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Synthesis, Characterization and Application of Benzoxazine Acrylic and Allylic Functional

作　者: BAKANGURA ERIGENE
导　师: 林晓丹
学　校: 华南理工大学
专　业: 材料学
关键词: 苯并恶嗪 benzoxazine poly allyl Polym exothermic 树脂聚丙烯残炭率 thermal temperature 残碳率烯丙基苯苯酚 properties phenolic epoxy curing monomer improved
分类号: TQ316.3
类　型: 硕士论文
年　份: 2013年
下　载: 8次
引　用: 0次
阅　读: 论文下载

内容摘要

本研究探讨了以丙烯酰胺与苯酚和甲醛制备苯并恶嗪树脂的反应条件,研究比较了该苯并恶嗪树脂的固化特性,同时与传统的苯并恶嗪树脂(由苯酚、苯胺、甲醛缩合制备)、烯丙基苯酚制备的苯并恶嗪树脂固化反应特性进行了对比研究；采用十二胺制备的苯并恶嗪与之共聚合制备含长碳链的共聚聚苯并恶嗪,并将该共聚物与聚丙烯(PP)及红磷共混,研究其协同阻燃情况；以1H和13C NMR和FTIR进行表征所得产物的结构,用红外光谱和差示扫描量热法(DSC)研究苯并恶嗪的聚合反应,采用热重(TG)对苯并恶嗪的热性能进行了分析,取得了丰富的研究成果。首先采用苯酚、甲醛与丙烯酰胺直接缩合制备了基于丙烯酰胺的苯并恶嗪树脂。使用氢谱(1H NMR)和红外光谱(FT-IR),差示扫描量热法(DSC)和热重分析法(TGA)分析了其结构,组成,并研究了其固化行为和热稳定性。研究表明采用无溶剂法能够获得更高的成环率。无溶剂法P-AA的比例为36.4%,而溶剂法中采用甲苯溶剂时约26%,B-AA相应的为44%和20%。单体混合物的起始热固化温度(ca.187oC)低于基于烯丙基苯苯酚制备的苯并恶嗪。不同固化温度的情况下的样品的FT-IR显示在1668cm-1处双键和在1232cm-1处嗪环吸收消失,以及在3446cm-1处羟基的出现。固化后苯并恶嗪的热稳定性,比传统的苯并恶嗪树脂(由苯酚-苯胺-甲醛缩合制备)的残炭率提高了4%。然后进行了丙烯酰胺基苯并恶嗪与烯丙基苯酚苯并恶嗪的共聚合。红外光谱(FT-IR)和差示扫描量热法(DSC)用于研究共聚的行为。丙烯酰胺基苯并恶嗪(Paa)加速恶嗪环的聚合和和支链与烯丙基苯酚苯并恶嗪(P-ala)的共聚。共聚产物组成中Paa含量没有比P-ala含量高。共聚物的热性能都得到改善。Paa残碳率提高4.3%,P-ala残炭率提高1.3%。其次,采用热诱导聚合法研究了几种苯并恶嗪树脂的自聚和共聚。聚烯丙基-苯并恶嗪(PP-ala),聚双十二烷基苯并恶嗪(PB-da)；聚烯丙基-苯并恶嗪-共聚-聚二(3,4-二氢-2H,1,3-苯并恶嗪)(PB),聚二(3,4-二氢-2H,1,3-苯并恶嗪)(PB)-共聚-聚双十二烷基苯并恶嗪(PB-da)。研究表明苯并恶嗪的共聚合依赖于分子间的的氢键和苯并恶嗪基团间的相互作用。烯丙基基团的聚合反应温度(ca.262℃)比恶嗪环开环聚合的温度高,对一些组成结构而言,烯丙基基团不能进行热聚合。最后,采用聚二(3,4-二氢-2H,1,3-苯并恶嗪)(PB)-共聚-聚双十二烷基苯并恶嗪(PB-da)与聚丙烯(PP)及红磷共混来作为聚丙烯(PP)的阻燃协效剂。通过极限氧指数(LOI)和UL-94对聚丙烯的易燃性进行了研究。热重(TG)用来表征共混物的热性能。研究发现,通过加入含有双(苯胺,3,4-二氢-2H,1,3-苯并恶嗪)和双(十二烷基3,4-二氢-2H,1,3-苯并恶嗪)的共聚苯并恶嗪可以减少聚丙烯的易燃性。加入共聚苯并恶嗪可以减少聚丙烯滴落,同时所得阻燃聚丙烯的残炭率增加3.4%。

全文目录

Abstract  5-7
摘要  7-9
TABLE OF CONTENTS  9-12
LIST OF TABLES  12
LIST OF SCHEMES  12-14
LIST OF FIGURES  14-17
CHAPTER Ⅰ:INTRODUCTION  17-24
  1.1 Preparation of benzoxazine  17-19
  1.2 Preparation of benzoxazine-amide  19
  1.3 PROBLEMATICS  19-21
  1.4 HYPOTHESIS  21
  1.5 OBJECTIVES  21-24
CHAPTER Ⅱ:LITERATURE REVIEW  24-50
  2.1 INTRODUCTION  24-26
  2.2 Synthesis of allyl containing Benzoxazine Monomers  26-31
    2.2.1 Factors affecting benzoxazine synthesis  26-27
    2.2.2 Synthesis of Allyl containing benzoxazine  27-31
  2.3 Preparations of blends and composites based allyl containing benzoxazine  31-36
    2.3.1 Glass-fiber-Reinforced Allyl-benzoxazine composites  31-32
    2.3.2 Polyhedral oligomeric silsesquioxane(POSS)with allyl containing benzoxazine monomer  32-34
    2.3.3 Epoxy resin with allyl containing benzoxazine monomer  34
    2.3.4 Benzoxazine containing allyl group with bismaleimide  34-35
    2.3.5 Organoclay-Modified Allyl-Functional Benzoxazine Resin  35-36
  2.4 Polymeric Benzoxazine precursors  36-37
  2.5 Preparation of polymer with Benzoxazine moieties  37-40
    2.5.1 Oligosiloxanes Containiing Allyl-benzoxazine Moieties in the Main Chain  37-38
    2.5.2 Polysiloxane Containing Allyl-benzoxazine Moieties in the Main Chain  38-39
    2.5.3 Methacrylate with ally containing benzoxazine monomer  39-40
  2.6 Polymerization mechanism  40-45
    2.6.1 Curing behavior of monofunctional benzoxazine  43-44
    2.6.2 Curing behavior of bifunctional benzoxazine  44-45
  2.7 Properties of polybenzoxazines based allyl and their blends and composites  45-48
    2.7.1 Benzoxazine monomers containing ally1 group;ortho-allylphenol derivative  45-46
    2.7.2 Allyl containing bifunctional benzoxazine monomer:o-allyl bisphenol-A derivative  46
    2.7.3 Benzoxazine monomers containing allyl group;allylamine derivative  46-47
    2.7.4 Allyl containing bifunctional benzoxazine monomer:allylamine derivative  47
    2.7.5 Naphthoxazine monomers containing allyl  47-48
  2.8 Conclusion  48-50
CHAPTER Ⅲ:SYNTHESIS AND CHARACTERIZATION OF POLYfACRYLAMIDE-BENZOXAZINE):LOW ENERGY THERMAL POLYMERIZATION  50-60
  3.1 Introduction  50-51
  3.2 Experimental  51-52
  3.3 Characterization  52-53
  3.4 Results and Discussions  53-56
  3.5 Thermal and mechanical properties of Poly (acrylamide-beiizoxaziiie)s  56-57
  3.6 Conclusion  57-60
CHAPTER Ⅳ:THERMAL INDUCED REACTIVE COPOLYMERIZATION OF ALLYLBENZOXAZINE AND ACRYLAMIDE-BENZOXAZINE  60-76
  4.1. Introduction  60-62
  4.2. Polymerization of benzoxazine structure  62-63
  4.3. Experimental  63-64
  4.4. Results and discussion  64-74
    4.4.1 Characterization of polymer structures  64-67
    4.4.2 Reactivity of the monomers  67-68
    4.4.3 Copolymerization analysis by FTIR  68-69
    4.4.4 Analysis of Copolymerization by DSC  69-71
    4.4.5 Oxazine ring polymerization versus allyl group polymerization  71-72
    4.4.6 Copolybenzoxazines thermal stability  72-74
  4.5 Conclusion  74-76
CHAPTER Ⅴ:EFFECT oF MOIETIES ON THE CURING PROCESS:COPOLYMERIZATION OFPOLYBENZOXAZINES  76-108
  5.1 Introduction  76-77
  5.2 EXPERIMENTAL  77-79
    5.2.1 Materials  77
    5.2.2 Characterization  77
    5.2.3 Preparation of Bis(4-dodecyl-3,4-dihydro-2H-1,3-benzoxazine)(P-da)  77
    5.2.4 Preparation of allyl-benzoxazine  77-78
    5.2.5 Preparation of Bis(3,4-dihydro-2H-1,3-benzoxazine)anline(PB)  78
    5.2.6 Copolymerization of benzoxazines  78-79
  5.3 RESULTS AND DISCUSSION  79-107
    5.3.1 Structure characterization  79-82
    5.3.2 Copolymerization of benzoxazines  82-83
    5.3.3 Copolymerization of P-ala with P-da  83-88
    5.3.4 Copolymerization of P-ala with PB  88-93
    5.3.5 Copolymerization of PB with P-da  93-96
    5.3.6 Copolymerization analysis by FTIR  96-102
    5.3.7 Thermal stability of the copolybenzoxazines  102-107
  5.4 CONCLUSION  107-108
CHAPTER Ⅵ:LOWERING POLYPROPYLENE FLAMMABILITY BY POLYBENZOXAZINE:Synergistic Effect with MRP Flame Retardant  108-115
  6.1 Introduction  108-109
  6.2 Experiment  109-111
  6.3 Testing  111
  6.4 Resullts and Discussion  111-114
  6.5 Conclusion  114-115
REFERENCES  115-131
DEDICACE  131-132
ACKNOWLEDGEMENTS  132-133
答辩委员会对论文的评定意见  133

Synthesis, Characterization and Application of Benzoxazine Acrylic and Allylic Functional

内容摘要

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