CN102131969A - 制造碳纤维的方法 - Google Patents
制造碳纤维的方法 Download PDFInfo
- Publication number
- CN102131969A CN102131969A CN200980132923XA CN200980132923A CN102131969A CN 102131969 A CN102131969 A CN 102131969A CN 200980132923X A CN200980132923X A CN 200980132923XA CN 200980132923 A CN200980132923 A CN 200980132923A CN 102131969 A CN102131969 A CN 102131969A
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- Prior art keywords
- fiber
- pan
- acrylonitrile
- glycerine
- acrolein
- Prior art date
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- Pending
Links
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000000944 linseed oil Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000001869 rapid Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Artificial Filaments (AREA)
Abstract
本发明涉及由可再生资源的原材料制造碳纤维的方法，包括：a)由植物甘油合成丙烯醛；b)将所述丙烯醛氨氧化以得到丙烯腈；c)将丙烯腈聚合为丙烯腈均聚物或共聚物(PAN)；d)将所述PAN转化为PAN纤维；e)将所述PAN纤维部分氧化；和f)将所述部分氧化的PAN纤维碳化。本发明还涉及能够根据所述方法得到的纤维及其用途。
Description
本发明涉及由可再生来源的原材料制造碳纤维的方法，并且还涉及能够根据这种方法得到的纤维。
碳纤维是由具有5～10微米直径的非常细的纤维组成的材料，碳是其主要的化学元素。通常存在其它原子例如氧、氮、氢和不太经常的硫。碳原子结合在一起并形成或多或少与所述纤维的轴平行排列的石墨型晶体。数千个这些纤维缠绕在一起以形成股。这些股可单独使用或制成织物的形式。
碳纤维是目前发展最快的材料之一。用作热固性塑料(thermoset)如交联的聚酯树脂和环氧树脂的增强物或者用作改善一些热塑性塑料如聚酰胺的试剂，它们实际上使得可得到相对于它们的重量非常强且甚至经常每单位重量比钢更强的复合材料。
因此，这些复合材料具有非常好的拉伸模量、非常高的拉伸强度和低的热膨胀系数。它们在许多应用例如航空器或航天器部件、运动器材(网球球拍和高尔夫球棒)和风轮机中使用的结构树脂中可代替金属。碳纤维还应用于高温气体的过滤，作为抗静电剂，由于它们的耐腐蚀性而作为特种电极，作为用于加压气罐特别是储存氢气的加压气罐的增强物。
碳纤维的起源追溯至1958年，当它们由Union Carbide提出的日期。第一代纤维具有中等质量，但是使用聚丙烯腈(PAN)作为前体得到了快速的改进。取决于前体，纤维不是相同的：由PAN得到的那些是相当湍层的，具有彼此具有非零角度并且任意折叠的石墨平面。在超过2200℃下热处理之后由沥青得到的纤维是石墨的。因此由这些不同的前体得到的纤维也具有不同的性质。因此，由PAN得到的那些通常具有更好的拉伸强度。
由PAN合成碳纤维典型地包括在约300℃下烧制纤维以使其稍微氧化的步骤，此后将所述纤维置于约2000℃的电炉中在氩气或氮气的惰性气氛下。在该步骤之后，所述纤维含有约95％的碳。随后在较高温度下的处理提高其热导率和其模量。
因此理解碳纤维由于在它们制造过程中所必须的高温是非常能量密集的产品。这种能量消耗并没有被它们容许制造较轻的交通工具并因此减少运输应用中能量消耗的能力抵偿。
在其中发电主要来自消耗化石资源的国家中，这种能量消费伴随着温室气体排放的增加，这对于环境是特别有害的。为了减小这种排放，作用于合成碳纤维的方法是不容易的。另一方面，似乎可使用环境影响比碳纤维合成中常规使用的PAN小的原材料，特别是可再生或生物基原材料。
关于这点，本发明的一个主题是由可再生或生物基来源的原材料合成碳纤维的新方法。
更具体地，本发明的一个主题是制造碳纤维的方法，包括：
a)由植物来源的甘油合成丙烯醛；
b)将所述丙烯醛氨氧化以得到丙烯腈；
c)将所述丙烯腈聚合为丙烯腈的均聚物或共聚物(PAN)；
d)将所述PAN转化为PAN纤维；
e)将所述PAN纤维部分氧化；和
f)将所述部分氧化的PAN纤维碳化。
现在将更详细地描述这种方法。应注意，作为介绍，其可包括除了上述那些之外的步骤，特别是在步骤(a)之前的一个或多个步骤、在步骤(f)之后的一个或多个步骤和/或一个或多个中间步骤，只要这些步骤没有消极地影响整个方法，特别是所得碳纤维的产率和/或质量。
在根据本发明的方法的第一步骤中，由植物来源的甘油合成丙烯醛。
根据本发明的一个优选实施方式，步骤(a)中使用的甘油是作为植物来源的甘油三酯的酯交换的副产物得到的。常规的酯交换反应实际上使用线型C1-C10一元醇如甲醇或乙醇、或者环状C3-C6一元醇，其与甘油三酯反应以得到C1-C10醇的烷基酯和甘油。甘油三酯是下式的化合物：R1-CO-O-CH2-CH(OCO-R2)-CH2-O-CO-R3，其中R1～R3表示饱和或(多)不饱和的、线型或支化的C10-C30例如C12-C18烷基，其是植物油和脂肪如棕榈油、亚麻子油、花生油、椰子油、向日葵油、豆油或菜籽油的重要成分。后者特别是在推荐作为化石燃料的替代燃料的生物柴油的制造中酯交换。因此，根据本发明使用的甘油可为来自植物油的生物柴油的制造的副产物。作为指示，约1吨甘油是由10吨脂肪酸甘油三酯获得的。
酯交换步骤通常是在20～150℃、优选25～100℃、更优选25～80℃的温度下，在酸或碱催化剂的存在下、优选在碱性催化剂如甲醇纳或甲醇钾的存在下，在搅拌反应器(特别是在高剪切下)或者固定或流化床反应器中，在溶剂如甲醇中进行例如4～8小时的时期。作为变型，酯交换可在超临界甲醇的存在下在高的温度和压力下进行。通常，将所有的反应物脱水以防止甘油三酯皂化并且使得能够较容易地分离甘油。
在根据本发明的方法的步骤(a)中，所述甘油在液相或气相中脱水为丙烯醛。根据本发明的一个优选实施方式，甘油脱水为丙烯醛在250～350℃和1～5巴下在分子氧的存在下并且有利地使用如申请WO 2006/087083所述的酸性固体催化剂，优选在如申请WO 2006/087084所述的具有-9～-18的哈米特酸度函数H0的强酸型催化剂的存在下进行。
作为变型，如申请US 2008/119663中所述的，甘油的脱水可通过在250～400℃、优选260～300℃的温度下加热而进行。在液相中反应的情况下，将压力调节例如为1～50巴，以保持所述反应介质为液态。均相或非均相的酸催化剂、和/或无机酸的盐如硫酸(氢)钾或钠可用于加速反应。因此可使用均相的酸催化剂如硫酸、磷酸、甲苯磺酸或甲烷磺酸，或者非均相的酸催化剂如HZSM-5或MCM-22型沸石，被无机酸如磷酸包覆的金属氧化物如氧化铝，或离子交换树脂。作为变型，可使用生物催化剂如脂肪酶或酯酶。
本说明书没有排除在如上所述脱水催化剂的存在下在甘油由甘油三酯形成的同时脱水为丙烯醛，如文献US 2008/0119663所教导的。在这种情况下，则建议然后通过任何适当的方式例如通过蒸馏、萃取、相分离或膜分离进行所述丙烯醛与反应介质的分离。然而，优选分别进行酯交换和脱水步骤以优化丙烯醛的产率。为此，有利地通过蒸馏、膜分离或相分离从所述酯交换反应介质中提取甘油。然后其可在转化为丙烯醛之前任选地纯化以除去其少量含有的皂、盐和碱。
根据本发明的方法的步骤(a)中产生的丙烯醛然后根据下列反应方案在步骤(b)中经历氨氧化以得到丙烯腈：
CH2＝CH-CHO+NH3+0.5O2→CH2＝CH-CN+2H2O
这种氨氧化步骤是本领域技术人员公知的，并且可具体地在200～450℃下通过使丙烯醛、氨、空气和惰性气体的混合物经过由砷和较小电负性元素的一种或多种氧化盐(oxygenated salt)形成的催化剂来进行。这种类型的方法描述于申请FR 1 410 967中。作为变型，其可如文献DE-1070170中所述通过使用基于钼的催化剂在250～350℃的温度下进行，或者如文献US-3,094,552中所述通过使所述反应混合物经过基于锡和锑的催化剂在300～550℃的温度下进行，或者如专利GB-709337中所述在由二氧化硅、氧化钼和磷酸的混合物形成的催化剂的存在下在250～600℃的温度下进行。
在根据本发明的方法的步骤(c)中使由此得到的丙烯腈聚合。所述丙烯腈可均聚，或者根据本发明的优选实施方式与至少一种其它单体共聚，所述其它单体优选丙烯酸类单体，即(甲基)丙烯酸或(甲基)丙烯酸烷基酯的单体，如丙烯酸甲酯、甲基丙烯酸甲酯或丙烯酸。实际上，只要这种共聚单体不超过相对于待聚合单体总重量的10重量％，这种共聚单体就容许更好地控制后续步骤(e)的热效应(Gupta，A.K.等，JMS-Rev.Macromol.Chem.Phys.C31，1991)。这种共聚单体本身可为可再生来源的。因此，丙烯酸可由甘油得到，并且甲基丙烯酸甲酯可经由其合成并入可再生来源的丙酮和甲醇。丙烯酸甲酯优选用于本发明，因为其与丙烯腈的极性非常接近。
丙烯腈的(共)聚合可以常规的方式使用二甲亚砜(DMSO)或二甲基酰胺(DMF)型溶剂通过自由基溶液聚合任选地在活化剂如偶氮二异丁腈(AIBN)或偶氮羧酸酯的存在下进行，如专利申请US 2004/068069中所述的。作为变型，例如，丙烯腈的(共)聚合可在水分散体中在硫氰酸钠、氯化锌或高氯酸钠的存在下进行。可使用的聚合方法具体描述于″Polymerization of acrylic fibers″，Encyclopedia of Polymer Science，Vol.1，pp.334～338，1985中。所得到的由PAN表示的均聚物或共聚物通常具有约80000～120000g/mol的重均分子量。
然后这种PAN在根据本发明的方法的步骤(d)中形成为纤维。该步骤可以若干方式进行。
根据一个方法，将所述PAN与至少一种增塑剂如碳酸烷基酯特别是碳酸亚乙酯(乙二醇与碳酸的酯)混合，然后将其在110～160℃下加热以使其软化，并将其注射通过精密模具(fine die)，使得其落入例如由水组成的浴中，其中其以纤维的形式凝结和固化。这种方法与用于制造丙烯酸类纺织纤维的方法非常类似。
根据另一方法，将PAN溶解在溶剂(DMSO、DMF、DMA或无机盐的水溶液)中并将其注射通过精细模具进入接收室或干燥炉中，其中所述聚合物在溶剂蒸发之后形成固体纤维。
在所有的情况下，将由此得到的纤维洗涤和拉伸，直至得到所需的纤维直径。拉伸还使得可排列分子物质，这将随后促进在碳化期间的碳-碳键的正确形成并提供具有大硬度的纤维。
在实际碳化之前，纤维需要稍微地化学改性以将它们的原子排列转化为更加交联的结构。这种称为稳定化的操作或部分氧化操作构成根据本发明的方法的步骤(e)。
该操作是通过将所述PAN纤维在空气的存在下在200～300℃下加热几十分钟进行的。以这种方式，所述纤维改变其原子排列并产生极性表面官能；其从塑料状态变为热稳定的难熔(不熔，infusible)状态。由于该反应是放热的，建议确保控制热传递，因为可发生热失控。
在稳定化操作之后，构成根据本发明的方法的步骤(f)的实际碳化是通过将来自步骤(e)的纤维在用惰性气体吹扫并保持在高于大气压的压力以防止空气再次进入炉子的炉子中在1200～1500℃的温度下加热而进行的。
在碳化期间，除碳之外的大部分原子是以下列形式排出的：对于氧和氢的水蒸汽、对于氮原子的氨和氰化氢、气态氮、源自极性表面官能的一氧化碳和二氧化碳。这些原子的排出容许碳通过产生强键而以微晶形式组织化(organize)。所述碳化可任选地以两个步骤在两个不同的温度下进行以更好地控制整个过程。因此第一碳化步骤可在400～800℃下进行，在该步骤期间所述纤维任选地进行拉伸。
在这种碳化步骤结束时，取决于处理温度，得到称为“高强度”或“中间模量”纤维的纤维。随后的在2000～3000℃下的石墨化步骤任选地使得可得到称为“高模量”纤维的纤维。
在碳化/石墨化之后，为了改善所述纤维与其中将引入所述纤维的基质的接触，可进行其它步骤。因此，例如，可通过在空气或一氧化碳的存在下的处理或在液相中使用次氯酸钠、硝酸、或硫酸、氢氧化钠和碳酸氢铵的溶液的处理，稍微氧化其表面。必须良好地控制所有这些操作以防止产生可导致与所述基质的有缺陷的粘合的表面缺陷。
所述纤维还可经历上浆(sizing)或上油(oiling)处理，其目的在于在其运输、编织或缠绕过程中保护它们。这种处理在于对所述纤维施加涂覆材料，这种涂覆材料选择为与在复合材料制造中使用的粘合剂相容并且其可例如选自环氧树脂、聚酯或聚氨酯。
本发明的另一主题是能够根据之前所述的方法得到的碳纤维。
这些碳纤维的特征在于它们包含不可忽略量的可再生或生物基来源的或同时代来源的碳，即14C。实际上，从活有机体、特别是在根据本发明的方法的第一步骤中使用的植物物质取得的所有碳样品是三种同位素的混合物：12C、13C和14C，其14C/12C比通过碳与环境的连续交换而保持恒定并等于1.2×10-12。虽然14C是放射性的并且其浓度因此随着时间降低，但是其半衰期为5730年，使得从植物物质的提取直到纤维的制造和甚至直到它们使用的结束，14C含量都被认为是恒定的。
更具体地，认为根据本发明的碳纤维的它们的14C含量与它们的12C含量的同位素比大于10-12但是不超过1.2×10-12，其中14C表示具有6个质子和8个中子的同位素，而12C表示具有6个质子和6个中子的稳定同位素。含有100％可再生碳的碳纤维含有至多1.2×10-12的14C。
所述碳纤维的14C含量可根据用于测定考古学遗物、老木头、骨头、泥煤或甚至海贝壳的年代的公知技术测量。例如，其可根据下列技术测量：
-通过液体闪烁光谱法：该方法在于对由14C的衰变产生的“β”颗粒进行计数。对由已知重量(已知碳原子数)的样品产生的β辐射进行一定时间的测量。该“放射性”与14C原子数成比例，由此可确定14C原子数。样品中存在的14C发射β辐射，其与闪烁液体(闪烁剂)接触时产生光子。这些光子具有不同的能量(0～156keV)并形成称为14C光谱的光谱。根据这种方法的两种变型，所述分析集中在合适的吸收剂溶液中由基于碳的样品在前产生的CO2、或者集中在基于碳的样品在先转化为苯后的苯。
-通过质谱法：将样品还原为石墨或气态CO2，然后在质谱仪中分析。该技术使用加速器和质谱仪以将14C离子与12C离子分离并由此确定两种同位素之比。
这些用于测量材料的14C含量的方法明确地描述于ASTM D 6866标准(特别是D6866-06)和ASTMD 7026标准(特别是7026-04)中。这些方法将测量样品的14C/12C比并将其与100％可再生来源的参比样品的14C/12C比进行比较，以得到该样品中可再生来源的碳的相对百分比。
因此本发明的另一主题是其14C含量与其12C含量的同位素比大于2×10-11、例如大于5×10-11、和优选大于10-12且至多等于1.2×10-12的碳纤维。
根据本发明的碳纤维可用于其中它们通常使用的所有应用中，特别是用于增强复合材料，尤其是在航空器或航天器部件、运动器材(网球球拍和高尔夫球棒)和风轮机的制造中的增强复合材料；用于高温气体的过滤；作为抗静电剂；作为特种电极；或作为用于加压气罐，尤其是储存氢气的加压气罐的增强物。
因此本发明的另一主题是如前所述的碳纤维的这些用途。
Claims (11)
1.制造碳纤维的方法，包括：
a)由植物来源的甘油合成丙烯醛；
b)将所述丙烯醛氨氧化以得到丙烯腈；
c)将所述丙烯腈聚合为丙烯腈的均聚物或共聚物(PAN)；
d)将所述PAN转化为PAN纤维；
e)将所述PAN纤维部分氧化；和
f)将所述部分氧化的PAN纤维碳化。
2.权利要求1的方法，其特征在于步骤(a)中使用的甘油是作为植物来源的甘油三酯的酯交换的副产物得到的。
3.权利要求2的方法，其特征在于所述甘油是作为在由植物油制造生物柴油中的副产物得到的。
4.权利要求1～3中任一项的方法，其特征在于在步骤(a)中，所述甘油通过在250～400℃、优选260～300℃的温度下加热而脱水为丙烯醛。
5.权利要求1～4中任一项的方法，其特征在于在步骤(c)中，所述丙烯腈与至少一种丙烯酸类共聚单体如丙烯酸甲酯、甲基丙烯酸甲酯或丙烯酸共聚。
6.权利要求5的方法，其特征在于所述共聚单体不超过相对于待聚合单体总重量的10重量％。
7.权利要求1～6中任一项的方法，其特征在于，在步骤(e)中，所述PAN纤维的部分氧化是通过在空气的存在下在200～300℃下将所述纤维加热几分钟进行的。
8.权利要求1～7中任一项的方法，其特征在于，在步骤(f)中，所述PAN纤维的碳化是在用惰性气体吹扫并维持在高于大气压的压力下的炉子中在1200～1500℃的温度下加热所述纤维进行的。
9.能够根据权利要求1～8中任一项的方法得到的碳纤维。
10.14C含量与12C含量的同位素比大于5×10-11且优选大于10-12的碳纤维。
11.权利要求9或10的碳纤维在增强复合材料，尤其是在航空器或航天器部件、运动器材(网球球拍和高尔夫球棒)和风轮机的制造中的增强复合材料中；在高温气体的过滤中；作为抗静电剂；作为特种电极；或作为用于加压气罐，特别是储存氢气的加压气罐的增强物的用途。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0855703A FR2935148B1 (fr) | 2008-08-25 | 2008-08-25 | Procede de fabrication de fibres de carbone. |
| FR0855703 | 2008-08-25 | ||
| PCT/FR2009/051622 WO2010023403A1 (fr) | 2008-08-25 | 2009-08-24 | Procede de fabrication de fibres de carbone |
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| CN102131969A true CN102131969A (zh) | 2011-07-20 |
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| CN200980132923XA Pending CN102131969A (zh) | 2008-08-25 | 2009-08-24 | 制造碳纤维的方法 |
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| US (1) | US20100047153A1 (zh) |
| EP (1) | EP2159309B1 (zh) |
| JP (1) | JP2012500910A (zh) |
| KR (1) | KR20110044922A (zh) |
| CN (1) | CN102131969A (zh) |
| AT (1) | ATE512239T1 (zh) |
| BR (1) | BRPI0916918A2 (zh) |
| ES (1) | ES2367095T3 (zh) |
| FR (1) | FR2935148B1 (zh) |
| PL (1) | PL2159309T3 (zh) |
| WO (1) | WO2010023403A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102996257A (zh) * | 2011-09-13 | 2013-03-27 | 金涌 | 一种粉煤直燃的整体联合循环发电系统 |
| CN110168153A (zh) * | 2016-11-01 | 2019-08-23 | 柯利亚·库赛 | 以二氧化碳为原料结合整体生产方法制造可再生或部分可再生碳纤维 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9802862B2 (en) * | 2008-11-27 | 2017-10-31 | Kolja Kuse | CO2 emission-free construction material made of CO2 |
| FR2950333B1 (fr) | 2009-09-23 | 2011-11-04 | Arkema France | Procede de fonctionnalisation de nanotubes |
| US20110104041A1 (en) * | 2009-10-30 | 2011-05-05 | Goodrich Corporation | Methods and systems for hcn removal |
| US9284191B2 (en) * | 2013-03-15 | 2016-03-15 | Mcalister Technologies, Llc | Carbon-based manufacturing of fiber and graphene materials |
| KR102004731B1 (ko) * | 2016-11-23 | 2019-07-29 | 주식회사 엘지화학 | 폴리아크릴로니트릴계 섬유의 제조방법 및 이에 이용되는 폴리아크릴로니트릴계 공중합체 |
| EP3947791B1 (en) * | 2019-03-29 | 2024-05-08 | Cytec Industries, Inc. | Process and system for the production of homogeneous solutions of polyacrylonitrile-based polymer |
| DE202022000235U1 (de) * | 2022-01-29 | 2022-02-11 | Britta Waschl | Baumaterialien aus Carbonfasern, die aus CO2 hergestellt werden |
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| US20080119663A1 (en) * | 2006-11-20 | 2008-05-22 | Evonik Degussa Gmbh | Process for preparing fatty acid alkyl esters and acrolein from triglycerides |
| FR2912742A1 (fr) * | 2007-02-16 | 2008-08-22 | Arkema France | Procede de synthese d'acrylonitrile a partir de glycerol |
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| US3976746A (en) * | 1974-06-06 | 1976-08-24 | Hitco | Graphitic fibers having superior composite properties and methods of making same |
| DE3037582A1 (de) * | 1980-10-04 | 1982-05-19 | Verseidag-Industrietextilien Gmbh, 4150 Krefeld | Verfahren zur herstellung eines aus aktivkohle bestehenden flaechengebildes |
| US5804108A (en) * | 1996-10-31 | 1998-09-08 | Wilkinson; Kenneth | Process for the preparation of carbon fiber |
| FR2813319A1 (fr) * | 2000-08-29 | 2002-03-01 | Atofina | Procede de fabrication de fibres a base d'acrylonitrile |
| FR2882053B1 (fr) | 2005-02-15 | 2007-03-23 | Arkema Sa | Procede de deshydratation du glycerol en acrolene |
| FR2882052B1 (fr) * | 2005-02-15 | 2007-03-23 | Arkema Sa | Procede de deshydratation du glycerol en acroleine |
| FR2884818B1 (fr) * | 2005-04-25 | 2007-07-13 | Arkema Sa | Procede de preparation d'acide acrylique a partir de glycerol |
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2008
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- 2009-08-24 EP EP09168453A patent/EP2159309B1/fr active Active
- 2009-08-24 ES ES09168453T patent/ES2367095T3/es active Active
- 2009-08-24 WO PCT/FR2009/051622 patent/WO2010023403A1/fr active Application Filing
- 2009-08-24 JP JP2011524435A patent/JP2012500910A/ja not_active Withdrawn
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- 2009-08-24 AT AT09168453T patent/ATE512239T1/de not_active IP Right Cessation
- 2009-08-24 KR KR1020117006781A patent/KR20110044922A/ko not_active Application Discontinuation
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|---|---|---|---|---|
| CN1930332A (zh) * | 2004-03-11 | 2007-03-14 | 东丽株式会社 | 碳纤维及其制造方法、预浸料坯以及高尔夫杆 |
| US20080119663A1 (en) * | 2006-11-20 | 2008-05-22 | Evonik Degussa Gmbh | Process for preparing fatty acid alkyl esters and acrolein from triglycerides |
| FR2912742A1 (fr) * | 2007-02-16 | 2008-08-22 | Arkema France | Procede de synthese d'acrylonitrile a partir de glycerol |
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| CN102996257A (zh) * | 2011-09-13 | 2013-03-27 | 金涌 | 一种粉煤直燃的整体联合循环发电系统 |
| CN110168153A (zh) * | 2016-11-01 | 2019-08-23 | 柯利亚·库赛 | 以二氧化碳为原料结合整体生产方法制造可再生或部分可再生碳纤维 |
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| Publication number | Publication date |
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| PL2159309T3 (pl) | 2011-10-31 |
| EP2159309A1 (fr) | 2010-03-03 |
| FR2935148B1 (fr) | 2010-08-27 |
| KR20110044922A (ko) | 2011-05-02 |
| ATE512239T1 (de) | 2011-06-15 |
| FR2935148A1 (fr) | 2010-02-26 |
| BRPI0916918A2 (pt) | 2015-11-24 |
| US20100047153A1 (en) | 2010-02-25 |
| WO2010023403A1 (fr) | 2010-03-04 |
| ES2367095T3 (es) | 2011-10-28 |
| JP2012500910A (ja) | 2012-01-12 |
| EP2159309B1 (fr) | 2011-06-08 |
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