CN109385043B - 一种基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料 - Google Patents
一种基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料 Download PDFInfo
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- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Reinforced Plastic Materials (AREA)
Abstract
本发明涉及高分子及复合材料领域,具体公开了一种基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料。以质量份计,所述复合材料是由100份螺旋环缩醛环氧树脂、5~100份固化剂、0~6份固化促进剂、0~30份环氧活性稀释剂、0~300份有机溶剂以及20~500份碳纤维制备得到。所述的基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料与传统环氧树脂/碳纤维复合材料相比,可以在十分温和的条件下去除粘接碳纤维的基体树脂,使得碳纤维能够被很好地回收,并能使回收后的碳纤维保持原有的优异性能。
Description
技术领域
本发明涉及高分子及复合材料领域,具体涉及一种基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料。
背景技术
碳纤维增强高分子复合材料,具有质轻、高模、高强等优点,在航天航空、风力发电、轻量化汽车、体育器材等领域具有广泛的应用。未来中国四大产业——大飞机项目、海上风力发电、汽车轻量化发展及高速铁路,无疑还将带动碳纤维需求的强势增长,然而飞机制件一般寿命为25-28年,风机叶片为20-25年,汽车制件为10-15年,这些产品寿命终结后,其回收再利用将成为非常重要的问题。
碳纤维复合材料回收方法可分为填埋、焚烧、粉碎、分离四种,目前虽然填埋是最便宜的处理选择,但由于碳纤维复合材料不能生物降解,填埋会对环境产生负面影响,因此最终将会被禁止使用,欧盟多数成员国2004年都颁布了法律,禁止复合材料的填埋处理;焚烧作为过去常用的处理方法,其回收方法及设备简单,投入成本少,通过焚烧可以获得能量,但焚烧过程中会释放有毒气体,造成二次污染;粉碎会破坏碳纤维的长度,影响二次使用;分离主要是把复合材料中的树脂与碳纤维分离,当前主要有高温裂解、微波热分解、亚超临界流体、电化学方法等,除了高温裂解方法已有工业化利用之外,其他都处理研究阶段,同时高温裂解的方法本身也需要大的能耗,同时碳纤维表面还会残留树脂或残碳,表面结构会被部分破坏。
现在的目标就是找到一种温和的处理方式,能够将价值比较高的碳纤维回收,不破坏其原有的优异性能。碳纤维复合材料难回收的主要原因是它使用的基体树脂是热固性高分子,在成型固化后,很难溶解或重新加工。赋予热固性树脂可降解性被认为是解决碳纤维复合材料回收问题的一条重要途径,因为树脂的可降解性,使碳纤维复合材料在相对比较温和的条件下就可以去除热固性基体树脂,从而使碳纤维得到回收,品质也能够得到保持。
当前报道用于可回收碳纤维复合材料的可降解热固性树脂主要有二硫醚键、缩醛结构、希夫碱结构等,然而这些可降解基团都存在稳定性差或柔性的问题,导致制得的复合材料的热稳定性、机械性能等不能跟传统热固性树脂基复合材料。
近年,IBM公司以及华南理工大学利用易酸解的六氢均三嗪结构得到了一类高化学交联度(高玻璃化转变温度Tg和模量)又可降解的热固性树脂,可制备高性能的可回收碳纤维复合材料,然而这些树脂固化会脱去小分子(固化收缩率大)、同时需使用高沸点溶剂(固化温度高)。如何获得可快速降解同时又具有优异综合性能的可降解热固性树脂从而实现碳纤维复合材料在温和条件下的回收是碳纤维复合材料的一个发展方向。
发明内容
本发明的目的在于提供了一种基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料,不仅可以在温和条件下回收碳纤维,还能保持碳纤维原有的优异性能。
一种基于螺旋环缩醛环氧树脂的可回收碳纤维复合材料,其特征在于,按质量份数计,由以下组分组成:
所述的螺旋环缩醛环氧树脂的结构式为:
其中R为H或甲氧基,n为0~10。
本发明螺旋环缩醛环氧树脂的可回收碳纤维复合材料中由螺旋环缩醛环氧树脂、固化剂和碳纤维固化而成,由于易降解的螺旋环缩醛结构在固化过程中被引入到了复合材料的树脂基体交联网络,使得复合材料在温和条件下就可以去除粘接碳纤维的基体树脂,使得碳纤维能够很好地得到回收,并使得回收后的碳纤维保持较高的质量。
作为优选,所述的可回收碳纤维复合材料按质量份数计,由以下组分组成:
作为优选,所述的可回收碳纤维复合材料按质量份数计,由以下组分组成:
上述方案中添加了固化促进剂,能大大缩短固化反应的时间,提高了制备复合材料的效率,在实际工业生产中具有极大的经济效益。
作为优选,所述的可回收碳纤维复合材料按质量份数计,由以下组分组成:
上述方案中添加了环氧活性稀释剂,其可以固化反应成为环氧树脂固化物交联网络结构的一部分,对固化产物的性能几乎无影响,还能增加固化体系的韧性。
所述的固化剂为胺类固化剂、酸酐类固化剂、酚醛树脂中的任意一种或多种,作为优选,所述的固化剂为二乙烯三胺、4,4′-二氨基二苯甲烷、4,4′-二氨基二苯砜、酰胺基胺、聚酰胺、聚醚胺、双氰胺、甲基六氢苯酐、衣康酸酐、桐油酸酐、酚醛树脂中的任意一种或多种。
所述的固化促进剂为叔胺、季胺盐、有机碱、路易斯酸中的任意一种或多种,作为优选,所述的固化促进剂为2-甲基咪唑、四丁基溴化铵、2,4,6-三(二甲胺基甲基)苯酚、三氟化硼(BF3)中的任意一种或多种。
所述环氧活性稀释剂为正丁基缩水甘油醚,烯丙基缩水甘油醚、5-乙基己基缩水甘油醚、苯乙烯氧化物、苯基缩水甘油醚、甲酚缩水甘油醚、对异丁基苯基缩水甘油醚、甲基丙烯酸缩水甘油酯、三级羧酸缩水甘油酯、二缩水甘油醚、聚乙醇二缩水甘油醚、聚丙二醇二缩水甘油醚、二缩水甘油基苯胺、三甲醇基丙烷三缩水甘油醚或丙三醇三缩水甘油醚中的任意一种或多种。
所述的有机溶剂为苯类、卤代烃类、醚类或醇类有机溶剂,作为优选,所述的有机溶剂为甲苯、二甲苯、三氯甲烷、二氯乙烷、四氢呋喃、乙醇中的任意一种或多种。
所述的碳纤维为短纤维、碳纤维单向布、碳纤维双向布或碳纤维毡。
相对于现有技术,本发明具有如下有益效果:
(1)本发明得到的可回收碳纤维复合材料可以在十分温和的条件下去除粘接碳纤维的基体树脂,使得碳纤维能够被很好地回收,并能使回收后的碳纤维保持原有的优异性能;
(2)本发明得到的可回收碳纤维复合材料,还可以在温和条件下得到分量相对小的基体树脂降解片段,其中活性基团很明确,是缩醛结构降解得到的醛基和醇羟基,方便后续对回收树脂基体进行再利用;
(3)本发明可回收碳纤维复合材料的制备可采用现在通用的碳纤维复合材料加工制备方法,可操作性强,可控性好,易于实施,有利于工业化大规模生产。
具体实施方式
下面通过实施例和对比例对本发明作进一步详细的描述,但本发明的实施方式不限于此。在以下实施例中,碳纤维单向布的单丝拉伸采用25mm的跨距,在5mm/min的拉伸速度下测得。
螺旋环缩醛环氧树脂的合成
将500g香草醛与224g季戊四醇按摩尔比2:1的量加入到三口烧瓶中,再加入1000gDMF,1000g石油醚和30g对甲苯磺酸,采用Dean-Stark装置进行分水回流反应12h,利用饱和碳酸氢钠水溶液沉降并水洗后得到螺旋环缩醛双酚A 560g。
再以200g双酚A和16g或8g环氧氯丙烷为原料(双酚与环氧氯丙烷的投料摩尔比为1:0.33,1:0.18),以400g二氧六环为溶剂,在2g四丁基溴化铵及20g 20%NaOH水溶液催化下,分别得到环氧值为0.071的螺旋环缩醛环氧树脂1,其结构式为:
和环氧值为0.039的螺旋环缩醛环氧树脂2,其结构式为:
以200g双酚1和800g环氧氯丙烷为原料(环氧氯丙烷过量并作为溶剂),在4g四丁基溴化铵及20g 30%NaOH水溶液催化下,得到环氧值为0.39的螺旋环缩醛环氧树脂3,其结构式为:
将500g对羟基苯甲醛与279g季戊四醇按摩尔比2:1的量加入到三口烧瓶中,再加入1000g DMF,1000g石油醚和30g对甲苯磺酸,采用Dean-Stark装置进行分水回流反应10h,利用饱和碳酸氢钠水溶液沉降并水洗后得到螺旋环缩醛双酚B 600g;
再以200g双酚B和850g环氧氯丙烷为原料(环氧氯丙烷过量并作为溶剂),在4g四丁基溴化铵及20g 30%NaOH水溶液催化下,得到环氧值为0.44的螺旋环缩醛环氧树脂4,其结构式为:
实施例1
将100g螺旋环缩醛环氧树脂3、80g甲基六氢苯酐、30g短碳纤维混合搅拌均匀后,在120℃下固化2小时,160℃下固化2小时,200℃下固化2小时,即得碳纤维复合材料。
将得到的碳纤维复合材料置于0.1M HCl水和乙醇(水:乙醇体积比为2:8)的混合溶液中,室温下3小时全部降解,洗涤后得到回收短碳纤维,外观与原始短碳纤维无区别。
实施例2
将100g螺旋环缩醛环氧树脂1、14g 4,4′-二氨基二苯甲烷、30g二缩水甘油醚和20g短碳纤维混合搅拌均匀后,在90℃下固化2小时,150℃下固化2小时,180℃下固化2小时,即得碳纤维复合材料。
将得到的碳纤维复合材料置于0.1M HCl水和丙酮(水:丙酮体积比为1:9)的混合溶液中,室温下3小时全部降解,洗涤后得到回收短碳纤维,外观与原始短碳纤维无区别。
实施例3
将100g螺旋环缩醛环氧树脂2、5g聚醚胺D230和300g甲苯混合搅拌均匀后,与50g碳纤维毡做成碳纤维毡预浸料,通过热压160℃下固化10小时,再在180℃下后固化2小时后,即得碳纤维复合材料。
将得到的碳纤维复合材料置于0.05M H2SO4水和四氢呋喃(水:四氢呋喃体积比为2:8)的混合溶液中,室温下5小时全部降解,洗涤后得到回收碳纤维毡,外观与原始碳纤维毡无区别。
实施例4
将100g螺旋环缩醛环氧树脂3、50g甲基六氢苯酐、桐油酸酐50g、四丁基溴化铵6g、100g二氯乙烷、60g四氢呋喃混合搅拌均匀后,与500g碳纤维单向布做成碳纤维预浸料,通过热压180℃下固化20min,再在180℃下后固化2小时,200℃下后固化2小时,即得碳纤维复合材料。
将得到的碳纤维复合材料置于0.1M HCl水和甲醇(水:甲醇体积比为0.5:9.5)的混合溶液中,50℃下1小时全部降解,洗涤后得到回收碳纤维单向布;回收得到的碳纤维单向布单丝拉伸强度为3.15GPa,原始碳纤维单丝拉伸为3.20GPa。
实施例5
将100g螺旋环缩醛环氧树脂4、30g酚醛树脂、20g聚酰胺(徐州中研科技工业有限公司提供)、2g 2,4,6-三(二甲胺基甲基)苯酚、1g 2-甲基咪唑、150g二甲苯、50g三氯甲烷和50g乙醇混合搅拌均匀后,与220g碳纤维双向平纹布做成碳纤维预浸料,通过热压180℃下固化20min,再在180℃下后固化2小时,200℃下后固化2小时,即得碳纤维复合材料。
将得到的碳纤维复合材料置于0.1M HCl水和四氢呋喃(水:四氢呋喃体积比为1:9)的混合溶液中,50℃下1小时全部降解,洗涤后得到回收碳纤维双向平纹布;回收得到的碳纤维双向平纹布单丝拉伸强度为3.18GPa,原始碳纤维单丝拉伸为3.20GPa。
对比例1
将100g双酚A型环氧树脂(E-44,巴陵石化提供)、30g酚醛树脂、20g聚酰胺(徐州中研科技工业有限公司提供)、2g 2,4,6-三(二甲胺基甲基)苯酚、1g 2-甲基咪唑、150g二甲苯、50g三氯甲烷和50g乙醇混合搅拌均匀后,与220g碳纤维双向平纹布做成碳纤维预浸料,通过热压180℃下固化20min,再在180℃下后固化2小时,200℃下后固化2小时,即得碳纤维复合材料。
将得到的碳纤维复合材料置于0.1M HCl水和四氢呋喃(水:甲醇体积比为1:9)的混合溶液中,50℃下30天无降解。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
5.根据权利要求1所述的基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料,其特征在于,所述的固化剂为胺类固化剂、酸酐类固化剂、酚醛树脂中的任意一种或多种。
6.根据权利要求1所述的基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料,其特征在于,所述的固化促进剂为叔胺、季铵盐、有机碱、路易斯酸中的任意一种或多种。
7.根据权利要求1所述的基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料,其特征在于,所述的环氧活性稀释剂为正丁基缩水甘油醚,烯丙基缩水甘油醚、5-乙基己基缩水甘油醚、苯乙烯氧化物、苯基缩水甘油醚、甲酚缩水甘油醚、对异丁基苯基缩水甘油醚、甲基丙烯酸缩水甘油酯、三级羧酸缩水甘油酯、二缩水甘油醚、聚乙醇二缩水甘油醚、聚丙二醇二缩水甘油醚、二缩水甘油基苯胺、三甲醇基丙烷三缩水甘油醚、丙三醇三缩水甘油醚的任意一种或多种。
8.根据权利要求1所述的基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料,其特征在于,所述的有机溶剂为甲苯、二甲苯、三氯甲烷、二氯乙烷、四氢呋喃、乙醇中的任意一种或多种。
9.根据权利要求1所述的基于螺旋环缩醛环氧树脂的易回收碳纤维复合材料,其特征在于,所述的碳纤维为短纤维、碳纤维单向布、碳纤维双向布或碳纤维毡。
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JPS58140090A (ja) * | 1982-02-16 | 1983-08-19 | Mitsubishi Petrochem Co Ltd | 新規なポリグリシジルエ−テルの製造方法 |
US4532308A (en) * | 1983-08-11 | 1985-07-30 | Mitsubishi Petrochemical Co., Ltd. | Epoxy resin composition |
JPS6041679A (ja) * | 1983-08-16 | 1985-03-05 | Mitsubishi Petrochem Co Ltd | ポリグリシジルエ−テルの製造方法 |
JPS61223019A (ja) * | 1985-03-29 | 1986-10-03 | Toray Ind Inc | 繊維強化用マトリツクス樹脂組成物 |
JPS61231021A (ja) * | 1985-04-05 | 1986-10-15 | Toray Ind Inc | エポキシ樹脂組成物 |
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