臺灣博碩士論文加值系統

本研究之主旨於將本質上不相容的聚胺酯(PU)與酚醛樹脂以互穿型網
狀結構及AB交聯 型網狀結構之合成法, 合成較具相容性之不均質微相結
構網狀聚合體, 其目的是使此種新材質具有不均質結構並能因熱固性成
份,即酚醛樹脂,之加入而賦多良好的機械強度, 以作為機能性分離膜之材
離或是生醫材料. 材質的研發過程中, 透過各種不同的改質方法, 成
功地合成五系列不同結構的聚胺酯/酚醛樹脂網狀聚合體. 首先, 為了去
除酚醛樹脂生成反應對聚胺酯反應的干擾, 利用丙烯氯 (allyl
chloride) 將酚醛樹脂改質成丙烯酚醛樹脂 (allyl novolac resin), 再
利用瞬時互穿型網狀聚合法合成第一系列網狀聚合體 (UT 系列), 經過各
種性質的測試, 發現 此系列網狀物仍具有明顯的相分離現象, 因此在聚
胺酯的鏈上引入官能基, 以便能接枝到酚醛樹脂上, 並希望能提高成份間
的相容性 (TUT 系列). 研究結果顯示相容性有明顯增加但是機械強度卻
降低了. 為了更進一步有效發揮互穿網狀的功用, 引入環氧基當做聚胺酯
的網狀物的交聯鏈結 (UT-G 系列). 測試結果顯示, UT-G 系列的試片在
機械強度有了改善但仍有明顯的相分離存在. 另外, AB 交聯型網狀結
構則是本論文的另一個研究重點. 由於醯胺基與醯亞胺基均是高強度,高
耐熱型結構, 因此使用含有此兩種結構的化合物當做聚胺酯的末端封止
劑, 再與丙烯酚醛樹脂合成 AB 交聯網狀聚合體 (UT-M 系列及 UT-I 系
列). 研究結果證實這兩系列材質不論是在相容性或是機械強度方面均較
上述三系列互穿型網狀聚合體優異, 因此也更具有實用價值. 對於此
材質在實際應用上的研究貢獻則是, UT-M 系列材質在芳香族與脂環或脂
肪族 C6成份的分離實驗中有相當優異的分離效果, 尤其對苯的滲透量
(flux) 高達 4-5 Kg/cm^2h.另外幾類新材質在機能分離膜及醫用材料方
面相信也有相當的實用性, 可供以後繼續研究之用.

Based on the inherently imcompatibile materials,
polyurethane and phenolicresin, the object of this dissertation
is to synthesize imhomogeneous network polymers by either
interpenetrating network technology or AB crosslinked
networkmethod. These novel network polymers would possess
imhomogeneous structure and pertain enough mechanical strength,
which may increase by the rigid structure of phenolic resin, for
the demand of liquid/liquid separation membrane or biomaterials.
There are five series polyurethan/phenolic resin network
polymers with different network structure had been synthesized
successfully. First of all, theallyl novolac resin was
synthesized by substituted the hydroxy group in phenolicresin
with allyl chloride for eliminating the interference reaction
between polyurethane and phenolic resin. Thus, the first UT
series SINs was synthesizedby SIN method to improve the
compatibility between PU and Phenolic resin. Afterthe thoroughly
studying by thermal analysis, dynamic-mechanical analysis, and
morphological observation, the UT series still had phase
separation evidently.Therefore, the improvement of grafting
reaction carried out by implant the double bond into PU main
chain, i.e., TMPME was used as the chain extender of PU.The
resultant TUT series SINs provide better phase mixing but the
mechanical strength also decrease simultaneously. For the
requirement of superior mechanical strength and less phase
separation, the epoxide group was used as thecrosslinking
element in the PU network (UT-G series SINs). The resultant UT-
Gseries SINs provide better mechanical strength, but the degree
of phase separation was no clearly improved. The other
modifying method was AB crosslinked network structure.
Themethacrylamide and maleinimide had been used as end-capped
compounds because of itshigh tensile strength and heat
resistence, i.e., the UT-M series ABCPs and UT-I series ABCPs
respectively. The experimental results reveal that those
ABCPsnetwork polymers have better mechanical strength and phase
mixing than that of the SINs specimens. The pervaporation
separation experiment of benzene/n-hexane, or benzene/
cyclohexane had carried out by using the UT-M series ABCPs as
separation membranes. It was concluded that those ABCPs
membranes behave higher permeatingflux of benzene than that of
toluene either in n-hexane or cyclohexane. Based onthose test
results of pervaporation separation by UT-M series ABCPs, it is
believed that the other series SINs or ABCPs would possess
similar properties inpervaporation separation.

CONTENTS
List of Figures
list of Tables
ABSTRACT (Chinese and English)
Chapter 1 Introduction
1.1 The Interpenetrating Network (IPN)
1.1.1 History ofIPNs
1.1.2 Kinds ofIPNs
1.1.3 Miscibility and Phase Separation ofIPNs
1.1.3.1 Equilibrium Thermodynamics
1.1.3.2 Dynamics Theories of Phase Separation
1.1.4 Methods for Investigation
1.1.5 The Specific Mechanical Properities
1.1.6 The Current Studying ofIPNs
1.2 The AB-crosslinked Polymer Networks (ABCPs)
1.3 The Initiation of this dissertation
Chapter 2 Experimental
2.1 Materials
2.2 Preparation ofAllyl Novoac Resin
2.3 Preparation ofPU/ Allyl Novolac Resin IPNs
2.3.1 Preparation ofPU/ Allyl Novolac Resin SINs
2.3.2 Preparation ofPU/ Allyl Novolac Resin Graft SINs
2.4 Preparation ofPU/ Allyl Novolac Resin (ABCPs)
2.5 Measurements
3.1 Compatibility and Mechanical Properties of the PU/Allyl Novolac Resin SINs
3.2 The Effect of Grafting between two Network Components
3.3 Could Epoxy Terminated PU Improve the Properties of the PU/Allyl Novolac Resin SINs
3.4 ABCPs: Another Way in Constructing Network Structures
3.5 Is the Imide Group More Effective than the Amide Group in PU/Allyl Novolac Resin ABCPs?
3.6 The Applicatibility of ABCPs in Permeation Separation
Chapter 4 Conclusion
REFERENCE
LIST OF PUBLICATION
APPENDIX