臺灣博碩士論文加值系統

一系列以3,3’,4,4’-Benzophenone tetracarboxylic dianhydride (BTDA)、Pyromellitic dianhydride (PMDA)和3,3’,4,4’- Biphenyl-tetracarboxylic dianhydride (s-BPDA)為基質，與Allyl alcohol反應，形成Di-allyl ester, system ( I ) 和Tetra-allyl ester, system ( II )，或由( I )與Glycidyl methacrylate (GMA)反應，生成Di-allyl di-glycidyl methacrylate ester, system ( III )，可與Butandithiol(BD)或4,4’-Thiol-bisbenzene-thiol (TBBT)進行附加反應(Thiol-ene addition)，生成紫外光自硬化功能多官能丙烯醇基樹脂。
Allyl alcohol作為樹脂的單體，使得樹脂具有多種的硬話機制，硬度增加到6H，也使氧對光硬化的影響減小，並提高了Tg點(166℃)，加強了樹脂本身的熱性質。
增加GMA莫耳數可使架構密度(crosslinking density)提高，並且造成皮膜擁有較高的楊氏係數和斷裂強度及較低的伸長量。同時探討Acrylate type resins與Thio-ene system resins的性質，並了解Thiol-ene system應用在光硬化樹脂上與以往壓克力型光硬化樹脂間有何差異。

A series of UV-autocurable 3,3’,4,4’-benzophenone tetracarboxylic dianhydride (BTDA), Pyromellitic dianhydride (PMDA) and 3,3’,4,4’-Biphenyltetracarboxylic dianhydride (s-BPDA) based multiacrylate resins were synthesized with allyl alcohol. They would become a di-allyl ester system (I); tetra-allyl ester system (II) and we also could add glycidyl methacrylate (GMA) to produce di-allyl di-glycidyl methacrylate ester system (III). These systems with Butandithiol (BD) or 4,4’-Thiolbisbenzenethiol (TBBT) were subjected to an additional reaction to form thio-ene system resins. The prepared autocurable resins (III) were cured easily when exposed to ultraviolet (UV) or sunlight radiation without the addition of any photoinitiator. This type of resin required a lower thermal curing temperature and had a fast curing rate. The diallyl ester system (I) and tetra-allyl ester system (II) required added benzophenone (BP) to increase the photosensitivity that would decrease the time of exposition. These resins used allyl alcohol as a monomer to successfully reduce the photocuring. This resin (BAG-122) had a Tg=166℃ and a hardness of 6H. The probability and differences between the thio-ene systems and acrylate type resins are discussed.

ABSTRACT (Chinese)．．．．．．．．．．．．．．．．． I
ACKNOWLEDGEMENTS ．．．．．．．．．．．．．．．．．．II
ABSTRACT (English)．．．．．．．．．．．．．．．．．．III
LIST OF SCHEMES．．．．．．．．．．．．．．．．．．VI
LIST OF TABLES．．．．．．．．．．．．．．．．．．．VII
LIST OF FIGURES．．．．．．．．．．．．．．．．．．VIII
CHAPTER 1 INTROUCTION．．．．．．．．．．．．．．．1
CHAPTER 2 RECIEW OF LITERATURE．．．．．．．．．．3
2.1 Market of Formulated UV-curable Products．．．．．3
2.2 Basic Chemistry of UV Curing．．．．．．．．．．．3
2.3 Photoinitiator．．．．．．．．．．．．．．．．．．4
2.4 Oligomer．．．．．．．．．．．．．．．．．．．．．8
2.5 Reactive Monomers．．．．．．．．．．．．．．．．8
2.6 Photocuring Mechanisms．．．．．．．．．．．．．．11
2.7 Oxygen Inhibition in Photopolymerization processes．．．．．．．．．．．．．．．．．．．．．．12
2.8 Crosslinking and Tensile behavior．．．．．．．．16
CHAPTER 3 EXPERIMENT．．．．．．．．．．．．．．．．18
3.1 Preparation of UV-Autocurable Resins．．．．．．．18
3.1.1 Materials．．．．．．．．．．．．．．．．．．．18
3.1.2 Synthetic Procedure．．．．．．．．．．．．．．20
3.1.2.1 Synthetic Procedure (R1:BTDA)．．．．．．．．20
3.1.2.2 Synthetic Procedure (R2:s-BPDA)．．．．．．．22
3.1.2.3 Synthetic Procedure (R3:PMDA)．．．．．．．．23
3.1.2.4 Thio-ene system．．．．．．．．．．．．．．．24
3.2 Measurement of Various Properties．．．．．．．．27
3.2.1 IR Spectra．．．．．．．．．．．．．．．．．．．27
3.2.2 Acid Value．．．．．．．．．．．．．．．．．．．27
3.2.3 NMR analysis．．．．．．．．．．．．．．．．．．27
3.2.4 Ultra-Violet Irradiation．．．．．．．．．．．．27
3.2.5 Gel Content．．．．．．．．．．．．．．．．．．28
3.2.6 The Double Bond Content．．．．．．．．．．．．28
3.2.7 Tensile Properties．．．．．．．．．．．．．．．28
3.2.8 Thermogravimetric Analysis (TGA)．．．．．．．．30
3.2.9 Differential Scanning Calorimeter (DSC)．．．．30
3.3 Coating Properties．．．．．．．．．．．．．．．．31
3.3.1 Hardness．．．．．．．．．．．．．．．．．．．．31
3.3.2 Adhesion．．．．．．．．．．．．．．．．．．．．31
3.3.3 Chemical Resistance．．．．．．．．．．．．．．31
CHAPTER 4 RESULTS OF DISCUSSION．．．．．．．．．32
4.1 IR Spectra Analysis．．．．．．．．．．．．．．．32
4.2 NMR Spectra Analysis．．．．．．．．．．．．．．．34
4.3 Acid Number．．．．．．．．．．．．．．．．．．．34
4.4 Tensile Properties．．．．．．．．．．．．．．．．38
4.5 Thermal properties．．．．．．．．．．．．．．．．39
4.6 Coating Properties．．．．．．．．．．．．．．．．40
CHAPTER 5 CONCLUSION．．．．．．． ．．．．．．．．56
REFERENCES．．．．．．．．．．．．．．．．．．．．．．58

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