CN101490320B - Polyoxadiazole composite fibers - Google Patents
Polyoxadiazole composite fibers Download PDFInfo
- Publication number
- CN101490320B CN101490320B CN2007800265937A CN200780026593A CN101490320B CN 101490320 B CN101490320 B CN 101490320B CN 2007800265937 A CN2007800265937 A CN 2007800265937A CN 200780026593 A CN200780026593 A CN 200780026593A CN 101490320 B CN101490320 B CN 101490320B
- Authority
- CN
- China
- Prior art keywords
- composite fibre
- polymer
- poly
- flexible
- aromatic
- 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.)
- Expired - Fee Related
Links
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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- 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
- Y10T428/2933—Coated or with bond, impregnation or core
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention is directed to preparation of a composite fiber comprising a polyoxadiazole and a flexible chain polymer which is not a polyoxadiazole polymer, and articles produced therefrom.
Description
Background of invention
The present invention relates to gather
The preparation method of diazole composite fibre and the goods that prepare from its.
It is poly-to demonstrate comprising of stainability and improved UV stable now
The composite fibre of diazole.
The general introduction of sending out
The present invention relates to comprise poly-
Aromatic oxadiozole polymer fa and flexible chain are non-poly-
The composite fibre of aromatic oxadiozole polymer fa.
Detailed Description Of The Invention
The present invention relates to gather
The composite fibre of diazole and flexible-chain polymer and this fiber preparation method.
For the purpose of this paper, term " fiber " here can exchange use with " long filament ", and refer to cross with long-pending relative flexible, the macroscopic view with high length and width ratio of the vertical fiber cross section of fibre length direction on uniform object.This fiber cross section can be an Any shape, but usually how much presents circle.Fiber on the bobbin of spinning in the packaging material is called continuous fibers.Be cut into the called staple fiber of short length.Be cut into even the fiber of littler length is called short flannel.Multifilament (multifilament yarn) can be in conjunction with forming cord.Yarn can tangle and/or twist.
The term spinning of Shi Yonging here refers to polymer solution extruding by spinning head.Can be used for of the present invention poly-
Diazole comprises that having suitable performance makes it to be become any poly-of fiber by solvent spinning from solvent
Aromatic oxadiozole polymer fa, second kind of polymer spinned fiber similarly in this solvent, this fiber can be used in produces composite fibre of the present invention.Preferably, this is poly-
Aromatic oxadiozole polymer fa is 1,3, and 4-is poly-
Aromatic oxadiozole polymer fa or copolymer.More preferably, comprise the poly-of copolymer
Aromatic oxadiozole polymer fa includes but not limited to comprise the poly-of following repetitive
Diazole:
Poly-
The preparation method of aromatic oxadiozole polymer fa is commonly known in the art.Poly-
The preparation method's of diazole (POD) polymer example can be at Journal of Polymer Science:Part A, and 3,45-54 (1965), Journal of Polymer Science:Part A-1,6,3357-3370, (1968), Advanced Materials, 9 (8), 601-613; (1997) and in the US patent application 11/415026 find.Preferably have the poly-of high inherent viscosity
Aromatic oxadiozole polymer fa, those as producing by disclosed method in U.S. Patent application 11/415026.
Second kind of polymer can be any polymer that is selected from the known flexible-chain polymer that comprises copolymer, but preferred polymer is those polymer that form isotropic aqueous solution in inorganic acid, this inorganic acid comprises chlorosulfonic acid and fluosulfonic acid, particularly sulfuric acid.The highly preferred polymer that is used for isotropic aqueous solution is polyvinylpyrrolidone (PVP).The example of suitable polymers comprises fatty polyamide (for example, 6-nylon, 6,6-nylon and 6,12-nylon), polyaniline, and PEKK (PEKK), aromatic polyamides (MPD-I, MPD-I/T) and the copolymer of PVP, as PVP/VA (vinyl acetate).
Poly-
Aromatic oxadiozole polymer fa and flexible-chain polymer can combine by any ratio, and this ratio allows gained solution to be spun to fiber.Typically, any ratio is poly-
Aromatic oxadiozole polymer fa and flexible-chain polymer can be spun to fiber.The those of ordinary skill of prior art typically uses the rule of mixture to determine to produce the polymer ratio of the fiber with desired properties.Typically, each polymer will exist with the amount of 2wt% at least, so that produce measurable variation on the performance of prepared composite fibre.
Composite fibre of the present invention can come spinning by the method that may further comprise the steps: mix poly-continuously
The isotropic polymer solution of aromatic oxadiozole polymer fa and the isotropic aqueous solution of second kind of polymer are to form the polymer solution that mixes; Allow the polymer solution that mixes form spinning solution by at least one static mixer; And spinning solution extruded the formation composite fibre via spinning head.In addition, this method can further comprise and allows composite fibre pass through air gap; Allow this compound stoste fiber contact and form the composite fibre that solidifies with quench solution; Allow the composite fibre of cohesion contact with washing lotion; Allow washed composite fibre contact and form neutralization and washed composite fibre with neutralization solution; Dry should the neutralization and washed composite fibre; And batch the composite fibre that this drying is crossed.This dry composite fibre can batch on the bobbin on the taking-up equipment.The extrusion method that is suitable for making composite fibre within the scope of the present invention has been disclosed in United States Patent (USP) 4,340, in 559,4,298,565 and 4,965,033.
With independent gathering
The aromatic oxadiozole polymer fa fiber is compared, and this is poly-
The diazole composite fibre demonstrates improved stainability.This composite fibre can use alkalescence or ACID DYES to carry out dope dyeing (solution dyeing).Basic-dyeable fibre (or cation dyes) is used to check the stainability of composite fibre.Cation dyes such as Basacryl Red GL (Basic Red 29 by Color Index) be through being usually used in this purpose, the degree of depth of the color that produces owing to its.Dyestuff dissolves in most organic solvent usually and is dissolved in the water-bearing media, but stainability is tested in water-bearing media.Slight acidity (pH of 4-6) is to realize that with basic-dyeable fibre level dyeing is needed.Do not wish to be bound by any theory, can believe, the diffusion admittance that the improved stainability of composite fibre should produce owing to the chain activity ratio by flexible-chain polymer.
With independent gathering
The aromatic oxadiozole polymer fa fiber is compared, and is poly-
The UV stable of diazole composite fibre typically is improved.When being exposed to xenon lamp in the time of 20 hours, independent gathers two
The azoles fiber does not typically demonstrate measurable toughness.When being exposed to the ultraviolet radiation of using xenon lamp and reaching 20 hours, have second kind of polymer poly-of 2wt% at least
The diazole composite fibre can keep measurable toughness.Preferably, poly-
The diazole composite fibre contains second kind of polymer of q.s so that keep more than 20% of their toughness after 20 hours being exposed to xenon lamp.More preferably, poly-
The diazole composite fibre contains second kind of polymer of q.s so that keep more than 35% of their toughness after 20 hours being exposed to xenon lamp.Most preferably, poly-two
The azoles composite fibre contains second kind of polymer of q.s so that keep more than 50% of their toughness after 20 hours being exposed to xenon lamp.
The stream thigh of each polymer solution and/or blending can contain the additive of common introducing, as antioxidant, and lubricant, screening uv-ray agent, colouring agent or the like.All percentage is by weight, except as otherwise noted.
Embodiment 1
By mix 86.885 the gram (0.668 mole) solid hydrazine sulfate, 88.74 the gram (0.534 mole) solid terephthalic acid and 22.18 the gram (0.133 mole) the solid isophthalic acid and in blender together blending prepared poly-in 30 minutes
The diazole copolymer.In the mixture of this blending of solid, add 30% fuming sulphuric acid first, be in 25 centigrade 534 gram fuming sulphuric acids (2.001 moles SO3).
Mixture under 25 Celsius temperatures mechanical agitation 15 minutes with the dissolved solid thing and form solution.This solution is heated to 120 Celsius temperatures then under mechanical agitation, till observing constant-torque (constant viscosity) on the blender (60 minutes).
In this solution, add 30% fuming sulphuric acid for the second time, be in the gram of 611 under 130 Celsius temperatures fuming sulphuric acid (2.290 moles SO3).Temperature was kept under 130 Celsius temperatures 2 hours, till the viscosity of solution reaches platform (constant).Solution is cooled to room temperature then.
From chilled solution, take out small sample and add in the 0 centigrade water to be settled out polymer.Polymer washes with water, till reaching neutral pH.Polymer is dry under vacuum, 2.60 inherent viscosity.By adding 581 concentrated sulfuric acids that restrain with solution dilution to 5.0% solid.
In the remainder of the polymer solution of above preparation, at room temperature add the K-90 polyvinylpyrrolidonepowder powder of the weight average molecular weight about 90,000 of 5.06 grams, and stir, till the solid dissolving of whole interpolations.Solution shows some shearing opalescences and a silk sample outward appearance.This solution by the air gap spinning in the coagulating bath of at room temperature 7% sulfuric acid solution, washing subsequently and neutralization and be spun to fiber in sodium bicarbonate.The gained fiber is a dry night in 120 ℃ of baking ovens.The stainability of this fiber is tested in the 0.5%Basacryl of acid pH=4-5 Red GL (basic-dyeable fibre) solution.This fiber is coloured to dark color, but does not add the not dyeing of the prepared fiber of PVP.
Embodiment 2
According to the fiber sample of the same manner preparation, just low molecular weight PVP (K-30 of weight average molecular weight about 60,000) replaces K-90, also uses Basacryl Red GL (basic-dyeable fibre) to be coloured to dark color.
Based on the above discussion and open, the present invention thereby the exemplary of following many aspects for example is provided:
1. composite fibre comprises: at least a poly-
Aromatic oxadiozole polymer fa; With at least a flexible-chain polymer, wherein, this flexible-chain polymer is not poly-
Aromatic oxadiozole polymer fa, and this flexible-chain polymer is selected from nylon-6, nylon-6,6, nylon-6,12, the copolymer of polyaniline, PEKK, aromatic polyamides, polyvinylpyrrolidone and polyvinylpyrrolidone.
2. the composite fibre of aspect 1, wherein: this is poly-
Aromatic oxadiozole polymer fa comprises and is selected from following repetitive
3. the composite fibre of aspect 2, wherein: this is poly-
Aromatic oxadiozole polymer fa comprises at least two kinds of repetitives that are selected from following
4. the composite fibre of aspect 1, wherein: this flexible-chain polymer is a polyvinylpyrrolidone, or the copolymer of polyvinylpyrrolidone.
5. the composite fibre of aspect 1, wherein: this is poly-
Aromatic oxadiozole polymer fa is a copolymer.
6. the composite fibre of aspect 5, wherein: this is poly-
The diazole copolymer comprises at least two kinds of aromatic ring systems that are selected from following:
7. the composite fibre of aspect 1, wherein: this composite fibre be exposed to xenon lamp keep after 20 hours it toughness at least 15%.
8. the composite fibre of aspect 1, wherein: this composite fibre is stainable.
9. the composite fibre of aspect 1, wherein: this flexible-chain polymer is that the amount with 2-98wt% exists.
10. the composite fibre of aspect 9, wherein: this flexible-chain polymer is that the amount with 5-98wt% exists.
11. the composite fibre of aspect 9, wherein: this composite fibre be exposed to xenon lamp keep after 20 hours it toughness at least 15%.
12. the composite fibre of aspect 9, wherein: this composite fibre be exposed to xenon lamp keep after 20 hours it toughness at least 35%.
13. contain the goods of the composite fibre of aspect 1.
Claims (13)
1. composite fibre comprises: at least a poly-
Aromatic oxadiozole polymer fa; With at least a flexible-chain polymer, wherein, this flexible-chain polymer is not poly-
Aromatic oxadiozole polymer fa, and this flexible-chain polymer is selected from nylon-6, nylon-6,6, nylon-6,12, the copolymer of polyaniline, PEKK, aromatic polyamides, polyvinylpyrrolidone and polyvinylpyrrolidone.
2. the composite fibre of claim 1, wherein: this is poly-
Aromatic oxadiozole polymer fa comprises and is selected from following repetitive
3. the composite fibre of claim 2, wherein: this is poly-
Aromatic oxadiozole polymer fa comprises at least two kinds of repetitives that are selected from following
4. the composite fibre of claim 1, wherein: this flexible-chain polymer is the copolymer of polyvinylpyrrolidone or polyvinylpyrrolidone.
5. the composite fibre of claim 1, wherein: this is poly-
Aromatic oxadiozole polymer fa is a copolymer.
6. the composite fibre of claim 5, wherein: this is poly-
The diazole copolymer comprises at least two kinds of aromatic ring systems that are selected from following:
7. the composite fibre of claim 1, wherein: this composite fibre be exposed to xenon lamp keep after 20 hours it toughness at least 15%.
8. the composite fibre of claim 1, wherein: this composite fibre is stainable.
9. the composite fibre of claim 1, wherein: this flexible-chain polymer is that the amount with 2-98wt% exists.
10. the composite fibre of claim 9, wherein: this flexible-chain polymer is that the amount with 5-98wt% exists.
11. the composite fibre of claim 9, wherein: this composite fibre be exposed to xenon lamp keep after 20 hours it toughness at least 15%.
12. the composite fibre of claim 9, wherein: this composite fibre be exposed to xenon lamp keep after 20 hours it toughness at least 35%.
13. contain the goods of the composite fibre of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/486,243 | 2006-07-13 | ||
| US11/486,243 US20080014440A1 (en) | 2006-07-13 | 2006-07-13 | Polyoxadiazole composite fibers |
| PCT/US2007/014973 WO2008008185A2 (en) | 2006-07-13 | 2007-06-27 | Polyoxadiazole composite fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101490320A CN101490320A (en) | 2009-07-22 |
| CN101490320B true CN101490320B (en) | 2011-11-23 |
Family
ID=38779507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800265937A Expired - Fee Related CN101490320B (en) | 2006-07-13 | 2007-06-27 | Polyoxadiazole composite fibers |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20080014440A1 (en) |
| EP (1) | EP2041340A2 (en) |
| JP (1) | JP2009542935A (en) |
| KR (1) | KR20090031431A (en) |
| CN (1) | CN101490320B (en) |
| BR (1) | BRPI0713241A2 (en) |
| CA (1) | CA2655858A1 (en) |
| MX (1) | MX2009000354A (en) |
| WO (1) | WO2008008185A2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7528217B2 (en) * | 2006-10-06 | 2009-05-05 | E.I. Du Pont De Nemours And Company | Polymers and fibers formed therefrom |
| DE102008027499A1 (en) * | 2008-06-10 | 2009-12-17 | Gkss-Forschungszentrum Geesthacht Gmbh | Production of composites from polyoxadiazole polymers |
| JP6112683B2 (en) * | 2012-06-15 | 2017-04-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Flame retardant spun short fiber yarns made from blends of fibers obtained from sulfonated naphthalene polyoxadiazole polymers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054633A (en) * | 1976-05-13 | 1977-10-18 | Monsanto Company | Process for continuously preparing shaped articles of aromatic oxadiazole or aromatic oxadiazole/N-alkylhydrazide polymers from monomer solutions |
| US4132757A (en) * | 1977-12-27 | 1979-01-02 | Monsanto Company | Twist efficiency of oxadiazole/hydrazide yarn |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4839776B1 (en) * | 1970-10-08 | 1973-11-27 | ||
| JPS4929298B1 (en) * | 1970-12-16 | 1974-08-02 | ||
| JPS518414B2 (en) * | 1971-11-04 | 1976-03-16 | ||
| GB1529360A (en) * | 1975-10-13 | 1978-10-18 | Ici Ltd | Polyarylene-oxadiazole bonded structures |
| GB1589615A (en) * | 1977-01-25 | 1981-05-13 | Ici Ltd | Production of oriented fibrillar products |
| US5057600A (en) * | 1987-10-09 | 1991-10-15 | The Dow Chemical Company | Process for forming an article comprising poly(etheretherketone) (PEEK) type polymers |
| DD279509A1 (en) * | 1989-01-16 | 1990-06-06 | Schwarza Chemiefaser | METHOD FOR STABILIZING NITROGEN-CONTAINING POLYMERS |
| JP3804097B2 (en) * | 1996-03-29 | 2006-08-02 | 東レ株式会社 | Support stockings with excellent wearing comfort |
| DE10040897B4 (en) * | 2000-08-18 | 2006-04-13 | TransMIT Gesellschaft für Technologietransfer mbH | Nanoscale porous fibers of polymeric materials |
-
2006
- 2006-07-13 US US11/486,243 patent/US20080014440A1/en not_active Abandoned
-
2007
- 2007-06-27 BR BRPI0713241-7A patent/BRPI0713241A2/en not_active Application Discontinuation
- 2007-06-27 MX MX2009000354A patent/MX2009000354A/en unknown
- 2007-06-27 EP EP07796527A patent/EP2041340A2/en not_active Withdrawn
- 2007-06-27 CA CA002655858A patent/CA2655858A1/en not_active Abandoned
- 2007-06-27 KR KR1020097001306A patent/KR20090031431A/en not_active Application Discontinuation
- 2007-06-27 JP JP2009519446A patent/JP2009542935A/en active Pending
- 2007-06-27 WO PCT/US2007/014973 patent/WO2008008185A2/en active Application Filing
- 2007-06-27 CN CN2007800265937A patent/CN101490320B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054633A (en) * | 1976-05-13 | 1977-10-18 | Monsanto Company | Process for continuously preparing shaped articles of aromatic oxadiazole or aromatic oxadiazole/N-alkylhydrazide polymers from monomer solutions |
| US4132757A (en) * | 1977-12-27 | 1979-01-02 | Monsanto Company | Twist efficiency of oxadiazole/hydrazide yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008008185A3 (en) | 2008-05-02 |
| WO2008008185A2 (en) | 2008-01-17 |
| CN101490320A (en) | 2009-07-22 |
| KR20090031431A (en) | 2009-03-25 |
| EP2041340A2 (en) | 2009-04-01 |
| BRPI0713241A2 (en) | 2012-04-17 |
| MX2009000354A (en) | 2009-01-27 |
| CA2655858A1 (en) | 2008-01-17 |
| JP2009542935A (en) | 2009-12-03 |
| US20080014440A1 (en) | 2008-01-17 |
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Granted publication date: 20111123 Termination date: 20200627 |