion line, this spin pack design is installed.It is designed to be assemblied in α Design in the identical package shell (pack envelope) used.The new design of configuration is with enough in the offer of component head Space so as to allowing with the directly Contact Temperature control of the heating tape (high wattage heater band) of high wattage.Newly Design provides closer and faster thermal control in filament spinning component face (in the key component during melt spinning).
PEI description is manufactured with new β nozzle designs
Drying material will cause depolymerization in 4 to 8 hours to remove under melt state under 300 degrees Fahrenheits Any moisture.
Assembled in preheating oven and place filament spinning component, to reach it before being attached in machine and melt flow Operation temperature.
Before any material is introduced into extruder, opens machine and preheat several hours.Once reaching temperature, squeezing Go out and automatic loader is utilized on the funnel above machine, spherolite is loaded into extruder.Melt Pump is opened, extruder is then opened. These are controlled manually until two melt flows stock comes out from machine, and realize rational melt pressure and speed.With Afterwards, in the whole remainder of process, melt pressure is automatically controlled by pressure.
When temperature and pressure reaches desired balance, stop pump and extruder, and from baking oven remove spinning head and It is mounted in machine.Outside heating tape controls thermocouple to be attached on filament spinning component together with it.Then turn on this Individual unit and the setting set point desired by.
Then, Melt Pump and extruder are reopened.The fiber of extrusion is collected in pail for used dressings, and cultivates spinning head and reaches Operating temperature.When this happens, melt sample is taken to make fiber, to determine melt proportion.
Once temperature and pressure becomes level, then fiber is stretched in thread suction gun, and in optional spinning oil-feeding It is collected under kiss roll on the charging of (spin finish kiss roll) or propulsion roller.Pump and the speed restriction for promoting roller The diameter of obtained fiber, or the danier (dpf) per filament.Once desired dpf is obtained, followed by fiber to wrapping head In.Fibre bundle is wound up at least one bobbin or multiple reels by wrapping head to be used to then use in downstream process.
For 2dpf and the PEI fibers of more low denier, we run pumps with 4 to 6rpm, and with 1500m/min extremely 2500m/min operations promote roller.Need not further it be stretched in any reel off raw silk from cocoons on roller (draw roll), or with this mistake It need not be annealed on any loose roller (relaxing roll) of journey configuration.
PEI description is manufactured with old α nozzle designs
The step of α nozzle designs is identical in terms of the process steps for starting and operating.When you want to realize 2dpf or During finer fiber, there is difference.Be necessary in this case reel off raw silk from cocoons on roller stretch fiber and attempt control in pine Shrinkage factor on relaxation roller (relax roll).
For the 2dpf PEI fibers using this set, we are 5 to operating Melt Pump, and feed roller between 7rpm For 1500m/min to 2500m/min.1500m/min is maintained at a temperature of 200 degrees Celsius to operate between 2500m/min Feed roller, 2250m/min is maintained at a temperature of 200 degrees Celsius to the draw-off roller (draw roll) between 3000m/min And 2250m/min is maintained also at a temperature of 200 degrees Celsius to the relaxation roller between 3000m/min.By increasing in seal wire The shrinkage factor that winding quantity and the temperature of godet can control the annealing of fiber and obtain on roller (godet).
Technology for measuring fiber denier
The danier or line density of fiber are measured according to ASTM D1907-07 test methods.For the rotation of specified quantity, Fiber is wound on the spool that one meter of girth, is then weighed.The quality and length of sample determine each fiber filaments line density or Danier.
Technology for measuring fibre shrinkage
Fibre shrinkage test is implemented according to ASTM D2559 dry heat methods.Long 1 meter fiber sample is put into baking oven simultaneously And exposed to the time for being adapted to constant temperature scheduled volume.Sample then is removed from baking oven, subsequent length is measured.It is with initial 1 Meter Chang Du deviation determines its percentage for changing or shrinking.
Embodiment 1
The purpose of this embodiment is to manufacture PEI fibers according to our invention.Except using 1 1/4 inch extruders and The design of β components is outer, and fiber is manufactured according to steps described above.Using the 0.6mm capillary spinnerets with 4L/D, and make With 325 mesh screen modules filters.
Shrinkage factor of the fiber of production with 2 dpf and less than 2%.Unexpectedly, after being originally received, not Need to stretch or fiber of annealing in the case of, directly from spinnerette when, fiber shows low denier and low-shrinkage Combination.In the case of no destruction, with 1500m/min to 2250m/min speed manufacture fiber continue be within least 2 hours can Can.This embodiment is advantageously proved, low denier Buddhist nun can be made up of the PEI of the molecular weight distribution with least 2.5 That fiber.
Embodiment 2
The purpose of this embodiment is the execution for the method for repeating embodiment 1, and according to the various embodiment party of the present invention Formula manufactures polyether-imide fiber.Fiber is manufactured according to steps described above.0.6mm capillary spinnerets and 4L/D and 325 Mesh screen modules filter is used together.Obtained fiber has 1.8dpf and the shrinkage factor less than 2%.
In the case where needing not extend from (extraction) or annealing fiber, directly produced from spinning head under low shear conditions When, obtained fiber shows the combination of low denier and low-shrinkage.In the case of no destruction, with 1500m/min extremely 2250m/min speed manufacture fiber continue at least 2 hours be possible.This embodiment advantageously proves, can by with Low denier fiber is made in the PEI of at least 2.5 molecular weight distribution.
Embodiment 3
The purpose of this embodiment is when including lower purpose screen modules filter, according to the embodiment party of the present invention Formula manufactures polyether-imide fiber.Except using 200US mesh number screen modules filter (200US mesh screen pack Filter) outside, fiber is manufactured according to the process of embodiment 1 and embodiment 2.
In the case where needing not extend from or annealing fiber, under low shear conditions, when directly being produced from spinning head, obtain Fiber show the combination of low denier and low-shrinkage.2dpf fiber of the manufacture with 1.9% shrinkage factor is possible. In the case of not destroying, these fibers are manufactured with 1500m/min to 2250m/min speed and continue at least 2 hours.This reality Applying example advantageously proves, low denier fiber can be made by the PEI of the molecular weight distribution with least 2.5.
Embodiment 4
The purpose of this embodiment is in the screen modules filter including more low mesh number, according to the implementation of the present invention Mode manufactures polyether-imide fiber.Except using in addition to 400 mesh screen modules filters, according to embodiment 1 and embodiment 2 Process manufactures fiber.
In the case where needing not extend from or annealing fiber, under low shear conditions, when directly being produced from spinning head, obtain Fiber show the combination of low denier and low-shrinkage.2dpf fiber of the manufacture with 1.8% shrinkage factor is possible. In the case of not destroying, these fibers are manufactured with 1500m/min to 2250m/min speed and continue at least 2 hours.This reality Applying example advantageously proves, low denier fiber can be made by the PEI of the molecular weight distribution with least 2.5.
Embodiment 5
The purpose of this embodiment is to manufacture polyether-imide fiber according to the embodiment of the present invention.Except using 2L/D Spinning head, fiber is manufactured according to the process described in example 4.
In the case where needing not extend from or annealing fiber, when directly being produced from spinning head, obtained fiber shows low The combination of danier and low-shrinkage.Manufacture is possible with the 2dpf fibers less than 2% shrinkage factor.In the feelings without destruction Under condition, these fibers are manufactured with 1500m/min to 2250m/min speed and continue at least 2 hours.This embodiment is advantageously demonstrate,proved It is bright, low denier fiber can be made by the PEI of the molecular weight distribution with least 2.5.
Embodiment 6
The purpose of this embodiment is the execution of repetition embodiment 5 and manufacture PEI is fine according to the embodiment of the present invention Dimension.
In the case where needing not extend from or annealing fiber, under low shear conditions, when directly being produced from spinning head, obtain Fiber show the combination of low denier and low-shrinkage.Manufacture is possible with the 2dpf fibers less than 2% shrinkage factor. In the case of no destruction, these fibers are manufactured with 1500m/min to 2250m/min speed and continue at least 2 hours.This Embodiment is advantageously proved, low denier fiber can be made by the PEI of the molecular weight distribution with least 2.5.
Embodiment 7
The purpose of this embodiment is to manufacture polyether-imide fiber according to the embodiment of the present invention.Except with β On 1 inch screw of component design outside operation the present embodiment, fiber is manufactured according to process described above.This set uses tool There are 4L/D 0.2mm capillaries and 200 mesh screen modules filters.
In the case where needing not extend from or annealing fiber, under low shear conditions, when directly being produced from spinning head, obtain Fiber show the combination of low denier and low-shrinkage.1.7dpf fiber of the manufacture with 1.1% shrinkage factor is possible. In the case of no destruction, these fibers are manufactured with 1500m/min to 2250m/min speed and continue at least 2 hours.For This embodiment, less capillary size causes component pressure to rise to 1400psi.This embodiment advantageously proves, can be with Low denier fiber is made by the PEI of the molecular weight distribution with least 2.5.
Embodiment 8
The purpose of this embodiment is to manufacture polyether-imide fiber according to the embodiment of the present invention.Except using β groups Part design is run outside the present embodiment on 1 inch extruder, and fiber is manufactured according to process described above.Spinning head is that have The 0.4mm capillary diameters of 4L/D ratios.Equally in this scheme, using 200 mesh screen modules filters.
In the case where needing not extend from or annealing fiber, under low shear conditions, when directly being produced from spinning head, obtain Fiber show the combination of low denier and low-shrinkage.2dpf fiber of the manufacture with 1.5% shrinkage factor is possible. In the case of not destroying, these fibers are manufactured with 1500m/min to 2250m/min speed and continue at least 2 hours.This reality Applying example advantageously proves, low denier fiber can be made by the PEI of the molecular weight distribution with least 2.5.
Embodiment 9 (comparative example)
The purpose of this embodiment is according to prior art " α " spin pack design (as shown in figure 1, it includes distribution grid) Manufacture polyether-imide fiber.Fiber is manufactured according to process above and following result is obtained.Use 9011 manufacture PEI fibers.The present embodiment is run on 1 inch of extruder.Use the 0.6mm capillary spinnerets with 4L/D And 325 mesh screen modules filters.
As a result show, when under high shear conditions., for example, pressure manufactures PEI more than or equal under conditions of 1400psi During fiber, the unpumped of the low-shrinkage that is shown of fiber that is produced according to the various embodiments of the present invention and not is manufactured The PEI fibers of annealing are impossible.More particularly, in the present embodiment, produce fine under 2.2dpf and 4% shrinkage factor Dimension.In addition, in order that obtaining fiber with α filament spinning components, it is necessary to extract fiber out, then they are annealed to attempt to realize 2dpf.This subsequent method causes shrinkage factor to be higher than the method according to various embodiments of the invention.In addition, with major part with The pressure (400 to 600psi) of preceding embodiment compares, and this example utilizes more than 1500psi high component pressure.
Table 2 provides the summary of the result obtained in embodiment 1-9.
Although the present invention has been described in considerable detail with reference to some preferred forms of the present invention, other forms are possible 's.Therefore, the spirit and scope of appended claims, should not necessarily be limited to the description of preferred form included herein.
All paper and the content of document submitted simultaneously with this specification and for public examination those disclosed, lead to Reference is crossed to be incorporated herein.
Unless otherwise expressly stated, otherwise can be by the way that with identical, the alternative feature of equivalent or similar purpose be replaced All features changed disclosed in this specification (including any appended claims, summary and accompanying drawing).Therefore, unless bright in addition Really point out, disclosed each feature is only a kind of equivalent or similar characteristics embodiment of general series.

Claims (17)

1. a kind of method for producing fine amorphous polymer fiber, including：
By spinning head melt extrusion to produce spinning fibre under 400 to 1400psi pressure, wherein, the melt is included Amorphous polymer composition；
The spinning fibre is collected on feed roller in the case of no extraction spinning fibre,
The fiber of solidification is produced by the spinning fibre,
Wherein, the fiber of the solidification has the dpf more than 0 and less than or equal to 2.5dpf,
Wherein, the fiber of the solidification has the shrinkage factor less than or equal to 2%；And
In the case where not making the fiber experience extraction step of the solidification, the fiber of the solidification is wound on bobbin, Wherein described spinning head includes：
There is no distribution grid；And
Die head with multiple circular melt canals, wherein, each circle melt canal has length and diameter, and wherein, Each circle melt canal length:The ratio of diameter is 2:1 to 6:1.
2. according to the method described in claim 1, wherein, the amorphous polymer composition have 4 to 18g/10min it is molten Rate of flow of fluid.
3. method according to claim 1 or 2, wherein, the pressure is 400 to 1000psi.
4. method according to claim 1 or 2, further comprises in the case of no annealing steps, by the fiber Collect to the bobbin.
5. method according to claim 1 or 2, wherein, the fiber of the solidification is in no pressure air cooling step In the case of produce.
6. method according to claim 1 or 2, wherein, methods described further comprises leaving institute in the spinning fibre State after spinning head, heat the spinning fibre.
7. method according to claim 1 or 2, wherein, the melt includes one or more crystalline materials.
8. method according to claim 1 or 2, wherein, amorphous polymer composition includes PEI.
9. the unpumped amorphous polymer fiber that a kind of method as any one of preceding claims is produced.
10. unpumped amorphous polymer fiber according to claim 9, wherein, the polymer fiber is polyethers Imide fiber, wherein, the fiber has the polydispersity more than or equal to 2.5.
11. the unpumped amorphous polymer fiber according to claim 9 or 10, wherein, the fiber, which has, to be less than 2.2 danier.
12. the unpumped amorphous polymer fiber according to claim 9 or 10, wherein, the fiber has at least 2.6cN/dtex intensity.
13. a kind of fabric or the compound being made up of fabric, include not extracting out according to any one of claim 9 to 12 Amorphous polymer fiber.
14. a kind of spinning head, for by the at most 2.5dpf of the composition production comprising amorphous PEI it is amorphous not The polyether-imide fiber of extraction, the spinning head includes
There is no distribution grid；And
Die head with multiple circular melt canals, wherein, each circle melt canal has length and diameter, and wherein, Each circle melt canal length:The ratio of diameter is 2:1 to 6:1.
15. spinning head according to claim 14, wherein, the spinning head is than the identical spinning head including distribution grid Operating pressure at least low 40% pressure under operate.
16. the spinning head according to claims 14 or 15, wherein, the spinning head further comprises being combined with the die head At least one screen modules filter, the composition is distributed to the die head.
17. spinning head according to claim 16, wherein, the screen modules filter has the US of 200 to 400 mesh Screen size.
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JP6110491B2 (en) 2017-04-05
US20140037957A1 (en) 2014-02-06
KR20150039762A (en) 2015-04-13
EP2880207A1 (en) 2015-06-10
JP2015528532A (en) 2015-09-28
KR102049905B1 (en) 2019-11-28
IN2014DN10001A (en) 2015-08-14
WO2014025586A1 (en) 2014-02-13

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