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Modifications of Polyaspartimide and Poly(Ethylene-Co-Methacrylic Acid) :: Investigation of Potential Fungicidal Support Polymers in a Nylon 6 Blend/ Carl J

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University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations 1896 - February 2014 1-1-1985 Modifications of polyaspartimide and poly(ethylene-co-methacrylic acid) :: investigation of potential fungicidal support polymers in a nylon 6 blend/ Carl J. Sullivan University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_1 Recommended Citation Sullivan, Carl J., "Modifications of polyaspartimide and poly(ethylene-co-methacrylic acid) :: investigation of potential fungicidal support polymers in a nylon 6 blend/" (1985). Doctoral Dissertations 1896 - February 2014. 697. https://scholarworks.umass.edu/dissertations_1/697 This Open Access Dissertation is brought to you for free and open access by ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations 1896 - February 2014 by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. MODIFICATIONS OF POLYASPAilTIMIDE MD POLY(ETHrLENE-CO-MEmCRYLIC AGO) : INVESTIGATION OF POTENTIAL FUNGICIDAL SUPPORT POLYMERS IN A NYLON 6 BLEND A Dissertation Presented By Carl J. Sullivan Submitted to the Graduate School of the University of Massachusetts in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPEY February I985 Polymer Science and Engineering Carl J. Sullivan All Rights Reserved ii MODIFICATIONS OF POLYASPARTIMIDE AND P0LY(ETHYLENE-C0-METHACRYLIC ACID) ; INVESTIGATION OF POTENTIAL FUNGICIDAL SUPPORT POLYMERS IN A NYLON 6 BLEND A Dissertation Presented By Carl J. Sullivan Approved^ as to style and content by: / Robert W. Lenz, Chaiirman of Committee William J(J MacKnighy, Member c"! Peter Lillya, Member/) 0 W/J. MacKn^ht, Head Polymer Science and Engineering 111* • Dedicated to my wife, Joann. iv . ACKNOWLEDGEMENTS I wish to thank Dr. Robert W. Lenz for his gui- dance and support throughout this project. I would also like to thank Dr. MacKnight for the many discussions and suggestions, and Dr. LiUya for his time and effort spent in serving on my dissertation committee. I would also like to thank Dr. R.j. Somani, Mr. James Katsaros and Mr. Paul Nikolaidus for their assis- tance in analyzing the Nylon 6 blends. I am indebted to the Allied Corporation Fibers and Plastics Company for financial support of this research and to Dr. C. Cole for many helpful discussions. I am grateful to all my fellow students, in par- ticular Bret Vanzo, Dani Gula, and Dave Gagnon, not only for their advice, but also for their friendship. To my parents, I am forever grateful. To the Rittersbachers, I am deeply grateful for their support and assistance Finally, and most importantly, I thank my wife Joann. The sacrifices you made were countless, your sup- port was never ending, and your devotion will never be forgotten V ; ABSTRACT Modifications of Polyaspartimide and Poly (ethylene-co-methacrylic acid) Investigation of Potential Fungicidal Host Polymers in a Nylon 6 Blend (January 1985) Carl J. Sullivan B.S., Ursinus College M.S., Ph.D., University of Massachusetts Directed by: Dr. R.W. Lenz The investigation of polyaspartimide derivatives and polyethylene-co-methacrylic acid derivatives as poten tial polymer supports for 2- (4-thiazolyl) benzimidazole in nylon 6 blends was conducted. Nucleophilic ring opening of the polyaspartimide repeat unit provided substituted polyamides with and ^ repeat units which were found be thermally unstable above 200 °C because of the presence of <^ -aminoacid amide structures. Hence, such a polyas- partimide derivative is unacceptable as a polymeric host for 2- (4-thiazolyl ) benzimidazole in a nylon 6 blend. Blend properties of 90% nylon 6 and 10% polyethylene-co- methacrylic acid and derivatives were investigated. The specific derivatives investigated were the methyl ester, n-hexyl amide, £ -caprolactam imide, and the sodium salt of the methacrylic acid repeat unit in the copolymer. vi comparisons with previous results of the properties of blends of polyethylene-co-methacrylic acid with nylon 6 established that polyethylene-graf t-nylon 6 copolymers formed as a result of amidation of the carboxylic acid derivatives, but only a fraction of these functional groups were amidated. Based upon the blend properties of these derivatives it is predicted that a polyethylene-co- methacrylic acid is an appropriate choice for a support polymer in nylon 6 blend. Chemical bonding of 2-(4-thia- zolyDbenzimidazole to this copolymer was investigated. A direct amidation of polyethylene-co-methacrylic acid involving the acid chloride derivative was attempted but failed due to the steric bulk of the benzimidazole . Model acylations of 2- ( 4-thiazolyl) benzimidazole confirmed this conclusion. An N-carbamoyl adduct of 2- ( 4-thiazolyl) ben- zimidazole with toluene diisocyanate was found to be ther- mally and solvolytically unstable. 1- ( 2-hydroxyethyl) -2- (4-thiazolyl) benzimidazole was synthesized and subsequently reacted with polyethylene-co-methacryloyl chloride to obtain a polymerical ly bound derivative of this biocide. Biological activity of this derivative alone or in a nylon 6 blend have not been studied. vii TABLE OF CONTENTS ACKNOWLEDGEMENTS V ABSTRACT vi LIST OF TABLES xii LIST OF FIGURES. xiv Chapter I. INTRODUCTION . 1 Specialty Polymers - An overview. ... * i Polymer additives ! ! ! Specialized polymers * and copolyiliers ! ! K Polymer blending ] ] g Functionalized Polymers in Blends . [ [ [ 6 Technological advantages ....... \ 6 Theoretical requirements ........ Functionalized Polymers 7 in Nylon 6 Blends ! Introduction 11 Choice of * polymer ^2 Choice of 2- (4-thiazolyl) benzimidazole ! 18 Present Investigation Objectives in Summary 22 II. POLASPARTIMIDE AND DERIVATIVES 2i| Synthesis and Properties of Polyas- partimide 2^ Blend of Polyaspartimide with Nylon 6 . 26 Synthesis and Properties of Ethanolamine . Derivatives of Polyaspartimide 27 Copolymer synthesis 27 Copolymer composition 29 Infrared analysis 29 NMR characterization 35 NMR characterization - percent conversion i^q NMR characterization - copolymer mic restructure 1^2. NMR characterization - a / ^ ratios . I46 Summary of characterization 55 Effect of composition on properties ... 55 Polyblend of nylon 6 and poly (2-hy- droxyethyl aspartimide) 58 Polyaspartimide derivatives 60 Poly (aspartic acid) , PAAc 61 Attempted synthesis of poly (methyl aspartate) , PMAT 62 Vlll• • B Chapter Amine derivatives of PAIm: synthe- sis and characterization . * 63 Thermal analysis * Conclusions ! 67 \ 72 III. P(E/MAA) AS A POTENTIAL POLYMER SUPPORT 73 Introduction 73 Varied Moisture Content Effects on Nylon 6/P(E/MAA) Blends. 75 Modified P(E/MAA) and Blends '. with Nylon 6 78 Conversion to ester or amide derivatives 78 Partial conversion to methyl esters! '. Partial neutralization ] 8U 89 Attempted Synthesis of Polyethylene-* graft-Nylon 6 96 IV. INVESTIGATION OF CHEMICALLY BONDING 2 (4TH) B TO P(E/MAA) 105 Introduction -jO^ 1-Acylation Reactions of 2(4Th)B. ! ! 108 Reaction of 2(4Th)B with P(E/MAC1) ... 108 Model acylation of 2(4Th)B 113 Reactions of 2(4Th)B with adipyl chloride or terephthalyl chloride . 119 Reaction of 2(4Th)B with succinic anhydride Concluding remarks 12l|. Reactions of 2(4Th)B with Isocyanates ... 125 Introduction I25 Reaction of 2(4Th)B with phenyl isocyanate 128 Reaction of 2(4Th)B with toluene diisocyanate I3I Reactions of the TDI/2(4Th)B adduct. li^o Final remarks on a l-carbamoyl-2 ( 4Th) Functionalized P(E/MAA) li^^ Synthesis of P(E/MAA) Functionalized with l-alkyl-2 (4Th) B 11^9 V. CONCLUSIONS 1^3 VI. EXPERIMENTAL 159 Materials 1^9 Polymerization of Aspartic Acid 1^9 Synthesis of Poly ( aspartic acid), PAAc . 16I Reaction of PAIm with Ethanolamine 162 ix ) - Chapter Synthesis of poly (2-hydroxyethyl aspartamide) Synthesis of poly (2-hydroxyethyi aspartamide) -co- (aspartimide) .... igq Reaction of Polyaspartimide with Amines . 166 General procedure Jg^ With dicyclohexylamine With phene thy 1 amine ! ! ! ! ! 168 With 2-(4-thiazolyl) *. benzimidazile ! ! 168 With 6-amino caproic acid 158 With benzylamine .^-q With aniline 169 With * * methylamine hydrochloride ... 170 With phenetidine With \ \ cyclohexylamine ! ! ! ! ! With 2-hydroxypropylamine. .,.'..[[ 171 With n-hexylamine 171 1^2 With 3-phenyl propylamine Reaction [ [ ^72 of PAIm with Methanol I73 Synthesis of Polyethylene-co-methacryloyl chloride From Polyethylene-co- methacrylic acid IY3 Thionyl chloride method 173 Oxalyl chloride method 175 Attempted isolation of polyethylene- co-methacryloyl choride I76 Conversion of P(E/MAA) to P(E/MMA) 176 Conversion of P(E/MAA) to P(E/MAA/NaMA with Varying MAA/NaMA Ratios I77 Synthesis of P(E/nHMAm) I78 Synthesis of P (E/N-MACap) I78 Attempted Synthesis of P (E/MAA) -graft- Nylon 6 179 Attempted Synthesis of Poly (ethylene) CO- ( l-methacryloyl-2- (4-thiazolyl) benzimidazole) (PE/MA4ThB) I8I Attempts by P(E/MAC1) From thionyl chloride route I86 Attempts by P(E/MAC1) From oxalyl chloride route I87 Attempted synthesis of P(E/IVIAThB) From P( E/MAA) and 2(4Th)B I88 Attempted synthesis of P(E/MAThB) From P(E/MMA) I89 Synthesis of l-Acetyl-2 (4-thiazolyl benzimidazole I89 Attempts From the lithium salt of 2(4Th)B 189 Synthesis From 2(4Th)B directly 191 X Chapter Attempted Synthesis of 1-Pivalyl- 2- (4-thiazolyl) benzimidazole Attempted Synthesis of 1- (Monochloro adipyl)-2-(4-thiazolyl) benzimidazole . Attempted Synthesis of 1- (Monochloro terephthalyl-2- (4-thiazolyl) benzimidazole Reaction of 2(4Th)B with Succinic
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