CN107502998A - 一种高性能淀粉基碳纤维及其制备方法 - Google Patents

一种高性能淀粉基碳纤维及其制备方法 Download PDF

Info

Publication number
CN107502998A
CN107502998A CN201710749967.3A CN201710749967A CN107502998A CN 107502998 A CN107502998 A CN 107502998A CN 201710749967 A CN201710749967 A CN 201710749967A CN 107502998 A CN107502998 A CN 107502998A
Authority
CN
China
Prior art keywords
base carbon
parts
starch base
carbon fibre
starch
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.)
Withdrawn
Application number
CN201710749967.3A
Other languages
English (en)
Inventor
李红梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deyang Li Long Yun Intellectual Property Operation Co Ltd
Original Assignee
Deyang Li Long Yun Intellectual Property Operation Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Deyang Li Long Yun Intellectual Property Operation Co Ltd filed Critical Deyang Li Long Yun Intellectual Property Operation Co Ltd
Priority to CN201710749967.3A priority Critical patent/CN107502998A/zh
Publication of CN107502998A publication Critical patent/CN107502998A/zh
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/12—Disaccharides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/24—Preparation of compounds containing saccharide radicals produced by the action of an isomerase, e.g. fructose
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/58—Aldonic, ketoaldonic or saccharic acids
    • 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
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • 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
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • 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
    • 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
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2391/06—Waxes
    • 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
    • C08J2433/00—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
    • C08J2433/18—Homopolymers or copolymers of nitriles
    • C08J2433/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Toxicology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明公开了一种高性能淀粉基碳纤维及其制备方法，该淀粉基碳纤维包括以下重量份原材料制备而成：淀粉50‑80份、石蜡5‑10份、脱水催化剂1‑3份、交联剂3‑8份、生物酶0.01‑0.03份、聚丙烯腈10‑20份、5‑10份的乙烯基硅油；通过在淀粉基碳纤维中引入硅原子，形成少量碳硅键，从而将淀粉基碳纤维中的相邻碳原子通过硅原子键接起来，增加了碳原子之间的作用力，使淀粉基碳纤维的拉伸强度和拉伸模量显著提高，有利于淀粉基碳纤维替代聚丙烯腈(PAN)基碳纤维、沥青基碳纤维和粘胶基碳纤维在更多领域的推广应用。

Description

一种高性能淀粉基碳纤维及其制备方法
技术领域
本发明涉及碳纤维材料领域，具体涉及一种高性能淀粉基碳纤维及其制备方法。
背景技术
碳纤维(carbon fiber，简称CF)，是一种含碳量在95%以上的高强度、高模量的新型纤维材料。它是由片状石墨微晶等有机纤维沿纤维轴向方向堆砌而成，经碳化及石墨化处理而得到的微晶石墨材料。碳纤维具有许多优良性能，碳纤维的轴向强度和模量高，密度低、比性能高，无蠕变，非氧化环境下耐超高温，耐疲劳性好，比热及导电性介于非金属和金属之间，热膨胀系数小且具有各向异性，耐腐蚀性好，X射线透过性好，导电导热性能好、电磁屏蔽性好等，在国防军工和民用方面都是重要材料。它不仅具有碳材料的固有本征特性，又兼备纺织纤维的柔软可加工性，是新一代特种增强纤维。
随着碳纤维在更多领域的广泛应用，碳纤维需求量的不断增加，现有的聚丙烯腈(PAN)基碳纤维、沥青基碳纤维和粘胶基碳纤维由于其原材料的不可再生性和其制备工艺复杂、耗能大，生产成本高的缺点，导致碳纤维的大规模应用受到限制。而淀粉作为一种天然产物，具有来源丰富，种类多，产量大，含碳量高的特点，用淀粉制备淀粉基碳纤维成为人们的研究热点。但由于普通淀粉呈颗粒状，具有一定结晶度，在碳化过程中，会发生融熔、流淌、膨胀等现象，从而造成采用现有配方或制备方法制备得到的淀粉基碳纤维存在孔隙率高、拉伸强度和模量低的缺陷，不能满足人们对碳纤维的在力学性能上的要求，限制了淀粉基碳纤维的推广应用。
发明内容
本发明的目的在于克服淀粉基碳纤维存在拉伸强度和模量低的缺陷，提供一种淀粉基碳纤维及其制备方法；本发明通过在淀粉基碳纤维中引入硅原子，形成少量碳硅键，从而将淀粉基碳纤维中的相邻碳原子通过硅原子键接起来，增加了碳原子之间的作用力，使淀粉基碳纤维的拉伸强度和拉伸模量显著提高，有利于淀粉基碳纤维替代聚丙烯腈(PAN)基碳纤维、沥青基碳纤维和粘胶基碳纤维在更多领域的推广应用。
为了实现上述发明目的，本发明提供了一种高性能淀粉基碳纤维，包括以下重量份原材料制备而成：淀粉50-80份、石蜡5-10份、脱水催化剂1-3份、交联剂3-8份、生物酶0.01-0.03份、聚丙烯腈10-20份、5-10份的乙烯基硅油。
本发明一种高性能淀粉基碳纤维，含有硅原子，且在硅原子与碳原子之间形成了化学键，该化学键使淀粉基碳纤维中的相邻碳原子之间通过硅原子键接了起来，从而增加了相邻碳原子之间的作用力，使淀粉基碳纤维具有更优异的拉伸强度和拉伸模量，有利于淀粉基碳纤维在更多领域的推广应用。
上述一种高性能淀粉基碳纤维，其中，所述的生物酶包括葡萄糖异构酶和淀粉酶；淀粉酶能快速的将淀粉降解为葡萄糖或果糖；葡萄糖异构酶能将葡萄糖异构化为果糖，利于进行脱水形成5-羟甲基糠醛；优选的，所述的生物酶中葡萄糖异构酶和淀粉酶物质的量之比为2︰1；通过合理的将多种生物酶进行配合使用，能加快淀粉的降解和异构化，缩短处理周期，并达到最佳的处理效果。
上述一种高性能淀粉基碳纤维的制备方法，其中，所述的交联剂为邻苯二甲酸、苯二酚、乙二酸、乙二醇、丙三醇中的一种或多种。
上述一种高性能淀粉基碳纤维的制备方法，其中，所述的聚丙烯腈的分子量为2000-5000；在该分子量范围内，得到的碳纤维性能更好。
上述一种高性能淀粉基碳纤维的制备方法，其中，所述的脱水催化剂是指能催化果糖脱水形成5-羟甲基糠醛的物质；优选的，所述的脱水催化剂为氯化铁、氯化亚铁、氯化铜或盐酸中的一种或多种。
为了实现上述发明目的，进一步的，本发明提供了一种高性能淀粉基碳纤维的制备方法，包括以下步骤：
（1）将淀粉用生物酶进行降解和异构化处理得产物A；
（2）在产物A中加入脱水催化剂进行脱水处理，并分离、干燥得产物B；
（3）将产物B与石蜡、交联剂、聚丙烯腈、乙烯基硅油混合均匀后，在双螺杆挤出机中进行交联聚合反应得到产物C；
（4）将产物C进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝依次进行第一预氧化、第二预氧化和碳化得到高性能淀粉基碳纤维。
本发明高性淀粉基碳纤维的制备方法，先通过生物酶对淀粉进行快速降解和异构化处理，获得更容易进行脱水的果糖；然后通过脱水催化剂催化果糖脱水，形成5-羟甲基糠醛；再利用交联剂与石蜡、乙烯基硅油、聚丙烯腈进行交联聚合反应，将硅原子与碳原子键接起来，增加了相邻碳原子之间的作用力；最后利用两次预氧化的方法，进一步降低淀粉基碳纤维原丝在高温下产生的气体对纤维结构的影响，从而得到了拉伸强度和拉伸模量更好的高性能淀粉基碳纤维，且该制备方法简单、快速、可靠，适合高性能淀粉基碳纤维的大规模、工业化生产。
上述一种淀粉基碳纤维的制备方法，其中，步骤1中所述降解和异构化处理的温度为20-35℃；在该温度范围内，生物酶的活性最好，对淀粉的降解和异构化效果最好。
其中，步骤2中所述的脱水处理温度为85-120℃，时间为1-5h；该反应温度和时间条件下，淀粉的脱水效果最好。
其中，步骤3中双螺杆挤出机中工作区的最高温度为320-340℃，最低温度为260-290℃；物料在在挤出机中的停留时间控制在60-120s；温度太高，副反应多，不利于原材料的交联聚合反应，温度太低，原材料不熔融，交联反应不彻底。
其中，步骤4中熔融纺丝的温度为310-350℃；在该温度范围内纺丝得到的淀粉基碳纤维原丝品质最好。
其中，步骤5中第一预氧化的温度为200-240℃，时间为2-3h，在该温度下，原丝中的大部分含氧基团断裂生成水蒸发出来，为后面的第二预氧化和碳化提供更好的条件，能提高碳纤维的性能；第二预氧化的温度为360-390℃，时间为2-5h，在该温度下，进行环化反应并修复部分原丝中被第一预氧化过程中破坏的纤维结构；优选的，所述的碳化温度为1050-1250℃。
与现有技术相比，本发明的有益效果：
1、本发明高性能淀粉基碳纤维含有硅原子，且在硅原子与碳原子之间形成了化学键，增加了相邻碳原子之间的作用力，使淀粉基碳纤维具有更优异的拉伸强度和拉伸模量。
2、本发明制备方法通过对淀粉进行降解、异构化、脱水和两次预氧化处理，最大程度的减少了淀粉分子中的含氧基团，减少了碳化过程中气体对纤维结构的破坏，降低了碳纤维的孔洞率，从而保证制备得到拉伸强度和拉伸模量更好的高性能淀粉基碳纤维。
3、本发明制备方法简单、可靠，适合淀粉基碳纤维的大规模、工业化生产。
具体实施方式
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明内容所实现的技术均属于本发明的范围。
实施例1
（1）将65份的淀粉用0.02份的葡萄糖异构酶和0.01份的淀粉酶在25℃的温度下进行降解和异构化处理4h得产物A；
（2）在产物A中加入1份的氯化铁、1份的氯化铜在105℃的温度下进行脱水处理3h，并分离、干燥得产物B；
（3）将产物B与8份的石蜡、4份的邻苯二甲酸、4份的乙二酸、15份的聚丙烯腈、8份的乙烯基硅油混合均匀后，用双螺杆挤出机进行交联聚合反应；得到产物C；所述的双螺杆挤出机中工作区的最高温度设置为330℃，最低温度设置为280℃；物料在在挤出机中的停留时间控制在90s；
（4）将产物C在330℃的温度下进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝在220℃的温度下进行第一预氧化3h，在375℃的温度下进行第二预氧化3h后，再在1150℃的温度下进行碳化处理得到高性能淀粉基碳纤维。
实施例2
（1）将50份的淀粉用0.01份的葡萄糖异构酶和0.01份的淀粉酶在35℃的温度下进行降解和异构化处理5h得产物A；
（2）在产物A中加入1份的氯化亚铁在85℃的温度下进行脱水处理5h，并分离、干燥得产物B；
（3）将产物B与5份的石蜡、5份的苯二酚、5份的乙二醇、20份的聚丙烯腈、5份的乙烯基硅油混合均匀后用双螺杆挤出机进行交联聚合反应；得到产物C；所述的双螺杆挤出机中工作区的最高温度设置为320℃，最低温度设置为260℃；物料在在挤出机中的停留时间控制在120s；
（4）将产物C在350℃的温度下进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝在240℃的温度下进行第一预氧化3h，在360℃的温度下进行第二预氧化5h后，再在1250℃的温度下进行碳化处理得到高性能淀粉基碳纤维。
实施例3
（1）将80份的淀粉用0.03份的葡萄糖异构酶和0.02份的淀粉酶在35℃的温度下进行降解和异构化处理2h得产物A；
（2）在产物A中加入1份的氯化铁、1份的氯化亚铁、1份的盐酸，在120℃的温度下进行脱水处理1h，并分离、干燥得产物B；
（3）将产物B与10份的石蜡、2份的乙二醇、3份的丙三醇、10份的聚丙烯腈、10份的乙烯基硅油混合均匀后，用双螺杆挤出机进行交联聚合反应；得到产物C；所述的双螺杆挤出机中工作区的最高温度设置为340℃，最低温度设置为290℃；物料在在挤出机中的停留时间控制在60s；；
（4）将产物C在310℃的温度下进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝在200℃的温度下进行第一预氧化3h，在390℃的温度下进行第二预氧化2h后，再在1050℃的温度下进行碳化处理得到高性能淀粉基碳纤维。
对比例1
（1）将65份的淀粉用0.02份的葡萄糖异构酶和0.01份的淀粉酶在25℃的温度下进行降解和异构化处理4h得产物A；
（2）在产物A中加入1份的氯化铁、1份的氯化铜在105℃的温度下进行脱水处理3h，并分离、干燥得产物B；
（3）将产物B与8份的石蜡、4份的邻苯二甲酸、4份的乙二酸、15份的聚丙烯腈混合均匀后，用双螺杆挤出机进行交联聚合反应；得到产物C；所述的双螺杆挤出机中工作区的最高温度设置为330℃，最低温度设置为280℃；物料在在挤出机中的停留时间控制在90s；
（4）将产物C在330℃的温度下进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝在220℃的温度下进行第一预氧化3h，在375℃的温度下进行第二预氧化3h后，再在1150℃的温度下进行碳化处理得到高性能淀粉基碳纤维。
对比例2
（1）将65份的淀粉用0.02份的葡萄糖异构酶和0.01份的淀粉酶在25℃的温度下进行降解和异构化处理4h得产物A；
（2）将产物B与8份的石蜡、4份的邻苯二甲酸、4份的乙二酸、15份的聚丙烯腈、8份的乙烯基硅油混合均匀后，用双螺杆挤出机进行交联聚合反应；得到产物C；所述的双螺杆挤出机中工作区的最高温度设置为330℃，最低温度设置为280℃；物料在在挤出机中的停留时间控制在90s；
（3）将产物C在330℃的温度下进行熔融纺丝，得到淀粉基碳纤维原丝；
（4）将淀粉基碳纤维原丝在220℃的温度下进行第一预氧化3h，在375℃的温度下进行第二预氧化3h后，再在1150℃的温度下进行碳化处理得到高性能淀粉基碳纤维。
对比例3
（1）将65份的淀粉用0.02份的葡萄糖异构酶和0.01份的淀粉酶在25℃的温度下进行降解和异构化处理4h得产物A；
（2）在产物A中加入1份的氯化铁、1份的氯化铜在105℃的温度下进行脱水处理3h，并分离、干燥得产物B；
（3）将产物B与8份的石蜡、4份的邻苯二甲酸、4份的乙二酸、15份的聚丙烯腈、8份的乙烯基硅油混合均匀后，用双螺杆挤出机进行交联聚合反应；得到产物C；所述的双螺杆挤出机中工作区的最高温度设置为330℃，最低温度设置为280℃；物料在在挤出机中的停留时间控制在90s；
（4）将产物C在330℃的温度下进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝在375℃的温度下进行预氧化3h后，再在1150℃的温度下进行碳化处理得到高性能淀粉基碳纤维。
将上述实施例1-3和对比例1-3中所制备得到的淀粉基碳纤维进行性能检测，记录数据如下：
编号 拉伸强度（MPa） 拉伸模量（份Pa） 密度（份/cm3）
实施例1 1890 168 1.75
实施例2 1920 165 1.72
实施例3 1900 172 1.76
对比例1 1510 137 1.69
对比例2 1050 94 1.34
对比例3 1290 118 1.56
对上述实验数据分析可知，实施例1-3中采用本发明技术方案，得到的高性能淀粉基碳纤维拉伸强度和拉伸模量大；而对比例1中没有添加乙烯基硅油，相邻碳原子之间作用力小，得到的淀粉基碳纤维拉伸强度和模量显著降低；对比例2中没有添加脱水催化剂进行脱水处理，淀粉基碳纤维原丝中含氧基团多，碳化时产生大量气体，使碳纤维中出现较多孔洞，其拉伸强度、模量显著降低；对比例3中对淀粉基碳纤维原丝进行一次预氧化，碳纤维中存在一定的孔洞，碳纤维密度下降，碳纤维拉伸强度和拉伸模量显著降低。

Claims (10)

1.一种高性能淀粉基碳纤维，其特征在于，包括以下重量份原材料制备而成：淀粉50-80份、石蜡5-10份、脱水催化剂1-3份、交联剂3-8份、生物酶0.01-0.03份、聚丙烯腈10-20份、5-10份的乙烯基硅油。
2.根据权利要求1所述的淀粉基碳纤维，其特征在于，所述的生物酶包括葡萄糖异构酶和淀粉酶。
3.根据权利要求2所述的淀粉基碳纤维，其特征在于，所述的生物酶中葡萄糖异构酶和淀粉酶物质的量之比为2︰1。
4.根据权利要求1所述的淀粉基碳纤维，其特征在于，所述的交联剂为邻苯二甲酸、苯二酚、乙二酸、乙二醇、丙三醇中的一种或多种。
5.根据权利要求1所述的淀粉基碳纤维，其特征在于，所述的脱水催化剂为氯化铁、氯化亚铁、氯化铜或盐酸中的一种或多种。
6.一种如权利要求1-5任一项所述淀粉基碳纤维的制备方法，其特征在于，包括以下步骤：
（1）将淀粉用生物酶进行降解和异构化处理得产物A；
（2）在产物A中加入脱水催化剂进行脱水处理，并分离、干燥得产物B；
（3）将产物B与石蜡、交联剂、聚丙烯腈、乙烯基硅油混合均匀后，在双螺杆挤出机中进行交联聚合反应得到产物C；
（4）将产物C进行熔融纺丝，得到淀粉基碳纤维原丝；
（5）将淀粉基碳纤维原丝依次进行第一预氧化、第二预氧化和碳化得到高性能淀粉基碳纤维。
7.根据权利要求6所述的制备方法，其特征在于，步骤2中脱水处理温度为85-120℃，时间为1-5h。
8.根据权利要求6所述的制备方法，其特征在于，步骤3中用双螺杆挤出机进行交联聚合反应；所述的双螺杆挤出机中工作区的最高温度设置为320-340℃，最低温度设置为260-290℃；物料在在挤出机中的停留时间控制在60-120s。
9.根据权利要求6所述的制备方法，其特征在于，步骤4中熔融纺丝的温度为310-350℃。
10.根据权利要求6所述的制备方法，其特征在于，步骤5中第一预氧化的温度为200-240℃，时间为2-3h；第二预氧化的温度为360-390℃，时间为2-5h。
CN201710749967.3A 2017-08-28 2017-08-28 一种高性能淀粉基碳纤维及其制备方法 Withdrawn CN107502998A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710749967.3A CN107502998A (zh) 2017-08-28 2017-08-28 一种高性能淀粉基碳纤维及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710749967.3A CN107502998A (zh) 2017-08-28 2017-08-28 一种高性能淀粉基碳纤维及其制备方法

Publications (1)

Publication Number Publication Date
CN107502998A true CN107502998A (zh) 2017-12-22

Family

ID=60693982

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710749967.3A Withdrawn CN107502998A (zh) 2017-08-28 2017-08-28 一种高性能淀粉基碳纤维及其制备方法

Country Status (1)

Country Link
CN (1) CN107502998A (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109402792A (zh) * 2018-10-31 2019-03-01 北京化工大学 一种低直径高强度的聚丙烯腈基碳纤维及其制备方法
CN111039417A (zh) * 2019-12-26 2020-04-21 南京公诚节能新材料研究院有限公司 一种生物基人工水草
CN115650745A (zh) * 2022-11-07 2023-01-31 郑州东方炉衬材料有限公司 一种气化炉炉膛内衬浇注料及其生产工艺
CN115679709A (zh) * 2022-11-04 2023-02-03 苏州铂韬新材料科技有限公司 一种纤维吸波材料

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109402792A (zh) * 2018-10-31 2019-03-01 北京化工大学 一种低直径高强度的聚丙烯腈基碳纤维及其制备方法
CN111039417A (zh) * 2019-12-26 2020-04-21 南京公诚节能新材料研究院有限公司 一种生物基人工水草
CN115679709A (zh) * 2022-11-04 2023-02-03 苏州铂韬新材料科技有限公司 一种纤维吸波材料
CN115679709B (zh) * 2022-11-04 2023-10-03 苏州铂韬新材料科技有限公司 一种纤维吸波材料
CN115650745A (zh) * 2022-11-07 2023-01-31 郑州东方炉衬材料有限公司 一种气化炉炉膛内衬浇注料及其生产工艺

Similar Documents

Publication Publication Date Title
CN107502998A (zh) 一种高性能淀粉基碳纤维及其制备方法
KR101981416B1 (ko) 셀룰로오스를 원료로 바이오매스 그래핀을 제조하는 방법
KR101689861B1 (ko) 나노카본 복합 고성능 저가 탄소섬유 및 그 제조방법
Liu et al. Development of pitch-based carbon fibers: a review
CN101910480B (zh) 耐燃纤维和碳纤维的制造方法
CN102704043B (zh) 一种聚丙烯腈预氧纤维和碳纤维的制备方法
CN101956252A (zh) 一种硼改性聚丙烯腈原丝制备碳纤维的方法
JP2014105148A (ja) 炭素繊維強化炭素複合材料用の中間材料
KR101628461B1 (ko) 탄소섬유 단열재 및 이의 제조방법
CN102534866B (zh) 高模量碳纤维及其制造方法
WO2018115177A1 (en) Graphite material
CN113774720A (zh) 一种碳纤维纸及其制备方法
CN111690186A (zh) 一种高耐磨抗冲复合橡胶及其制备方法
CN107385564A (zh) 一种淀粉基碳纤维的制备方法
CN107502999A (zh) 一种淀粉基碳纤维及其制备方法
CN106978653B (zh) 一种纤维素晶须增强木质素基碳纤维的制备方法
CN105332098A (zh) 一种碳纤维活化工艺
CN107326477A (zh) 一种木质素基复合碳纤维及其制备方法
CN107299419A (zh) 一种高强度淀粉基碳纤维的制备方法
CN111285703A (zh) 一种低成本双元炭基体飞机炭刹车盘的制造方法
CN110656452A (zh) 一种碳纤维布毡制备工艺及应用
CN107881599B (zh) 一种提高聚丙烯腈基碳纤维强度的方法
CN101570904A (zh) 一种沥青碳纤维的制备方法
CN107956002A (zh) 一种碳纤维生产方法
CN103922780B (zh) 纳米粘土增强炭/炭复合材料的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20171222