KR20000069731A - Manufacture of elongate members - Google Patents
Manufacture of elongate members Download PDFInfo
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- KR20000069731A KR20000069731A KR1019997005821A KR19997005821A KR20000069731A KR 20000069731 A KR20000069731 A KR 20000069731A KR 1019997005821 A KR1019997005821 A KR 1019997005821A KR 19997005821 A KR19997005821 A KR 19997005821A KR 20000069731 A KR20000069731 A KR 20000069731A
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- Prior art keywords
- rectangular material
- acrylonitrile
- polymers
- rectangular
- oxidized
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 13
- 235000012438 extruded product Nutrition 0.000 abstract 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 239000000155 melt Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydroxymethylene group Chemical group 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Abstract
용융성 아크릴로니트릴 폴리머의 용융 압출 제품, 예를 들면 섬유 또는 필름은 비용융성으로 되도록 교차결합됨. 이어서 교차결합된 제품은 산화시킨 다음, 비용융성 아크릴로니트릴 폴리머의 습식 또는 건식 압출에 의하여 제조된 제품을 처리하는 방법과 유사한 방법으로 탄소시키거나 흑연화시킬 수 있음.Melt extruded products of meltable acrylonitrile polymers, such as fibers or films, are crosslinked to be insoluble. The crosslinked product can then be oxidized and then carbonized or graphitized in a similar manner to the process of treating a product produced by wet or dry extrusion of the insoluble fumed acrylonitrile polymer.
Description
아크릴로니트릴 폴리머는, 예를 들면 엔사이클로피디어 어브 폴리머 사이엔스 앤드 엔지니어링, 볼룸 1 (윌리-인터사이엔스, 1985), 426페이지에 "아크릴로니트릴 폴리머"란 제목으로 기재되어 있고, 334페이지에 "아크릴 섬유"란 제목으로 기재되어 있는 이미 알려진 물질이다. 아크릴 폴리머는 아크릴로니트릴 모노머 유니트를 85중량% 이상 포함하는 폴리머로 정의된다. 모다크릴 폴리머는 아크릴로니트릴 모노머 유니트를 40 내지 85중량% 포함하는 폴리머로 정의된다. 대부분의 아크릴 폴리머를 포함하는 많은 아크릴로니트릴 폴리머는 비용융성이며 가열하였을 때 용융되지 않고 분해된다. 이러한 폴리머를 습식 또는 건식 압출 기술을 이용하여 장방형 소재, 예를 들면 섬유로 가공하는 방법들은 이미 알려 졌다. 이러한 방법들은 적당한 용매에 용해시킨 폴리머 용액을 응고욕 또는 휘발성 분위기 속으로 압출하는 방법을 포함한다. 또한 가소화된 아크릴로니트릴 폴리머를 건식 방사조건하에 압출하고 가소제를 제거하여 장방형 소재를 제거하는 방법도 알려졌다. 용융성 아크릴로니트릴 폴리머는 이미 알려져 있는바, 예를 들면 본 발명에 인용된 미국특허 5,106,925호 및 5,286,828호에 기재되어 있다. 이러한 용융성 아크릴로니트릴 폴리머들은 그들이 분해되는 온도 이하의 온도에서 용융 압출하여 장방형 소재를 형성할 수 있다. 일반적으로 이러한 폴리머들은 습식 또는 건식 방사기술에 의하여 압출될 수도 있다.Acrylonitrile polymers are described, for example, in Ncyclopedia of Polymer Science and Engineering, Ballroom 1 (Willy-Inter-Sciences, 1985), page 426, entitled "Acrylonitrile Polymers," page 334. Is an already known material, entitled "Acrylic Fibers". Acrylic polymer is defined as a polymer comprising at least 85% by weight of acrylonitrile monomer units. Modacrylic polymers are defined as polymers containing from 40 to 85% by weight of acrylonitrile monomer units. Many acrylonitrile polymers, including most acrylic polymers, are insoluble and degrade without melting when heated. Methods of processing such polymers into rectangular materials, for example fibers, using wet or dry extrusion techniques are already known. Such methods include extrusion of a polymer solution dissolved in a suitable solvent into a coagulation bath or a volatile atmosphere. It is also known to extrude plasticized acrylonitrile polymers under dry spinning conditions and remove plasticizers to remove rectangular materials. Melt acrylonitrile polymers are already known and are described, for example, in US Pat. Nos. 5,106,925 and 5,286,828, which are cited herein. These meltable acrylonitrile polymers can be melt extruded at temperatures below the temperature at which they decompose to form rectangular materials. In general, such polymers may be extruded by wet or dry spinning techniques.
탄소섬유는, 예를 들면 엔사이클로피디어 어브 폴리머 사이엔스 앤드 엔지니어링, 볼룸 2, (윌리-인터사이엔스 1985), 640페이지에 "탄소섬유"란 제목으로 기재되어 있다. 탄소섬유는 섬유 형태의 유기 전구물질, 예를 들면 아크릴로니트릴 폴리머의 제어된 열분해에 의하여 제조된다. 아크릴로니트릴의 열분해는 전형적으로 다수의 열분해 단계를 포함한다. 안정화 단계나 산화 단계 또는 예비-산화 단계나 열고정 단계라 부르는 열분해의 제1 단계는 통상적으로 공기 중에서 200-450℃ 범위의 저온하에 실시된다. 산화된 섬유는 불활성 분위기 중에서 1000-2000℃ 범위의 온도로 가열하여 (탄소화된)탄소섬유로 전환시키거나, 또는 불활성 분위기 중에서 2500℃ 이상의 온도로 가열하여 흑연화시킨다.Carbon fibers are described, for example, in Ncyclopedia of Polymer Science and Engineering, Ballroom 2, (Willy-Intersciences 1985), page 640, entitled “Carbon Fibers”. Carbon fibers are produced by controlled pyrolysis of organic precursors in fiber form, for example acrylonitrile polymers. Pyrolysis of acrylonitrile typically includes a number of pyrolysis steps. The first step of pyrolysis, called the stabilization step or oxidation step or pre-oxidation step or heat setting step, is usually carried out at low temperature in the range of 200-450 ° C. in air. The oxidized fibers are heated to temperatures in the range of 1000-2000 ° C. in an inert atmosphere and converted to (carbonized) carbon fibers, or graphitized by heating to temperatures above 2500 ° C. in an inert atmosphere.
용융 압출기술은 장방형 소재를 제조함에 있어서 습식 및 건식 압출기술에 비하여 비교적 간단한 장비를 사용하여도 된다는 이점이 있다. 더구나, 용융 압출기술은 습식 및 건식 압출기술에 비하여 개량된 단면을 갖는 금형을 통한 압출에 의하여 개량된 단면의 압출물을 생산하는데 더 쉽게 적용될 수 있는 것으로 알려 졌다. 그러나, 용융 압출된 용융성 아크릴로니트릴 폴리머는 산화, 탄소화 또는 흑연화된 제품이 생산되도록 쉽게 열분해되지 않는다. 이러한 폴리머는 산화될수 있는 온도 이하의 온도에서 용융된다.The melt extrusion technique has the advantage of using relatively simple equipment in manufacturing rectangular materials as compared to wet and dry extrusion techniques. Moreover, it has been found that the melt extrusion technique can be more easily applied to produce an extrudate of improved cross section by extrusion through a mold having an improved cross section compared to wet and dry extrusion techniques. However, melt extruded meltable acrylonitrile polymers are not readily pyrolyzed to produce oxidized, carbonized or graphitized products. Such polymers melt at temperatures below those which can be oxidized.
본 발명은 아크릴로니트릴 폴리머를 주제로한 장방형 소재의 제조방법에 관계되는 것으로서, 특히 아크릴로니트릴의 산화, 탄소화 및 흑연화에 관한 것이다.The present invention relates to a method for producing a rectangular material based on an acrylonitrile polymer, and more particularly relates to oxidation, carbonization and graphitization of acrylonitrile.
본 발명은 장방형 소재를 만들기 위하여 용융성 아크릴로니트릴 폴리머를 용융 압출하는 단계(1)와 본 발명의 특징인 전술한 장방형 소재로된 폴리머를 비용융성으로 되도록 교차결합시키는 단계(2)를 포함하는 장방형 소재 제조방법을 제공한다.The present invention comprises the steps of (1) melt extruding a molten acrylonitrile polymer to produce a rectangular material and crosslinking (2) the polymer of the aforementioned rectangular material, which is a feature of the present invention, to be non-melt. It provides a rectangular material manufacturing method.
장방형 소재는 필름 형태일 수 있고 섬유 형태일 수도 있다.The rectangular material may be in film form or in fiber form.
본 발명에 사용하는데 적당한 용융성 아크릴로니트릴 폴리머와, 그들의 제조 및 용융 압출방법은, 예를 들면 미국특허 5,106,925호 및 미국특허 5,286,828호에 기재되어 있다. 용융성 아크릴로니트릴 폴리머는 대체로 아크릴로니트릴 모노머 유니트를 50% 이상 포함한다.Melt acrylonitrile polymers suitable for use in the present invention and their preparation and melt extrusion methods are described, for example, in US Pat. Nos. 5,106,925 and 5,286,828. Melt acrylonitrile polymers generally comprise at least 50% of acrylonitrile monomer units.
교차결합 단계(2)는 다양한 방법으로 실시될 수 있다. 예를 들면, 압출된 장방형 소재를 교차결합이 도입되도록 이온화 방사선에 노출시킬 수 있다. 또한 장방형 소재를 아크릴로니트릴 폴리머에 교차결합을 도입하는 화학 약품, 예를 들면 암모니아, 하이드라진 또는 1급 또는 2급 아민으로 처리할 수도 있다. 용융성 아크릴로니트릴 폴리머는 니트릴 그룹 이외의 교차결합성 그룹, 예를 들면 올레핀계 그룹이나 하이드록실 그룹을 갖고 있는 모노머 유니트를 포함할 수도 있다. 이러한 폴리머에서는 전술한 소재를 교차결합성 그룹이 반응할수 있는 조건, 예를 들면 올레핀계 그룹의 경우에는 자외선에 노출시키고 하이드록실 그룹의 경우에는 이관능성 약품에 의한 에테르화 또는 반응에 의하여 교차결합이 도입될 수 있다. 용융 압출단계에서의 과잉 교차결합은 용융 압출된 소재의 물리적 특성에 나쁜 영향을 미칠수 있으므로 과잉 교차결합이 용융 압출 중에 나타나지 않도록 주의하여야 한다. 따라서, 교차결합성 그룹들은 용융 압출 중에 과잉의 교차결합이 일어나지 않을 정도로 충분한 열 안정성을 갖고 있어야 한다. 더구나, 아크릴로니트릴 폴리머는 잠재 교차결합성 그룹을 포함할 수도 있다. 예를 들면, 이러한 폴리머는 잠재 교차결합성 그룹을 제공하는 역할을 하는 t-부틸 비닐 에텔 모노머 유니트를 포함할 수도 있다. 이 경우, 에텔 그룹은 용융 압출 후 가수분해되어 교차결합성 그룹인 하이드록시메틸렌 그룹으로 된다.The crosslinking step 2 can be carried out in various ways. For example, the extruded rectangular material can be exposed to ionizing radiation such that crosslinking is introduced. The rectangular material may also be treated with chemicals which introduce crosslinks into the acrylonitrile polymer, for example ammonia, hydrazine or primary or secondary amines. The meltable acrylonitrile polymer may include monomer units having a crosslinkable group other than a nitrile group, for example, an olefinic group or a hydroxyl group. In such polymers, the above-described materials may be exposed to ultraviolet light in the case of crosslinkable groups, for example, in the case of olefinic groups, and in the case of hydroxyl groups, crosslinking may be caused by etherification or reaction by a bifunctional chemical agent. Can be introduced. Excess crosslinking in the melt extrusion step may adversely affect the physical properties of the melt extruded material, so care must be taken to ensure that excess crosslinking does not appear during melt extrusion. Therefore, the crosslinkable groups must have sufficient thermal stability such that no excessive crosslinking occurs during melt extrusion. Moreover, the acrylonitrile polymer may comprise latent crosslinkable groups. For example, such polymers may include t-butyl vinyl ether monomer units that serve to provide latent crosslinkable groups. In this case, the ether group is hydrolyzed after melt extrusion into a hydroxymethylene group which is a crosslinkable group.
교차결합된 비용융성 폴리머는 약 300℃ 이하의 온도에서 용융되는 경향을 나타내지 않는 것이 바람직하다. 본 발명에 의하면 교차결합된 폴리머는 섬유를 포함하는 아크릴로니트릴 장방형 소재에 대하여 이미 알려진 통상의 기술에 의하여 산화되고 열분해된다. 본 발명은 또한 산화조건 하에서 교차결합된 장방형 소재를 열분해하는 단계(3)를 포함하는 산화된 아크릴로니트릴 장방형 소재를 제조하는 방법을 제공한다. 또한 본 발명은 단계(3)에 추가하여 무산소 조건하에서 산화된 장방형 소재를 열분해시키는 단계(4)를 포함하는 탄소화 또는 흑연화된 장방형 소재를 제조하는 방법을 제공한다.It is preferred that the crosslinked insoluble polymers do not exhibit a tendency to melt at temperatures below about 300 ° C. According to the present invention the crosslinked polymer is oxidized and pyrolyzed by conventional techniques already known for acrylonitrile rectangular material comprising fibers. The present invention also provides a process for producing an oxidized acrylonitrile rectangular material comprising the step (3) of pyrolyzing the crosslinked rectangular material under oxidizing conditions. The present invention also provides a method of producing a carbonized or graphitized rectangular material, in addition to step (3), comprising the step (4) of pyrolysing the rectangular material oxidized under anoxic conditions.
본 발명의 방법에 의하여 제조된 교차결합된 섬유 형태의 장방형 소재는, 예를 들면 난연성 재료 및 바테리 격리판에 사용하는 탄소섬유의 제조에 적당하다.Rectangle materials in the form of crosslinked fibers produced by the process of the invention are suitable for the production of carbon fibers for use in, for example, flame retardant materials and battery separators.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9700946.8 | 1997-01-17 | ||
| GB9700946A GB2321215A (en) | 1997-01-17 | 1997-01-17 | Cross-linked acrylonitrile precursors for carbon fibres |
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| Publication Number | Publication Date |
|---|---|
| KR20000069731A true KR20000069731A (en) | 2000-11-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019997005821A KR20000069731A (en) | 1997-01-17 | 1998-01-15 | Manufacture of elongate members |
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| Country | Link |
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| EP (1) | EP0953071A1 (en) |
| JP (1) | JP2001508842A (en) |
| KR (1) | KR20000069731A (en) |
| CN (1) | CN1091809C (en) |
| AU (1) | AU5670898A (en) |
| CA (1) | CA2278484A1 (en) |
| EA (1) | EA001275B1 (en) |
| GB (1) | GB2321215A (en) |
| IL (1) | IL130670A0 (en) |
| WO (1) | WO1998031852A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU3365400A (en) * | 1999-02-22 | 2000-09-14 | Standard Oil Company, The | Carbon fibers or sheets made from copolymers of acrylonitrile |
| US6630555B2 (en) | 2001-11-06 | 2003-10-07 | Lord Corporation | Internally blocked organoborate initiators and adhesives therefrom |
| CN101798392B (en) * | 2009-12-11 | 2012-01-04 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using gamma ray irradiation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1054137A (en) * | ||||
| GB1033141A (en) * | 1962-04-17 | 1966-06-15 | Courtaulds Ltd | Process for modifying synthetic fibres |
| DE1929849C3 (en) * | 1969-06-12 | 1973-10-18 | Sigri Elektrographit Gmbh | Process for the production of carbon or graphite fibers |
| GB1283714A (en) * | 1969-07-09 | 1972-08-02 | Ici Ltd | Process for the production of carbon fibres |
| BE755579A (en) * | 1970-04-07 | 1971-03-01 | Sigri Elektrographit Gmbh | CARBON AND GRAPHITE FIBER MANUFACTURING PROCESS |
| US3917776A (en) * | 1970-12-12 | 1975-11-04 | Mitsubishi Rayon Co | Process for producing carbon fiber |
| GB1580529A (en) * | 1975-10-24 | 1980-12-03 | Nat Res Dev | Polymers useful for producing carbon fibres |
| US4473372A (en) * | 1983-05-12 | 1984-09-25 | Celanese Corporation | Process for the stabilization of acrylic fibers |
| JPS62149918A (en) * | 1985-12-25 | 1987-07-03 | Mitsubishi Rayon Co Ltd | Production of heat-resistant acrylonitrile yarn |
| US4921656A (en) * | 1988-08-25 | 1990-05-01 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers |
| US5436275A (en) * | 1993-11-30 | 1995-07-25 | Japan Exlan Company Limited | Porous acrylonitrile polymer fiber |
| US5509986A (en) * | 1994-08-22 | 1996-04-23 | The Dow Chemical Company | Process for preparing an ignition resistant carbonaceous material comprising a melt blowing or spunbonding step, a radiation step and a carbonizing step |
-
1997
- 1997-01-17 GB GB9700946A patent/GB2321215A/en not_active Withdrawn
-
1998
- 1998-01-15 KR KR1019997005821A patent/KR20000069731A/en not_active Application Discontinuation
- 1998-01-15 AU AU56708/98A patent/AU5670898A/en not_active Abandoned
- 1998-01-15 IL IL13067098A patent/IL130670A0/en unknown
- 1998-01-15 EA EA199900666A patent/EA001275B1/en not_active IP Right Cessation
- 1998-01-15 CN CN98801838A patent/CN1091809C/en not_active Expired - Fee Related
- 1998-01-15 JP JP53393998A patent/JP2001508842A/en active Pending
- 1998-01-15 CA CA002278484A patent/CA2278484A1/en not_active Abandoned
- 1998-01-15 WO PCT/GB1998/000124 patent/WO1998031852A1/en not_active Application Discontinuation
- 1998-01-15 EP EP98900898A patent/EP0953071A1/en not_active Withdrawn
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| CA2278484A1 (en) | 1998-07-23 |
| EA001275B1 (en) | 2000-12-25 |
| GB9700946D0 (en) | 1997-03-05 |
| JP2001508842A (en) | 2001-07-03 |
| WO1998031852A1 (en) | 1998-07-23 |
| IL130670A0 (en) | 2000-06-01 |
| GB2321215A (en) | 1998-07-22 |
| EA199900666A1 (en) | 2000-02-28 |
| EP0953071A1 (en) | 1999-11-03 |
| CN1091809C (en) | 2002-10-02 |
| CN1243554A (en) | 2000-02-02 |
| AU5670898A (en) | 1998-08-07 |
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