WO2014044146A1 - 一种高容量高分子聚合物储氢材料及其制备方法 - Google Patents

一种高容量高分子聚合物储氢材料及其制备方法 Download PDF

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WO2014044146A1
WO2014044146A1 PCT/CN2013/083371 CN2013083371W WO2014044146A1 WO 2014044146 A1 WO2014044146 A1 WO 2014044146A1 CN 2013083371 W CN2013083371 W CN 2013083371W WO 2014044146 A1 WO2014044146 A1 WO 2014044146A1
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hydrogen storage
polymer
storage material
capacity
hydrogen
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PCT/CN2013/083371
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French (fr)
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方章建
陈义龙
张岩丰
郑兴才
薛永杰
陶磊明
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武汉凯迪工程技术研究总院有限公司
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Priority to JP2015531450A priority Critical patent/JP6012872B2/ja
Priority to KR1020157008560A priority patent/KR101739498B1/ko
Priority to BR112015005969A priority patent/BR112015005969A2/zh
Priority to CA2885357A priority patent/CA2885357A1/en
Priority to AU2013317452A priority patent/AU2013317452B2/en
Priority to EP13839381.4A priority patent/EP2899156A4/en
Priority to RU2015114482/05A priority patent/RU2595667C1/ru
Publication of WO2014044146A1 publication Critical patent/WO2014044146A1/zh
Priority to US14/660,962 priority patent/US9234082B2/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C08G73/0226—Quaternisation of polyalkylene(poly)amines
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing 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
    • C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • 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
    • C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • 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
    • C08J2327/00—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 at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the invention relates to the field of polymer materials, hydrogen storage materials and energy, and in particular to a high-capacity polymer hydrogen storage material and a preparation method thereof.
  • hydrogen storage materials can be roughly divided into two categories: chemical adsorption materials and physical adsorption materials.
  • Chemical adsorption refers to the insertion of a hydrogen atom from a hydrogen molecule into a crystal lattice of a substrate or formation of a new compound.
  • the chemical adsorption material mainly includes a metal hydride material, a hydride material, an ammonia borane derivative, and the like.
  • Ammonia borane compound (NH3BH3, AB) is a new type of hydride hydrogen storage material that has received close attention in recent years. It has an ultra-high hydrogen density (19.6 Wt%), with both thermal stability and good chemical stability, is an excellent hydrogen storage material with great application prospects.
  • the preparation method mainly has the following two methods: a borane method and a sodium borohydride method.
  • the borane method directly uses borane as a boron source to react with liquid ammonia to form a product; as in patent CN102030313A, a composite ammonia borane hydrogen storage material is prepared by using ammonia borane and organic materials as raw materials at a lower hydrogen release temperature. The materials have low temperature hydrogen evolution characteristics.
  • the sodium borohydride process is generally prepared by the reaction of sodium borohydride with an amine compound.
  • the patent CN102180445A discloses a method for preparing a high-capacity hydrogen storage material, hydroboration p-/m-phenylenediamine, which can be NH3+ from p-m-phenylenediamine hydrochloride and borohydride.
  • the BH4-molar ratio 1:1 mixture is obtained by grinding or ball milling in an inert gas.
  • the existing ammonia borane derivatives have some problems that restrict their on-board hydrogen storage applications, including: the slow hydrogen release kinetics of such hydrogen storage materials under mild operating conditions, and the release of harmful impurity gases during hydrogen release. .
  • the technical problem to be solved by the present invention is to provide a high-capacity high-molecular polymer hydrogen storage material and a preparation method thereof, which have high hydrogen storage capacity and low hydrogen release temperature; and are transparent solid materials, which can form a transparent The film is easy to use.
  • the technical solution adopted by the present invention is:
  • a high-capacity high-molecular polymer hydrogen storage material characterized in that it comprises a linear polymer as a main chain and is aminated with a polyamine compound by a side chain and/or a terminal group thereof and then boron.
  • An ammonia borane derivative grafted onto its side chains and/or ends by a hydride reaction.
  • the linear polymer as the main chain includes, but is not limited to, polyvinyl chloride, polyvinyl chloride-polyethylene copolymer, polyethyleneimine, acrylate copolymer, polyacrylic acid, polystyrene. a styrene-acrylate copolymer, a polysiloxane or the like; a polyamine compound used for amination of a side chain and/or a terminal group of the polymer, including but not limited to: 1-methylindole, Bismuth, ethylenediamine, diethylenetriamine.
  • the linear polymer of the high-capacity polymer hydrogen storage material as a main chain has a molecular weight of 5,000 to 50,000; the ammonia borane derivative of the high-capacity polymer hydrogen storage material The content is in the range of 25-75 wt%.
  • the high-capacity high molecular polymer hydrogen storage material can be used in a film form after post-treatment into a film.
  • a method for preparing a high-capacity high-molecular polymer hydrogen storage material characterized in that it comprises the following steps:
  • the linear polymer as the main chain includes, but is not limited to, polyvinyl chloride, polyvinyl chloride-polyethylene copolymer, polyethyleneimine, acrylate copolymer, polyacrylic acid, polystyrene. , styrene-acrylate copolymer, polysiloxane, etc.;
  • the polyamine compound used for amination of the polymer polymer side chain and/or terminal group includes, but is not limited to, 1-methyl hydrazine, hydrazine, ethylene diamine, diethylene triamine, and the like.
  • the organic solvent includes, but is not limited to, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, etc.;
  • the borohydride is selected from sodium borohydride, lithium borohydride or potassium borohydride.
  • the step (1) is that the linear polymer is chemically modified in the side chain and/or the terminal which is pre-aminated, and then the polyamine compound is added for amination reaction to obtain an amine group. Functionalized polymer.
  • the method for preparing the high-capacity high-molecular polymer hydrogen storage material further comprises post-processing to obtain a film-like high-capacity high-molecular polymer hydrogen storage material.
  • the present invention bonds a polyamine compound to a side chain and/or a terminal of a polymer by chemically modifying a linear high molecular polymer to obtain a functionalized polymer containing an amine group, and finally by a suitable chemical reaction in the polymer.
  • the ammonia chain borane derivative is formed at the side chain and/or the end, and the obtained high-capacity high-molecular polymer hydrogen storage material can adjust the hydrogen storage capacity by selecting different polymers, and at the same time effectively reduce the temperature of the heat liberation hydrogen (60). °C-250 ° C, preferably 90-160 ° C), and effectively inhibit the generation of harmful gas impurities such as borazine, diborane, ammonia.
  • the film forming performance is good, and can be processed to form a transparent film form for use, thereby avoiding the problem that the hydrogen storage of the existing hydrogen storage material may be uncontrollable due to uneven heating. If it is applied to the field of automotive hydrogen energy storage, by applying it to components such as heat sinks of automobiles, it will release hydrogen energy evenly by heat, and better control the hydrogen release performance of the hydrogen storage material.
  • the high-capacity polymer hydrogen storage material prepared by the surface modification of the polymer and the high-capacity aminoborane derivative bonded on the polymerization surface has the following advantages: (1) the hydrogen storage capacity is high and can be Adjustment, low hydrogen release temperature, no harmful impurity gas generated during hydrogen release; (2) is a solid flexible material with good film forming properties, which can be post-processed to form a film for use, avoiding existing hydrogen storage materials The problem of uncontrollable hydrogen release due to uneven heating; (3) The preparation process is simple, the cost is moderate, and there is a good prospect of large-scale industrial production.
  • Example 1 is a synthetic route diagram of a hydrogen storage material polymer c in Example 1;
  • Example 2 is a synthetic route diagram of a hydrogen storage material polymer d in Example 2;
  • Figure 4 is a temperature-programming drawing of the hydrogen storage material polymer d
  • Figure 5 is the effect of Wilkinson catalyst on the hydrogen evolution kinetics of hydrogen storage material polymer d; in the figure: "! Indicates that the Wilkinson catalyst is added; “-" means that no Wilkinson catalyst is added;
  • FIG. 6 is a process flow diagram of a method for preparing a hydrogen storage material polymer h in Embodiment 3;
  • Example 7 is a synthetic route diagram of a hydrogen storage material polymer e in Example 3.
  • Figure 8 is another high capacity polymer hydrogen storage material prepared in Examples 5-7.
  • polymer a (polyacrylic acid, molecular weight 5000) was added to ice-cold dichloromethane, then an excess of thionyl chloride was added, and the reaction was stirred at 0 ° C for 1 h, then the solvent was dried, and then dried. Methyl chloride is dissolved, and then added hydrazine and triethylamine to the above solution and reacted at 0 ° C for 2 hours, then the solution is spun dry, washed three times with deionized water and dried to obtain polymer b;
  • the aminated polymer b and sodium borohydride were stirred at a stoichiometric ratio in a tetrahydrofuran suspension at 25 ° C for 12 h, and the lower organic phase was collected by filtration, and the solvent was evaporated under reduced pressure.
  • the ratio of the c-borane derivative in c to the entire polymer was 57% by weight.
  • the hydrogen storage material polymer c was subjected to a hydrogen discharge performance test, and it was found that the hydrogen evolution temperature of the polymer c was about 105 ° C, and about 6.2 wt% of pure hydrogen was released at 105 ° C.
  • a polyvinyl chloride-polyethylene copolymer m (having a molecular weight of 50,000, wherein the degree of polymerization of the polyvinyl chloride monomer n is 750) is added to dry dichloromethane to dissolve it, and then 1-methyl hydrazine is added. After adding triethylamine to the above solution at 20 ° C for 12 hours, the solution was spun dry, washed three times with deionized water and dried to obtain polymer n.
  • the amine group-containing polymer n and sodium borohydride are stoichiometrically in a tetrahydrofuran suspension at 20 ° C After stirring for 8 hours, the lower organic phase was collected by filtration, the solvent was evaporated under reduced pressure, and the mixture was washed twice with diethyl ether to obtain a hydrogen storage material polymer d.
  • the ammonia borane derivative in polymer d constitutes 75% by weight of the entire polymer material.
  • the hydrogen storage material polymer d is subjected to hydrogen discharge performance test, and FIG. 3 and FIG. 4 respectively show the hydrogen evolution kinetic curve and the temperature programmed release of the polymer hydrogen storage material. It can be seen from the figure that the hydrogen storage material polymer d has a lower initial hydrogen evolution temperature (about 50 ° C), and as the temperature increases, the hydrogen evolution reaction proceeds in a step, and the hydrogen discharge peak temperature is 100 ° C. The amount of hydrogen released is about 8 wt%. And no harmful gas substances are produced during the entire hydrogen release process.
  • polymer j (molecular weight 16000) was added to ice-cold dichloromethane, then excess thionyl chloride was added, and the reaction was stirred at 0 ° C for 2 h, then the solvent was dried, then dried dichloromethane was added. After dissolving, ethylenediamine and potassium carbonate were added to the above solution for 5 hours at 5 ° C, and the solution was spun dry, washed three times with deionized water and dried to obtain an aminated polymer k.
  • the aminated polymer k and sodium borohydride were stirred in a dimethyl sulfoxide suspension at 50 ° C for 6 h, and the lower organic phase was collected by filtration, and the solvent was evaporated under reduced pressure.
  • the ratio of the ammonia borane derivative to the entire polymer in the obtained polymer was 39.6 wt%.
  • the hydrogen storage peak of the hydrogen storage material polymer h is 110 ° C, and about 3.8 wt% of pure hydrogen can be released at 110 ° C. And no harmful impurity gas is generated during the hydrogen release process.
  • polyethyleneimine (molecular weight 5000) is first added to acetonitrile, then stoichiometric bromoethanol is added, and the reaction is stirred for 24 hours at 80 ° C. The precipitate is filtered, washed with water, dried, and then dried. The polymer was dissolved in anhydrous dichloromethane, reacted with 1.5 equivalents of methylsulfonyl chloride and triethylamine for 2 hours, then the solvent was evaporated, extracted with dichloromethane, dried, and then reacted with hydrazine and triethylamine at 25 ° C. After overnight filtration and washing with water, an amine-functionalized polymer was obtained.
  • aminated polymer and potassium borohydride were stirred at a concentration of 50 ° C for 6 hours in a dimethyl sulfoxide suspension, followed by filtration.
  • the lower organic phase was distilled off under reduced pressure, and finally washed twice with diethyl ether to give a synthetic polymer hydrogen storage material e.
  • the high molecular hydrogen storage material e has a hydrogen evolution peak temperature of 115 ° C, and about 6.7 wt% of pure hydrogen can be released at 110 ° C. And no harmful impurity gas is generated during the hydrogen release process.
  • the polymer a (polyacrylic acid, molecular weight 20000) was used as a raw material, and ethyleneamine was used as a polymer a side chain group to bond a polyamine compound to carry out an amine.
  • the base material is then further prepared with sodium borohydride to obtain a hydrogen storage material polymer f, as shown in FIG.
  • the hydrogen storage material polymer f has a hydrogen evolution peak temperature of 109 ° C, and approximately 4.6 wt% of pure hydrogen can be released at 115 ° C. And no harmful impurity gas is generated during the hydrogen release process.
  • a polyvinylamine (molecular weight of 50,000) is used as a raw material, and a diamine triamine is used as a polyvinyl chloride side chain group to bond a polyamine compound for amination. Then, a hydrogen storage material polymer g is further prepared with sodium borohydride, as shown in FIG.
  • the hydrogen storage material polymer g has a hydrogen evolution peak temperature of 103 ° C, and about 7.8 wt% of pure hydrogen can be released at 110 ° C. And no harmful impurity gas is generated during the hydrogen release process.
  • the hydrogen storage material polymer i can be used for film formation on the surface of an automobile exhaust sheet by a film forming method.
  • the hydrogen storage material polymer i has a hydrogen evolution peak temperature of 116 ° C, and about 2.8 wt% of pure hydrogen can be released at 120 ° C. And no harmful impurity gas is generated during the hydrogen release process.

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Abstract

提供一种高容量高分子聚合物储氢材料，包括作为主链的线形高分子聚合物，和由其侧链和/或末端基团经多胺类化合物胺基化后再与硼氢化物反应而接枝于其侧链和/或末端上的氨硼烷衍生物。还提供一种高容量高分子聚合物储氢材料的制备方法。

Description

一种高容量高分子聚合物储氢材料及其制备方法 技术领域
本发明涉及高分子材料、储氢材料及能源领域，具体的是指一种高容量高分子聚合物储氢材料及其制备方法。
背景技术
工业革命开启了人类走向现代化的进程。一个多世纪以来，人类社会快速发展，能源一直是强大的推动力。为了人类的可持续发展，寻找一种可再生、具高燃烧值、易于利用又不污染环境的新型燃料已迫在眉睫。氢能具有环境友好、资源丰富、热值高、燃烧性能好等特点，是未来最有发展前景的绿色能源之一，但氢气的安全高效储存问题一直是制约氢能开发和利用的瓶颈。目前利用氢与材料的相互作用发展起来的储氢方法由于其储氢能量密度高、安全性好而备受世人关注。储氢材料与此也已成为国际上高度关注的研究领域之一。高容量储氢材料的发展是解决人类未来能源的关键，对于氢能的规模化利用具有巨大的推动作用。
根据吸附氢气作用力的不同，储氢材料可大体分为两类：化学吸附材料和物理吸附材料。化学吸附是指氢分子解离后的氢原子插入底物的晶格或者形成新化合物。化学吸附材料主要包括金属氢化物材料、氢化物材料、氨硼烷衍生物等。氨硼烷化合物（NH3BH3, AB）是近年来受到密切关注的一种新型氢化物储氢材料。它具有超高氢密度（19.6 wt%），并兼具热稳定性适中和化学稳定性良好等优点，是一种极具应用前景的优良储氢材料。其制备方法主要有下述两种方式：硼烷法和硼氢化钠法。硼烷法是用硼烷作为硼源与液氨反应直接生成产物；如专利CN102030313A以氨硼烷与有机物为原料，在较低的放氢温度下制备一种复合氨硼烷储氢材料，这种材料具有低温的放氢特性。硼氢化钠法一般通过硼氢化钠和胺类化合物反应制得。如专利CN102180445A公开了一种高容量储氢材料硼氢化对/间苯二胺的制备方法，该物质可由对/间苯二胺盐酸盐与硼氢化物以NH3+ : BH4-摩尔比1:1混合物在惰性气体中研磨或球磨制得。目前，现有氨硼烷衍生物多存在一些制约其车载储氢应用的问题，主要包括：这类储氢材料在温和操作条件下放氢动力学缓慢，而且放氢过程中伴随有害杂质气体的释放。此外其在应用中往往会出现受热不均匀的问题。
 技术问题
本发明所要解决的技术问题是提供一种高容量高分子聚合物储氢材料及其制备方法，其具有高的储氢容量和低的放氢温度等特性；为固态柔性材料，可形成透明的薄膜，便于使用。
 技术解决方案
为解决上述技术问题，本发明采用的技术方案为：
一种高容量高分子聚合物储氢材料，其特征在于：它包括作为主链的线形高分子聚合物和由其侧链和/或末端基团经多胺类化合物胺基化后再和硼氢化物反应而接枝于其侧链和/或末端上的氨硼烷衍生物。
按上述方案，所述作为主链的线形高分子聚合物包括但不限于：聚氯乙烯、聚氯乙烯-聚乙烯共聚物、聚乙烯亚胺、丙烯酸酯类共聚物、聚丙烯酸、聚苯乙烯、苯乙烯-丙烯酸酯类共聚物、聚硅氧烷等；所述高分子聚合物侧链和/或末端基团胺基化所用的多胺类化合物包括但不限于：1-甲基胍、胍、乙二胺、二乙烯三胺。
按上述方案，所述高容量高分子聚合物储氢材料中作为主链的线形高分子聚合物的分子量为5000-50000；所述高容量高分子聚合物储氢材料中氨硼烷衍生物的含量在25-75wt%。
按上述方案，所述的高容量高分子聚合物储氢材料可经后处理成膜以膜状形式使用。
一种高容量高分子聚合物储氢材料的制备方法，其特征在于：它包括以下步骤：
（1）将线形高分子聚合物预进行胺基化的侧链和/或末端基团采用多胺类化合物进行胺基化反应得到含有胺基功能化的聚合物；
（2）将步骤（1）得到的胺基化聚合物和硼氢化物按化学计量比在有机溶剂悬浮液中在5-50℃下搅拌1-12h后过滤收集下层有机相，减压蒸馏除去溶剂，洗涤得到本发明所述的高容量高分子聚合物储氢材料。
按上述方案，所述作为主链的线形高分子聚合物包括但不限于：聚氯乙烯、聚氯乙烯-聚乙烯共聚物、聚乙烯亚胺、丙烯酸酯类共聚物、聚丙烯酸、聚苯乙烯、苯乙烯-丙烯酸酯类共聚物、聚硅氧烷等；
所述高分子聚合物侧链和/或末端基团胺基化所用的多胺类化合物包括但不限于：1-甲基胍、胍、乙二胺、二乙烯三胺等。
按上述方案，所述的有机溶剂包括但不限于四氢呋喃、乙腈、二甲基亚砜等；所述的硼氢化物选自硼氢化钠、硼氢化锂或硼氢化钾。
按上述方案，所述的步骤（1）为将线形高分子聚合物在预进行胺基化的侧链和/或末端经化学修饰后再加入多胺类化合物进行胺化反应，得到含有胺基功能化的聚合物。
按上述方案，所述的高容量高分子聚合物储氢材料的制备方法还包括将其进行后处理以得到膜状高容量高分子聚合物储氢材料。
本发明通过对线性高分子聚合物进行化学修饰而将多胺类化合物键连到聚合物的侧链和/或末端，得到含有胺基的功能化聚合物，最后通过合适的化学反应在聚合物侧链和/或末端形成氨硼烷衍生物，而得到的新型高容量高分子聚合物储氢材料可通过选择不同的聚合物，调节其储氢容量，同时有效降低其热解放氢温度（60 ℃-250℃，优选为90-160℃），并有效抑制硼嗪、乙硼烷、氨气等有害气体杂质的产生。在放氢过程中通过加入Wilkinson催化剂，还可提高其放氢量，改善放氢性能。另，其作为一种固态柔性材料，成膜性能好，可经处理形成透明的薄膜形式以进行使用，避免了现有储氢材料因受热不均而可能导致的氢气释放不可控的问题。如将其应用于汽车氢能储放领域，通过将其涂覆在汽车的散热片等部件，其则会经均匀受热释放氢能，而较好地控制该储氢材料的放氢性能。
 有益效果
本发明通过对聚合物进行表面改性，在聚合表面键连高容量的氨硼烷衍生物而制备得到的高容量高分子聚合物储氢材料具有以下优点：（1）储氢容量高且可调节，放氢温度低，在放氢过程中无有害杂质气体产生；（2）是一种固态柔性材料，成膜性能好，可经后处理形成薄膜以进行使用，避免了现有储氢材料因受热不均而可能导致的氢气释放不可控的问题；（3）制备工艺简单，成本适中，有大规模工业化生产的良好前景。
 附图说明
图1为实施例1中储氢材料聚合物c的合成路线图；
图2为实施例2中储氢材料聚合物d的合成路线图；
图3为储氢材料聚合物d的的放氢动力学曲线；
图4为储氢材料聚合物d的程序升温脱附图；
图5为Wilkinson催化剂对储氢材料聚合物d的放氢动力学的影响；图中：“…” 表示加入Wilkinson催化剂；“—” 表示不加入Wilkinson催化剂；
图6为实施例3中储氢材料聚合物h的制备方法工艺流程图；
图7为实施例3中储氢材料聚合物e的合成路线图；
图8为实施例5-7中制备的其他高容量高分子聚合物储氢材料。
 本发明的实施方式
为了更好地解释本发明，以下结合附图和具体实施例进一步阐明本发明的主要内容，但本发明的内容不仅仅局限于以下实施例。
实施例1：储氢材料聚合物 c的合成
参考图1，将聚合物a（聚丙烯酸，分子量5000）加入到冰冷的二氯甲烷中，然后加入过量的二氯亚砜，0℃下搅拌反应1h后旋干溶剂，然后加入干燥过的二氯甲烷将其溶解，再将胍、三乙胺加入到上述溶液中在0℃反应2小时后，旋干溶液，去离子水洗涤三次后干燥得到聚合物b；
将胺基化的聚合物b和硼氢化钠按化学计量比在四氢呋喃悬浮液中25℃搅拌12h后过滤收集下层有机相，减压蒸馏除去溶剂，最后用乙醚洗涤两次得到产物，所得聚合物c中氨硼烷衍生物占整个聚合物的比例为57wt%。
将该储氢材料聚合物c进行放氢性能测试，得：该聚合物c放氢温度大约为105℃，在105℃大约可以放出6.2wt%的纯氢。
 本发明的实施方式
实施例2：聚合物d储氢材料的合成
参考图2，将聚氯乙烯-聚乙烯共聚物m（分子量为50000，其中聚氯乙烯单体的聚合度n为750）加入到干燥的二氯甲烷将其溶解，再将1-甲基胍、三乙胺加入到上述溶液中20℃反应12小时后，旋干溶液，去离子水洗涤三次后干燥得到聚合物n。
将含胺基的聚合物n和硼氢化钠按化学计量比在四氢呋喃悬浮液中20℃ 搅拌8h后过滤收集下层有机相，减压蒸馏除去溶剂，最后用乙醚洗涤两次得到储氢材料聚合物d。聚合物d中氨硼烷衍生物占整个聚合物材料的75wt%。
将所述储氢材料聚合物d进行放氢性能测试，图3和图4分别为该聚合物储氢材料的放氢动力学曲线和程序升温脱附图。由图可以看出，该储氢材料聚合物d具有较低的起始放氢温度（约50℃），随着温度升高，放氢反应近以一步进行，放氢峰温为100℃，放氢量为8wt%左右。且在整个放氢过程中没有任何有害气体物质产生。
另，在放氢过程中加入Wilkinson催化剂进行放氢性能的测试，作为比较试验，见图5。从图5可以看出，加入Wilkinson催化剂后，聚合物储氢材料的放氢性能得到明显改善。
 本发明的实施方式
实施例3：聚合物h储氢材料的合成
参考图6，将聚合物j（分子量为16000）加入到冰冷的二氯甲烷中，然后加入过量的二氯亚砜，0℃搅拌反应2h后旋干溶剂，然后加入干燥的二氯甲烷将其溶解，再将乙二胺、碳酸钾加入到上述溶液中5℃反应2小时后，旋干溶液，去离子水洗涤三次后干燥得到胺基化的聚合物k。
将胺基化的聚合物k和硼氢化钠按计量比在二甲基亚砜悬浮液中在50℃下搅拌6h后过滤收集下层有机相，减压蒸馏除去溶剂，最后用乙醚洗涤两次得到产物，所得聚合物中氨硼烷衍生物占整个聚合物的比例为39.6wt%。
经测试，该储氢材料聚合物h的放氢峰温为110℃，在110℃大约可以放出3.8wt%的纯氢。且在放氢过程中没有有害杂质气体的产生。
 本发明的实施方式
实施例4
参考图7，先将聚乙烯亚胺（分子量5000）加入到乙腈中，然后加入化学计量比的溴乙醇，碳酸钾80℃下搅拌反应24h后将沉淀过滤、水洗、干燥，然后将干燥后的聚合物溶解在无水二氯甲烷中，加入1.5当量的甲基磺酰氯、三乙胺反应2小时后旋干溶剂，二氯甲烷萃取、干燥后再加入胍、三乙胺在25℃下反应过夜后过滤、水洗后得到胺基功能化的聚合物，最后将得到的胺基化的聚合物和硼氢化钾按计量比在二甲基亚砜悬浮液中在50℃下搅拌6h后过滤收集下层有机相，减压蒸馏除去溶剂，最后用乙醚洗涤两次得到合成的聚合物储氢材料e。
该高分子聚合物储氢材料e的放氢峰温为115℃，在110℃大约可以放出6.7wt%的纯氢。且在放氢过程中没有有害杂质气体的产生。
 本发明的实施方式
实施例5
参考实施例1中储氢材料聚合物c的合成方法，以聚合物a（聚丙烯酸，分子量20000）为原料，采用乙二胺做聚合物a侧链基团键连用多胺类化合物以进行胺基化，然后和硼氢化钠进一步制备得到储氢材料聚合物f，见图8。
该储氢材料聚合物f的放氢峰温为109℃，在115℃大约可以放出4.6wt%的纯氢。且在放氢过程中没有有害杂质气体的产生。
 本发明的实施方式
实施例6
参考实施例2中储氢材料聚合物d的合成方法，以聚氯乙烯（分子量50000）为原料，采用二乙烯三胺做聚氯乙烯侧链基团键连用多胺类化合物以进行胺基化，然后和硼氢化钠进一步制备得到储氢材料聚合物g，见图8。
储氢材料聚合物g的放氢峰温为103℃，在110℃大约可以放出7.8wt%的纯氢。且在放氢过程中没有有害杂质气体的产生。
 本发明的实施方式
实施例7
将聚对溴苯乙烯-聚丙烯酸丁酯（分子量为30000，其中溴苯乙烯单体的聚合度n为100）溶解在二氧六环中，然后按计量比将乙二胺、碳酸钾加入到上述溶液中回流反应12小时后，旋干溶液，去离子水洗涤三次后干燥得到含胺基的聚合物；将含胺基的聚合物和硼氢化钠按化学计量比在四氢呋喃悬浮液中室温搅拌8h后过滤收集下层有机相，减压蒸馏除去溶剂最后用乙醚洗涤两次得到储氢材料聚合物i，见图8，所得聚合物中氨硼烷衍生物占整个聚合物的比例为25wt%。
该储氢材料聚合物i可以通过涂覆成膜的方法在汽车尾气片表面成膜使用。
该储氢材料聚合物i的放氢峰温为116℃，在120℃大约可以放出2.8wt%的纯氢。且在放氢过程中没有有害杂质气体的产生。

Claims (9)

1、一种高容量高分子聚合物储氢材料，其特征在于：它包括作为主链的线形高分子聚合物和由其侧链和/或末端基团经多胺类化合物胺基化后再和硼氢化物反应而接枝于其侧链和/或末端上的氨硼烷衍生物。
2、根据权利要求所述的高容量高分子聚合物储氢材料，其特征在于：所述作为主链的线形高分子聚合物包括但不限于：聚氯乙烯、聚氯乙烯-聚乙烯共聚物、聚乙烯亚胺、丙烯酸酯类共聚物、聚丙烯酸、聚苯乙烯、苯乙烯-丙烯酸酯类共聚物、聚硅氧烷； 所述高分子聚合物侧链和/或末端基团胺基化所用的多胺类化合物包括但不限于：1-甲基胍、胍、乙二胺、二乙烯三胺。
3、根据权利要求所述的高容量高分子聚合物储氢材料，其特征在于：所述高容量高分子聚合物储氢材料中作为主链的线形高分子聚合物的分子量为5000-50000；所述高容量高分子聚合物储氢材料中氨硼烷衍生物的含量在25-75wt%。
4、根据权利要求所述的高容量高分子聚合物储氢材料，其特征在于：所述的高容量高分子聚合物储氢材料可经后处理成膜以膜状形式使用。
5、一种高容量高分子聚合物储氢材料的制备方法，其特征在于：它包括以下步骤：
（1）将线形高分子聚合物预进行胺基化的侧链和/或末端基团采用多胺类化合物进行胺基化反应得到含有胺基功能化的聚合物；
（2）将步骤（1）得到的胺基化聚合物和硼氢化物按化学计量比在有机溶剂悬浮液中在5-50℃下搅拌1-12h后过滤收集下层有机相，减压蒸馏除去溶剂，洗涤得到本发明所述的高容量高分子聚合物储氢材料。
6、根据权利要求5所述的高容量高分子聚合物储氢材料的制备方法，其特征在于：所述作为主链的线形高分子聚合物包括但不限于：聚氯乙烯、聚氯乙烯-聚乙烯共聚物、聚乙烯亚胺、丙烯酸酯类共聚物、聚丙烯酸、聚苯乙烯、苯乙烯-丙烯酸酯类共聚物、聚硅氧烷；
所述高分子聚合物侧链和/或末端基团胺基化所用的多胺类化合物包括但不限于：1-甲基胍、胍、乙二胺、二乙烯三胺。
7、根据权利要求5所述的高容量高分子聚合物储氢材料的制备方法，其特征在于：所述的有机溶剂包括但不限于四氢呋喃、乙腈、二甲基亚砜；所述的硼氢化物选自硼氢化钠、硼氢化锂或硼氢化钾。
8、根据权利要求5所述的高容量高分子聚合物储氢材料的制备方法，其特征在于：所述的步骤（1）为将线形高分子聚合物在预进行胺基化的侧链和/或末端经化学修饰后再加入多胺类化合物进行胺化反应，得到含有胺基功能化的聚合物。
9、根据权利要求5所述的高容量高分子聚合物储氢材料的制备方法，其特征在于：它还包括将其进行后处理以得到膜状高容量高分子聚合物储氢材料。
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CA2885357A1 (en) 2014-03-27
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EP2899156A4 (en) 2016-05-25
CN102838085A (zh) 2012-12-26
EP2899156A1 (en) 2015-07-29
US20150191573A1 (en) 2015-07-09
AU2013317452A1 (en) 2015-04-09
AU2013317452B2 (en) 2015-10-22
RU2595667C1 (ru) 2016-08-27
BR112015005969A2 (zh) 2019-11-05
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