TW201529612A - 具有低聚合度分佈性指數(pdi)的聚丙烯腈(pan)聚合物及從其製成的碳纖維 - Google Patents
具有低聚合度分佈性指數(pdi)的聚丙烯腈(pan)聚合物及從其製成的碳纖維 Download PDFInfo
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- TW201529612A TW201529612A TW103143528A TW103143528A TW201529612A TW 201529612 A TW201529612 A TW 201529612A TW 103143528 A TW103143528 A TW 103143528A TW 103143528 A TW103143528 A TW 103143528A TW 201529612 A TW201529612 A TW 201529612A
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- polymer
- pdi
- polymerization
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- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 75
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 28
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
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- JGHKDVSIFPFNIJ-UHFFFAOYSA-N dodecylsulfanylmethanedithioic acid Chemical compound CCCCCCCCCCCCSC(S)=S JGHKDVSIFPFNIJ-UHFFFAOYSA-N 0.000 claims description 3
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- IDSLBLWCPSAZBL-UHFFFAOYSA-N 2-cyanopropan-2-yl benzenecarbodithioate Chemical compound N#CC(C)(C)SC(=S)C1=CC=CC=C1 IDSLBLWCPSAZBL-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010998 test method Methods 0.000 claims description 2
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims 1
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- 238000004519 manufacturing process Methods 0.000 abstract description 5
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Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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 a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/42—Nitriles
- C08F120/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- 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
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- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/0078—Producing filamentary materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29L2031/00—Other particular articles
- B29L2031/731—Filamentary material, i.e. comprised of a single element, e.g. filaments, strands, threads, fibres
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Abstract
本發明揭示一種合成具有窄分子量分佈之聚丙烯腈(PAN)聚合物之方法。較佳PAN聚合物具有約2或更小之PDI(Mw/Mn)。該PAN聚合物係藉由受控/活性自由基聚合使用特定RAFT(可逆加成-斷裂鏈轉移)劑來合成。亦揭示自具有低PDI之PAN聚合物產生碳纖維之方法。
Description
本揭示內容概言之係關於聚丙烯腈(PAN)聚合物之合成及自PAN聚合物形成碳纖維之方法。
因諸如高比強度及勁度、高抗化學性及低熱膨脹等性質,碳纖維已廣泛用於航空、運動及汽車、風能及其他節能領域之商業工業。通常,碳纖維係自基於聚丙烯腈(PAN)之聚合物製成。
PAN聚合物通常係藉由自由基聚合方法製成。在自由基聚合中,觸媒或起始劑首先引發以形成起始自由基物質。該等自由基物質開始與單體發生反應以產生活性中心,從而形成單體自由基。然後,單體自由基與其他單體發生反應以增長分子鏈,從而形成聚合物自由基。
在聚合期間,有時一個自由基與另一自由基發生反應以偶合並形成長死鏈(作為組合終止),而一個鏈末端之某一自由基可攻擊第二自由基鏈中第二至最後碳原子處之氫原子以形成歧化終止。聚合物自由基亦可與另一化合物(例如鏈轉移劑)發生反應以終止聚合物自由基之增長反應,且自鏈轉移劑形成新自由基。此新形成鏈轉移自由基開
始其新鏈增長。因此,鏈轉移劑減小了所生長聚合物自由基鏈之長度。若此終止速率遠高於增長速率,則形成具有短鏈長度之極小聚合物。因此,使用鏈轉移劑控制聚合物之分子長度或分子量。因不同終止機制,所得分子鏈具有不同長度或不同分子量。因此,聚合物之分子量具有一定分佈。此分佈可如下所述藉由其聚合度分佈性指數(PDI)來定義:
另一選擇為,PDI可表示如下:
藉由GPC(凝膠滲透層析)方法量測Mw、Mn、Mz。此處,Mw係重量平均分子量。Mn係數量平均分子量且Mz係Z-平均分子量或尺寸平均分子量。
高PDI指示聚合物具有大分子量分佈,此意味著聚合物具有極高分子量物質或極低分子量物質或二者。換言之,聚合物由長度變化較大之分子鏈構成。存在過高分子量或過小分子量物質將影響藉由紡絲使聚合物變為纖維之可處理性及所得纖維性質(尤其過小分子量物質),此乃因實際上小分子量物質係聚合物機械性質之一類分子缺陷。
藉由習用自由基聚合製得之PAN聚合物並不容許控制聚合。所得聚合物具有大分子量分佈。因此,自該PAN紡絲之纖維難以取得機械性質之發展。
本揭示內容提供合成具有窄分子量分佈之聚丙烯腈(PAN)聚合物之方法及自該聚合物產生碳纖維前體之方法。較佳PAN聚合物具有約2或更小之PDI(Mw/Mn)。藉由受控/活性自由基聚合使用特定RAFT
(可逆加成-斷裂鏈轉移)劑來合成該PAN聚合物。
自纖維前體產生之碳纖維展現良好性質,例如均勻橫截面、低微缺陷及分子缺陷。該等良好性質係源於實際上低-PDI聚合物具有均勻Mw,且在碳纖維製造製程期間得到低分子缺陷及微缺陷。
圖1係展示自低-PDI PAN聚合物產生之凍乾PAN凝結纖維之微孔分佈之汞孔隙率測定圖。
圖2係自低-PDI PAN聚合物產生之PAN纖維前體之橫截面區域之顯微影像。
圖3係圖2中所提及同一PAN纖維前體之橫截面區域之變異性圖表。
本揭示內容之一態樣係關於藉由受控/活性自由基聚合使用特定RAFT劑來控制PAN分子量分佈或PDI之機制。PDI(Mw/Mn)之目標為2或更小,較佳地PDI(Mw/Mn)為1.2至1.9(或替代PDI(Mz/Mw)為1.2至1.7)。
若鏈終止僅發生於所有單體在自由基聚合期間皆消耗之後,則此聚合稱為活性聚合。在此聚合反應中,若向反應中添加額外單體,則增長可繼續。作為活性聚合,在反應開始時所有鏈皆引發且以類似速率生長。並無不可逆鏈轉移或終止。若引發較增長較為快速,則分子量分佈極窄且可藉由進一步向反應中添加單體來延伸鏈。然而,在自由基聚合中,所有鏈不會同時為活性。因此,使用一些試劑藉由形成休眠階段來控制增長及其速率。藉由可逆地鈍化或活化增長,可在活性鏈與休眠鏈之間達成快速平衡以在類似速率下控制鏈生長,從而可獲得窄分子量分佈。此稱為「受控/活性自由基聚合」。本文所用
之化學物質稱為RAFT(可逆加成/斷裂鏈轉移)劑。
製備具有窄分子量分佈之PAN聚合物之方法係溶液聚合方法,其包含:a.組合丙烯腈(AN)單體與溶劑、一或多種共單體及RAFT劑(如本文中所定義)以形成溶液;b.將溶液加熱至高於室溫之溫度(亦即>25℃,例如40℃-85℃);及c.向溶液中添加起始劑以引發聚合反應。
在完成聚合之後,移除(例如在高真空下脫氣)未反應AN單體,且冷卻所得PAN聚合物溶液。在此階段,PAN聚合物呈備用於紡絲之溶液或濃液形式。
藉由受控/活性自由基聚合使用RAFT劑來影響AN單體之聚合,RAFT劑係具有下列結構之硫代羰基硫基化合物:
RAFT劑之有效性依賴於取代基R及Z。取代基影響聚合反應動力學及結構控制程度。R基團係自由基離去基團。其在RAFT聚合期間控制再引發聚合。另外,Z基團控制C=S鍵反應性之穩定性且影響自由基加成及斷裂之速率。
較佳RAFT劑係選自由具有下列結構之硫代羰基硫基化合物組成之群:
其中Z1=-CH2-(CH2)10-CH3;-(CH2)n-CH3,n=0-20;
-C(CH3)m-COOH,m=1-2;-C(CH3)m-COOCH3,m=1-2;-C(CH3)m-COOC2H5,m=1-2。
其中;
,R=F、Cl、CN、OCH3;
R’2=-CN;,X=0-1;-C(CH3)m-COOCH3,m=1-2;-C(CH3)m-COOC2H5,m=1-2;R”2=H;-CH3;-(CH2)m-COOH,m=1-2;R’’’2=H;-CH3
其中Z3=-CH2-(CH2)10-CH3;-(CH2)y-CH3,y=1-20;R3=-CH2-(CH2)10-CH3;-(CH2)y-CH3,y=1-20。
具有上述結構I、II及III之RAFT劑之具體實例分別如下:
1)三硫代碳酸酯:三硫代碳酸2-氰基-2-丙基酯十二烷基酯(CPDTC)
2)二硫代苯甲酸酯:二硫代苯甲酸2-氰基-2-丙基酯(CPBZ)
3)硫代羰基二硫醚:雙-十二烷基硫基硫代羰基二硫醚(BDSTD)
用於聚合之適宜溶劑包含:二甲基亞碸(DMSO)、二甲基甲醯胺(DMF)、二甲基乙醯胺(DMAc)、碳酸乙二酯(EC)、氯化鋅(ZnCl2)/水及硫代氰酸鈉(NaSCN)/水。
適於合成PAN聚合物之共單體可為一或多種以下物質:基於乙烯基之酸(包含甲基丙烯酸(MAA)、丙烯酸(AA)、衣康酸(ITA))、基於乙烯基之酯(例如甲基丙烯酸酯(MA)、甲基丙烯酸甲酯(MMA)、乙酸乙烯酯(VA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、甲基丙烯酸乙酯(EMA))及其他乙烯基衍生物(例如乙烯基咪唑(VIM)、丙烯醯胺(AAm)及二丙酮丙烯醯胺(DAAm))。
可藉由以下起始劑(或觸媒)來引發PAN聚合:基於偶氮之化合物,例如:偶氮-雙異丁腈(AIBN)、偶氮雙氰基戊酸(ACVA)及2,2'-偶氮雙-(2,4-二甲基)戊腈(ABVN)或其他;或有機過氧化物,例如過氧化二月桂醯(LPO)、二第三丁基過氧化物(TBPO)、過氧化二碳酸二異丙酯(IPP)及其他。
根據一較佳實施例,基於下列調配物(重量%(wt%))來實施PAN聚合:>90% AN單體;<5%共單體;<1%起始劑;<1% RAFT劑,基於該4種組份之總重量;及足夠量溶劑,其足以形成含有5wt%至28wt%最終PAN聚合物、較佳地15wt%至25wt%最終PAN聚合物之溶液。
受控/活性自由基聚合方法使得能夠控制聚合物構造。此包含分子量、分子量分佈(亦即聚合度分佈性)、功能性及組成。上述RAFT劑在AN單體至PAN之受控/活性自由基聚合期間用作鏈轉移劑。
RAFT聚合機制具有4個反應步驟:引發、加成-斷裂、再引發及平衡,如下文使用(作為實例)CPDTC作為RAFT劑所圖解說明。在PAN聚合期間,使用偶氮-雙異丁腈(AIBN)作為起始劑且使用DMSO作為溶劑。
藉由AIBN引發聚合。其分解以形成兩個自由基(方程式1)且然後該等自由基開始與AN單體進行反應以引發聚合(方程式2)。更多單體(AN)與自由基進行反應且形成活性聚合物或聚合自由基Pn.(方程式
3)。CPDTC(作為RAFT劑)與Pn.反應或加合以形成RAFT加合物自由基。此RAFT加合物自由基可在任一方向引起斷裂反應以得到起始物質或新自由基及聚合RAFT-Pn(方程式4)。此係不可逆步驟。在反應方程式5中,新形成自由基再引發聚合物生長以得到另一活性聚合物或聚合自由基Pm.。此活性聚合物Pm.與聚合RAFT-Pn反應形成RAFT加合物自由基中間體(方程式6)。此中間體可在任一方向斷裂以控制具有同等Pn.或Pm.生長機會及窄PDI之鏈。在所有單體及共單體皆消耗時,聚合將結束。
藉由上述方法所產生PAN聚合物之分子量可在60kg/莫耳至500kg/莫耳、較佳地90kg/莫耳至250kg/莫耳及最佳地115kg/莫耳至180kg/莫耳之範圍內,且PDI為約2或更小。藉由Viscotek GPCmax凝膠滲透層析(GPC)系統量測分子量。在表徵期間,使用含有0.02M LiBr之DMF(二甲基甲醯胺)作為流動相且流速為1ml/min。且將管柱溫度設定為45℃。
上述低PDI PAN聚合物適用於濕式紡絲及氣隙紡絲(或另一選擇為「乾噴濕式紡絲」)以製備連續碳纖維前體(亦即白纖維)。已發現,低PDI PAN聚合物具有良好紡絲能力;亦即易於自該等聚合物藉由紡絲製程製備纖維。根據ASTM 2256,自該等聚合物產生之所得纖維前體展示橫截面均勻性、韌度>5g/丹尼爾(denier)且起始模數>125g/丹尼爾。
為製備PAN白纖維,在藉由真空去除氣泡之後,對PAN聚合物溶液(亦即紡絲「濃液」)實施習用濕式紡絲及/或氣隙紡絲。基於溶液之總重量,紡絲「濃液」之聚合物濃度可在5重量%-28重量%、較佳地15wt%至25wt%之範圍內。在濕式紡絲中,過濾濃液且經由噴絲板(由金屬製得)孔擠出至用於聚合物之液體凝結浴中以形成長絲。噴絲
板孔決定PAN纖維之期望長絲計數(例如對於3K碳纖維而言3,000個孔)。在氣隙紡絲中,在噴絲板與凝結浴之間提供1mm至50mm、較佳地2mm至15mm之垂直氣隙。在此紡絲方法中,過濾聚合物溶液且自噴絲板在空氣中擠出,且然後在凝結浴中凝結所擠出長絲。製程中所使用之凝結液體係溶劑及非溶劑之混合物。通常使用水或醇作為非溶劑。使用溶劑與非溶劑之比率及浴溫度來調節凝結中所擠出初生長絲之固化速率。
然後自凝結浴藉由輥汲取紡絲長絲通過洗滌浴以去除過量凝結劑且在熱(例如40℃至100℃)水浴中拉伸以賦予長絲分子定向,此係作為控制纖維直徑之第一步驟。然後乾燥(例如在乾燥輥上)經拉伸長絲。乾燥輥可由複數個串聯且以蛇形構形配置之可旋轉輥構成,長絲自輥至輥且在足以在輥上向長絲提供拉伸或鬆弛之張力下依序通過乾燥輥上方。藉助在內部或穿過輥循環之增壓蒸汽或藉由輥內側之電加熱元件加熱至少一些輥。可在乾燥之前向經拉伸纖維施加紡絲油劑以防止長絲在下游製程中彼此黏附。
作為控制纖維直徑之第二步驟,在第一纖維抽拉後進行超拉伸。在高於纖維之玻璃轉變溫度100℃至185℃、較佳地135℃至175℃之溫度下實施此超拉伸製程。該拉伸進一步將分子定向成長絲。超拉伸纖維可具有約0.4丹尼爾至1.5丹尼爾、較佳地0.5-1.0丹尼爾之直徑。
與處理條件(包含紡絲溶液及凝結浴之組成、總拉伸量、溫度及長絲速度)相關聯以提供具有期望結構及丹尼爾之長絲。在超拉伸步驟後,纖維長絲可通過一或多個熱輥上方且然後纏繞於線軸上。
為將PAN白纖維轉化成碳纖維,對PAN纖維實施氧化及碳化。
在氧化階段期間,將PAN纖維在張力下供給穿過一或多個經供給經加熱空氣之特定烘箱。氧化烘箱溫度可介於200℃至300℃、較佳地
220℃至285℃之間。氧化製程組合來自空氣之氧分子與PAN纖維且使得聚合物鏈開始交聯,由此將纖維密度增加至1.3g/cm3至1.4g/cm3。在氧化製程中,施加至纖維之張力通常係控制纖維以0.8至1.35、較佳地1.0至1.2之拉伸比率來抽拉或收縮。在拉伸比率為1時,並無拉伸。另外,在拉伸比率大於1時,所施加張力導致纖維被拉伸。該經氧化PAN纖維具有不熔性梯狀芳族分子結構且其備用於碳化處理。
碳化發生於一或多個特定設計之爐內側之惰性(無氧)氛圍中。在一較佳實施例中,使經氧化纖維通過預碳化爐,其中使纖維經受約300℃至900℃、較佳地350℃至750℃之加熱溫度,同時暴露於惰性氣體(例如氮),隨後藉由使纖維通過經加熱至約700℃至1650℃、較佳地800℃至1450℃之較高溫度之爐來實施碳化,同時暴露於惰性氣體。在整個預碳化及碳化製程中應進行纖維張力調整。在預碳化中,所施加纖維張力應足以控制拉伸比率在0.9至1.2、較佳地1.0至1.15之範圍內。在碳化中,所使用張力應足以提供0.9至1.05之拉伸比率。碳化使得碳分子發生結晶且由此產生具有大於90%之碳含量之最終碳纖維。
基質樹脂與碳纖維之間之黏附係碳纖維增強之聚合物複合物的重要標準。因此,在碳纖維製造期間,可在氧化及碳化之後實施表面處理以增強此黏附。
表面處理可包含牽引碳化纖維穿過含有電解質(例如碳酸氫銨或次氯酸鈉)之電解浴。電解浴之化學物質蝕刻或粗糙化纖維表面,由此增加可用於界面纖維/基質鍵結之表面積且增加反應性化學基團。
接下來,可對碳纖維實施上漿,其中將上漿塗層(例如基於環氧樹脂之塗層)施加於纖維上。可藉由使纖維通過含有液體塗層材料之上漿浴實施上漿。在處置及處理成中間體形式(例如乾織物及預浸體)期間,上漿會保護碳纖維。上漿亦將長絲一起保持於個別纖維束中以
減小絨毛,改良可處理性且增加纖維與基質樹脂之間之界面剪切強度。
在上漿後,將塗覆碳纖維乾燥且然後纏繞於線軸上。
根據ASTM D4018測試方法,發現自上述低PDI PAN聚合物闡述之碳纖維具有下列機械性質:拉伸強度大於700Ksi(4826MPa)且拉伸起始模數大於35Msi(241GPa)。
藉由下列實例進一步闡釋上述PAN聚合物及自其產生之碳纖維之益處及性質。
根據表1A-1C中所展示用於PAN聚合之調配物來製備PAN聚合物。
在上述表中,CPDTC、CPBZ、BDSTD係RAFT劑,其中:CPDTC=三硫代碳酸2-氰基-2-丙基酯十二烷基酯
CPBZ=二硫代苯甲酸2-氰基-2-丙基酯
BDSTD=雙-十二烷基硫基硫代羰基二硫醚
注意:*藉由基於單體總量之莫耳%使用RAFT劑。
如下所述來實施受控/活性自由基PAN聚合:使用偶氮-雙異丁腈(AIBN)作為起始劑/觸媒且使用DMSO作為溶劑。使用RAFT劑作為鏈轉移劑。在聚合期間,實施下列步驟序列:a)自DMSO儲存罐將DMSO計量至反應器中,然後自AN儲存罐將AN計量至反應器中;b)使用氮吹掃反應器;c)預加熱反應器且向高於室溫(25℃)之反應器中添加共單體及RAFT劑;d)加熱反應器且然後在40-85℃之期望溫度點添加起始劑/觸媒;e)在60-80℃之溫度下開始聚合15-23小時之時間;f)冷卻至低溫(40-50℃)且排放聚合物溶液。
在聚合後,量測所產生PAN聚合物之分子量及PDI且結果展示於表2A-2C中。
使用凝膠滲透層析(GPC)分析所得PAN聚合物之分子量及聚合度
分佈性指數(PDI)。使用具有低角度及正角度光散射檢測器及RI檢測器之Viscotek GPCmax/SEC層析系統。收集數據且使用Viscotek OMNISEC 4.06版軟體分析絕對重量平均分子量(Mw)及其分佈測定。
自含有RAFT劑之調配物產生之所有PAN聚合物皆得到PDI(Mw/Mn)為約2或更小之PAN聚合物。在相對於調配物5調節RAFT劑之劑量及溶液濃度之後,自調配物6產生之PAN聚合物具有217778g/莫耳之較高分子量(Mw)且PDI為1.69。
使用自調配物5(如實例1中所闡述)產生之PAN聚合物藉由濕式紡絲形成碳纖維前體(或白纖維)。使用自調配物12(如實例1中所闡述)產生之PAN聚合物藉由氣隙紡絲方法利用150μm噴絲板形成白纖維。
如下所述來測定白纖維之性質。
將白纖維束試樣浸沒於丙烯酸樹脂中且然後固化。在研磨機上使用不同等級砂紙將經固化纖維樹脂棒拋光以達成平滑橫截面。然後,在光學顯微鏡下使用影像分析系統量測纖維橫截面之橫截面均勻性。
對於氣隙紡絲而言,將離開凝結浴之纖維試樣在-60℃下凍乾且藉由汞孔隙度儀測試凍乾試樣之孔隙率及多孔結構分析。
根據ASTM D2256方法量測纖維韌度及起始模數。
發現基於調配物5及12之PAN聚合物具有良好紡絲能力。來自濕
潤及氣隙紡絲之所得白纖維前體亦具有良好韌度及模數,如自表3可看到。
圖1係凍乾凝結纖維之孔徑分佈之汞孔隙率測定。Y軸係log差異侵入(ml/g或dV/dlog D)。V係侵入試樣孔隙中之汞之體積。X軸係孔徑對數。因此,該圖展示侵入體積關於孔徑對數之導數。總體積或空隙曲線下面積。圖1展示藉由氣隙紡絲自低PDI PAN聚合物根據調配物12產生之凍乾PAN凝結纖維具有低微孔缺陷。圖2之顯微影像及圖3之變異性圖表展示,藉由氣隙紡絲進行紡絲之低PDI白纖維具有均勻橫截面。圖3係橫截面區域之變異性圖表,其展示分散或擴散。
在空氣中於220℃-285℃之溫度範圍內將白纖維前體氧化,且在氮中於350℃-650℃(預碳化)且然後800℃-1300℃之溫度範圍內進行碳化。
測定所得碳纖維之拉伸強度及拉伸模數且展示於表4中。
根據ASTM D4018測定碳纖維之拉伸強度及起始模數。將碳纖維首先浸漬於環氧樹脂浴中且然後固化。在MTS上以0.5in/min十字頭速度測試經固化碳纖維股之拉伸強度及模數。
藉由液體浸漬方法根據ASTM D3800測定纖維密度。
Claims (16)
- 一種合成具有窄分子量分佈之聚丙烯腈(PAN)聚合物之方法,該方法包括:a)組合丙烯腈(AN)單體與溶劑、至少一種共單體及硫代羰基硫基化合物以形成溶液;b)將該溶液加熱至高於25℃之溫度;及c)向該溶液中添加起始劑以發生聚合反應,其中藉由受控/活性自由基聚合來發生聚合,其中該硫代羰基硫基化合物用作可逆加成/斷裂鏈轉移(RAFT)劑,其中該硫代羰基硫基化合物係選自下列結構:
- 如請求項1之方法,其中該PAN聚合物之分子量在60kg/莫耳至500kg/莫耳之範圍內。
- 如請求項2之方法,其中該PAN聚合物之分子量在115kg/莫耳至180kg/莫耳之範圍內。
- 如請求項1之方法,其中該PAN聚合物具有1.2至1.9之PDI(Mw/Mn)(或1.2至1.7之替代PDI(Mz/Mw))。
- 如請求項1之方法,其中該溶劑係選自由以下組成之群:二甲基亞碸(DMSO)、二甲基甲醯胺(DMF)及二甲基乙醯胺(DMAc)、碳酸乙二酯(EC)、氯化鋅(ZnCl2)及水之混合物、及硫代氰酸鈉(NaSCN)及水之混合物。
- 如請求項1之方法,其中該至少一種共單體係選自由以下組成之群:基於乙烯基之酸、基於乙烯基之酯及乙烯基衍生物。
- 如請求項6之方法,其中該至少一種共單體係選自由以下組成之群:甲基丙烯酸(MAA)、丙烯酸(AA)、衣康酸(ITA)、甲基丙烯酸酯(MA)、甲基丙烯酸甲酯(MMA)、乙酸乙烯酯(VA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、甲基丙烯酸乙酯(EMA)、乙烯基咪唑(VIM)、丙烯醯胺(AAm)、二丙酮丙烯醯胺(DAAm)。
- 如請求項1之方法,其中該起始劑係偶氮化合物或有機過氧化物。
- 如請求項8之方法,其中該起始劑係選自由以下組成之群:偶氮雙異丁腈(AIBN)、偶氮雙氰基戊酸(ACVA)、2,2'-偶氮雙-(2,4-二甲基)戊腈(ABVN)、過氧化二月桂醯(LPO)、二第三丁基過氧化物(TBPO)、過氧化二碳酸二異丙酯(IPP)。
- 如請求項1之方法,其中步驟(b)中之溫度係在40℃至85℃之範圍內。
- 如請求項1之方法,其中該硫代羰基硫基化合物係選自:a)三硫代碳酸2-氰基-2-丙基酯十二烷基酯(CPDTC)
- 一種聚丙烯腈(PAN)聚合物,其係藉由如請求項1之方法產生。
- 一種產生碳纖維之方法,其包括:形成根據請求項1之方法產生之PAN聚合物之聚合物溶液;藉由濕式紡絲或氣隙紡絲對該聚合物溶液實施紡絲以形成PAN纖維前體;對該PAN纖維前體實施氧化;及對該經氧化纖維前體實施碳化,其中根據ASTM D4018測試方法,該碳纖維具有大於700ksi(或4826MPa)之拉伸強度及大於35msi(或241GPa)之起始模數。
- 如請求項13之方法,其中用於紡絲之PAN聚合物之該聚合物溶液之聚合物濃度基於該溶液之總重量係在5重量%至28重量%之範圍內。
- 如請求項13之方法,其中在200℃至300℃之溫度範圍內實施氧 化。
- 如請求項13之方法,其中碳化包含在惰性氣體中於300℃至900℃範圍內之較低第一溫度下實施預碳化,隨後在700℃至1650℃溫度範圍內之較高第二溫度下實施碳化,該第二溫度係高於該第一溫度。
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TWI832071B (zh) * | 2021-07-19 | 2024-02-11 | 臺灣塑膠工業股份有限公司 | 碳纖維的製造方法 |
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KR102322305B1 (ko) | 2021-11-05 |
JP6495326B2 (ja) | 2019-04-03 |
MX2016008340A (es) | 2016-12-15 |
CN110078860B (zh) | 2021-11-30 |
RU2647861C2 (ru) | 2018-03-21 |
US9957645B2 (en) | 2018-05-01 |
CA2934795A1 (en) | 2015-07-02 |
MY182047A (en) | 2021-01-18 |
TWI675853B (zh) | 2019-11-01 |
AU2014370386B2 (en) | 2018-07-19 |
CN106459229A (zh) | 2017-02-22 |
BR112016014668A2 (pt) | 2017-08-08 |
KR20160103013A (ko) | 2016-08-31 |
US20150174807A1 (en) | 2015-06-25 |
US20190153211A1 (en) | 2019-05-23 |
WO2015099913A1 (en) | 2015-07-02 |
US10189985B2 (en) | 2019-01-29 |
US10647844B2 (en) | 2020-05-12 |
EP3087107A1 (en) | 2016-11-02 |
CN110078860A (zh) | 2019-08-02 |
US20180207849A1 (en) | 2018-07-26 |
AU2014370386A1 (en) | 2016-06-30 |
RU2016129965A (ru) | 2018-01-30 |
CN106459229B (zh) | 2019-03-01 |
AU2014370386C1 (en) | 2021-11-18 |
JP2017503066A (ja) | 2017-01-26 |
CA2934795C (en) | 2021-09-21 |
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