DOCSLIB.ORG

ABSTRACT KOLELL, HANNAH JOY. Hydrophobic

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
ABSTRACT KOLELL, HANNAH JOY. Hydrophobic ABSTRACT KOLELL, HANNAH JOY. Hydrophobic Disperse and Polymeric Dyes for the Coloration of UHMWPE Medical Sutures. (Under the direction of Dr. Harold S. Freeman). Ultra-high molecular weight polyethylene (UHMWPE) has extremely beneficial properties, including being high strength at a relatively low weight. However, its high crystallinity and very hydrophobic nature make coloration from a dyebath difficult. Attempts at surface modification of the polymer to increase dyeability often adversely affect the desired high-performance properties. UHMWPE has applications in the medical field, including as sutures, and for surgical purposes coloration at sufficient visibility levels is of high importance. Currently, there is one FDA certified dye, D&C Violet 2, that has the ability to dye UHMWPE sutures. Thus, having additional dyes is of interest as long as the resulting color is not red. To achieve this goal, the present study pertained to the modification of various FDA certified dyes to make them suitable for dyeing PE sutures. Specifically, dyes such as C.I. Solvent Yellow 18 and C.I. Solvent Green 3 (D&C Green 6) were modified with C-4 to C-6 alkyl groups and after structure confirmation through HPLC, UV-Vis, NMR, and HR-MS, the resulting 6 dyes were tested for their ability to dye UHMWPE fibers. The dyeing study showed visibly darker fibers from the modified dye structures in comparison to the D&C Violet 2 prototype. Overall the C-4 substituted dyes showed darker coloration of the fibers and in general showed lower dye release levels during extractions, making them the preferred choices for PE sutures. All synthesized dyes were also tested under a modified Ames protocol using strain YG1041 both with and without S9 enzyme activation and none of the dyes showed mutagenicity. Poly dyes were also examined for PE sutures coloration through mass coloration. Four yellow anthraquinone polymeric dyes and the group of monomer dyes were incorporated into PE films pressed from the corresponding powder. Most of the polymeric dyes afforded no detectable color following extractions, except for the dye X26669-91 from the Weaver Dye Library. On the other hand, the monomeric dyes were more readily extracted from the films, probably because of the lower crystallinity of the polymer. These films would have a higher ability to swell in the extraction media which leads to the removal of the dyes from the polymer matrix. For UHMWPE fibers 6 new dyes were identified, synthesized and applied in a manner which led to sufficient coloration and small amounts of extracted dye under physiological conditions. The use of polymeric dyes in mass coloration also showed the ability to color PE films through a mass coloration process with little to no dye leaching. © Copyright 2019 by Hannah Kolell All Rights Reserved Hydrophobic Disperse and Polymeric Dyes for the Coloration of UHMWPE Medical Sutures by Hannah Joy Kolell A thesis submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the degree of Master of Science Textile Chemistry Raleigh, North Carolina 2019 APPROVED BY: _______________________________ _______________________________ Dr. Harold S. Freeman Dr. Richard Kotek Committee Chair _______________________________ _______________________________ Dr. Lisa Parrillo-Chapman Dr. Malgorzata Szymczyk External Member BIOGRAPHY Hannah Kolell was born in Menomonee Falls, WI and lived there until she earned her Bachelor of Science Degree in Biochemistry with a minor in Mathematics from Valparaiso University in spring of 2017. During her time at Valparaiso she studied abroad in Cambridge, England. She also participated in a summer REU program at the University of Southern Mississippi where she worked on polymer synthesis for a medical application. When it came time to decide on her next step, her love for textiles and sewing as well as for chemistry made the textile chemistry field a perfect fit and combination of these two interests. The pursuit of this field brought her to studying for a masters at North Carolina State University at the Wilson College of Textiles. Under the direction of Dr. Harold Freeman, she developed an interest in dyes and color science. She has enjoyed her time in North Carolina through hiking, beach trips, and exploring the city of Raleigh. ii ACKNOWLEDGMENTS I would first like to thank Dr. Harold Freeman for his continued guidance and knowledge throughout the project. I would also like to thank Dr. Malgorzata Szymczyk for her expertise in the lab and help with the dye synthesis and purification. I also thank the other members of my committee, Dr. Richard Kotek and Dr. Lisa Chapman for their helpful suggestions, advice, and availability. Dr.Gisela Umbuzeiro, Judy Elson, Birgit Andersen, Dr. Hanna Gracz, and Danielle Lehman were all essential for laboratory and instrumental studies. Personally, I would like to thank my fellow graduate students for support and I am so glad to have met and spent time with you all. I cannot say that I would be the chemist that I am today without Megan Cullinan, and I would specifically like to acknowledge her part in the completion of this research. I cannot express enough how thankful I am for the support that I have received from my parents to pursue this as well as from my siblings and friends who took the time to visit me in North Carolina during my time here. iii TABLE OF CONTENTS LIST OF TABLES ........................................................................................................................ vi LIST OF FIGURES ..................................................................................................................... vii Chapter 1: Literature Review and Background ....................................................................... 1 1.1. Polyethylene ...................................................................................................................... 1 1.1.1. Dyeability of Polyethylene ...................................................................................... 2 1.2. Medical Sutures ................................................................................................................ 5 1.2.1. FDA approved dyes used for sutures ....................................................................... 7 1.3. Extraction studies ............................................................................................................. 9 1.4. Mutagenicity and aquatic toxicity studies...................................................................... 10 1.5. Proposed dye structures ................................................................................................. 15 1.5.1. Long alkyl chains for dyeing improvement ........................................................... 16 1.5.2. Target dyes ............................................................................................................. 21 1.6. Polymeric colorants ....................................................................................................... 23 1.6.1 Proposed polymeric dye structures ......................................................................... 24 1.6.2. Mass coloration ...................................................................................................... 26 Chapter 2: Experimental ........................................................................................................... 28 2.1. General ........................................................................................................................... 28 2.1.1. Materials ................................................................................................................ 28 2.1.2. Instruments ............................................................................................................. 29 2.2 Synthesis of dyes............................................................................................................. 31 2.2.1. Mono-azo dyes ....................................................................................................... 31 2.2.2. Mono-anilino-substituted anthraquinone dyes ....................................................... 32 2.2.3. Di-anilino-substituted anthraquinone dyes ............................................................ 33 2.3. Fiber dyeing experiments ............................................................................................... 34 2.4. Mass coloration of PE films ........................................................................................... 35 2.5. Microscopy .................................................................................................................... 35 2.6. Extraction studies ........................................................................................................... 35 2.7. Mutagenetic and toxicity studies ................................................................................... 36 Chapter 3: Results and Discussion ........................................................................................... 37 3.1. Mono-azo and Anthraquinone dyes ............................................................................... 37 3.1.1. NMR spectra of dyes ............................................................................................. 37 3.1.2. Mass Spectrometry of dyes .................................................................................... 51 3.1.3. HPLC of crude dye mixtures ................................................................................
Load more

Recommended publications
  • Annexes Table of Content
    Annexes Table of content Annexes ................................................................................................................... 1 Table of content ........................................................................................................ 1 List of tables ............................................................................................................. 6 List of figures ............................................................................................................ 8 Annex A: Manufacture and uses ................................................................................. 10 A.1. Manufacture, import and export ........................................................................... 10 A.1.1. Manufacture, import and export of textiles and leather ........................................ 10 A.1.2. Estimated volumes on of the chemicals used in textile and leather articles ............. 12 A.2. Uses ................................................................................................................. 13 A.2.1. The use of chemicals in textile and leather processing ......................................... 13 A.2.1.1. Textile processing ................................................................................... 13 A.2.1.2. Leather processing ................................................................................. 19 A.2.1.3. Textile and leather formulations ............................................................... 20 A.2.1.4. Chemicals used in
    [Show full text]
  • The Effect of Dyes, Pigments and Ionic Liquids on the Properties of Elastomer Com- Posites
    The effect of dyes, pigments and ionic liquids onthe properties of elastomer composites Anna Marzec To cite this version: Anna Marzec. The effect of dyes, pigments and ionic liquids on the properties of elastomer com- posites. Polymers. Université Claude Bernard - Lyon I; Uniwersytet lódzki, 2014. English. NNT : 2014LYO10285. tel-01166530v2 HAL Id: tel-01166530 https://tel.archives-ouvertes.fr/tel-01166530v2 Submitted on 23 Jun 2015 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Year 2014 PH.D. THESIS COMPLETED IN “COTUTELLE” THE EFFECT OF DYES, PIGMENTS AND IONIC LIQUIDS ON THE PROPERTIES OF ELASTOMER COMPOSITES presented by MSc. ANNA MARZEC between TECHNICAL UNIVERSITY OF LODZ (POLAND) and UNIVERSITY CLAUDE BERNARD – LYON 1 (FRANCE) For obtaining the degree of Doctor of Philosophy Specialty: Polymers and Composites Materials Defence of the thesis will be held in Lodz, 2 December 2014 Thesis supervisors : Professor MARIAN ZABORSKI (Poland) Doctor GISÈLE BOITEUX (France) JURY ZABORSKI Marian Professor Thesis supervisor BOITEUX Gisèle Doctor Thesis supervisor BEYOU Emmanuel Professor Examiner JESIONOWSKI Teofil Professor Reviewer PIELICHOWSKI Krzysztof Professor Reviewer GAIN Olivier Doctor Thesis co-supervisor Année 2014 Thèse “COTUTELLE” L'EFFET DE COLORANTS, DE PIGMENTS ET LIQUIDES IONIQUES SUR LES PROPRIETES DE COMPOSITES ELASTOMERES présentée par MSc.
    [Show full text]
  • MACROLEX® Violet B FG
    Technical Data Sheet MACROLEX® Violet B FG Colour Index Part I Solvent Violet 13 Part II 60725 Chemical description Anthraquinone dyestuff Form supplied powder Shade violet with a blue cast 1/3 Standard depth 0.18% dyestuff (determined in GP-PS with 2% TiO2) Density (23°C) approx. 1.35 g/cm3 Bulk density approx. 0.39 g/cm3 (according to DIN ISO 787-11) Melting point approx. 189°C Main fields of application Transparent and opaque dyeing of PS, SAN, PMMA, PC, PET, ABS and ABS / PC blends. Storage stability 60 months from delivery ex plant LANXESS Deutschland GmbH Solubility in g/l at temperature 23°C (approximate figures) Water Acetone Benzyl Butyl Ethanol Methyl Methylene Styrene Xylene alcohol acetate methacrylate chloride (monomer) insoluble 1.5 4.0 3.0 0.1 5.5 30 12 8.0 Heat stability in °C at 1/3 standard depth with 1% TiO2 (ABS 4% TiO2 and PS 2% TiO2) evaluated according to DIN EN 12877; (approximate figures) PS SB* ABS SAN PMMA PC PA 6 PA 6.6 PET PBT 300 300 280 280 300 350 - - 290 280 * For Styrene-butadiene block copolymer the use of this dye is not recommended. Lightfastness 1/3 standard depth with 1% TiO2 (PS 2% TiO2) according to DIN EN ISO 4892-2; transparent coloration with 0.05% dye; evaluated with 8-step blue wool scale PC PS PMMA Dye content reduction transparent Dye content reduction transparent Dye content reduction transparent in % in % in % 0.090 6-7 7-8 0.180 5-6 7-8 0.090 6-7 7-8 Materials used for testing of Heat stability and Lightfastness: PS: BASF Polystyrene 143E PA 6: LANXESS Durethan B30S SB: BASF Polystyrene 472C PA 6.6: LANXESS Durethan A30H 1.0 Page 1 of 3 Edition: 22.
    [Show full text]
  • ABSTRACT WILLIAMS, TOVA N. Approaches
    ABSTRACT WILLIAMS, TOVA N. Approaches to the Design of Sustainable Permanent Hair Dyes (Under the direction of Harold S. Freeman). Interest in designing sustainable permanent hair dyes derives from the toxicological concerns associated with certain commercial dyes, in particular the moderate to strong/extreme skin sensitization potential of certain precursors used to develop the dyes. While work has been undertaken to help address toxicological concerns of hair dyes, alternatives having commercial success are based on the conventional permanent hair dye coloration process and still may pose health problems. The conventional process involves the oxidation of small and essentially colorless precursors (e.g., p-phenylenediamine and resorcinol) within the hair fiber that couple to build oligomeric indo dyes that are difficult to desorb. The resultant depth of shade achieved is superior that of other hair dyes and provides a high degree of gray coverage. In fact, these dyes dominate the commercial realm and stimulate the multibillion-dollar global hair dye market for the millions of consumers (men and women) who use them. Approaches to the design of sustainable (less toxic) permanent hair dyes lie at the heart of the present study. In Part 1 of this study, two types of keratin films (opaque and translucent) were characterized for their potential as screening tools for predicting the efficacy of potential hair dyes using the hair dye, C.I. Acid Orange 7. Translucent keratin films, which were found to be less porous than opaque films and more like hair in this regard, were deemed better tools for predicting the efficacy of potential hair dyes on hair.
    [Show full text]
  • The Coloration
    The coloration OF PLASTICS AND RUBBER The coloration OF PLASTICS AND RUBBER TRADEMARKS: GRAPHTOL® HOSTASIN™ 1 HANSA® HOSTASOL™ 1 HOSTALEN® 1 HOSTAVIN® 1 TELALUX™ NOVOPERM® HOSTANOX® 1 POLYSYNTHREN® HOSTAPERM® 1 PV FAST® HOSTAPRINT™ 1 SOLVAPERM® TELASPERSE™ SECTION 1 of this brochure is an introduction and NOTE ON THE THERMAL STABILITY The coloration of plastics is an area guide to the coloration of plastics and includes chapters OF DIARYLIDE PIGMENTS covering colorant classification, colorant selection Pigments indicated with the symbol ❖ throughout of technology in which everyone has criteria and an overview of the Clariant product ranges this brochure are collectively identified chemically for plastics coloration. This is followed by a product as diarylide pigments. Due to the potential for thermal an opinion, everyone else can do it by product guide to the main areas of application using decomposition (refer to the relevant material safety data the following key: sheets) from these pigments, a heat stability of 200 °C is better and cheaper and where the given, even when the coloring attributes of the pigment ■ Suitable would remain stable at higher temperatures. mistakes are highly visible and usually ● Limited suitability (preliminary testing required) — Not suitable Further information can be found in ETAD INFORMATION expensive. This brochure sets out NOTICE No. 2 » Thermal Decompo sition of Diarylide SECTION 2 provides a concise guide; polymer by Pigments« – September 1990. to provide the reader with a practical polymer to the coloring possibilities with Clariant organic colorants which includes polymer properties, CLARIANT SHADE CARDS AND insight in polymers, processes and processing and coloring techniques and details of the TECHNICAL BROCHURES individual colorants, their suitability for an application The Clariant Plastics & Coatings Business strives to applications applying to the plastics and their application data in the selected polymer and provide a high level of technical information regarding process.
    [Show full text]
  • • for Amendment – Terms of Reference [Tor]
    SEAC, Gujarat Page 1 • For Amendment – Terms of Reference [ToR] 1. Earlier ToR letter no. and Date: TOR letter no.: SEIAA/GUJ/TOR/5(f)&1(d)/905/2017 dated 12/10/2017 TOR-Amendment letter no.: SEIAA/GUJ/TOR/5(f)&1(d)/490/2018 dated 17/05/2018 2. Basic Information of the Project: i Name & Address of the Project site M/s. Colourtex Industries Pvt. Ltd. (Unit-1) (Complete details with plot no./Survey Block Nos. 272/P, 273/P, 274, 278/P, no., Landmark etc. ) 283/P, 284/P, 285 to 288, 294 to 297, 310, Plot Nos. 288/1, 288/2, 289/1, 289/2, 8108/2, 364, 801, 268/3 GIDC Sachin, Dist. Surat - 394 230 ii Name of the Applicant Mr. Kirit G. Gandhi iii Address for correspondence M/s. Colourtex Industries Pvt. Ltd. Plot No.158/-3, GIDC Estate, Pandesara, Dist: Surat, Gujarat – 394 221 iv Contact no. and e-mail ID of the Mo. no. : +919825056865 Applicant eMail: [email protected] [email protected] v Aerial distance of nearest Habitat 0.5 Km (KM) vi Longitude & Latitude of the Project Site: Lat.: 21° 6'21.60"N &Long.: 72°51'2.38"E (4 corners of the site) Lat.: 21° 6'11.42"N & Long.: 72°50'43.71"E Lat.: 21° 6'1.42"N &Long.: 72°50'58.76"E Lat.: 21° 6'9.37"N &Long.: 72°51'16.98"E vii Category as per the Schedule to the 5(f) EIA Notification 2006 i.e.
    [Show full text]
  • Quality Shines
    QUALITY SHINES. Unlimited colors Colorants for plastics MACROLEX® DYES – MACROLEX® DYES – PRODUCT RANGE AND PROPERTIES PRODUCT RANGE AND PROPERTIES The LANXESS Rhein Chemie business unit supplies a broad Some dyes have a high solubility in solvents like Macrolex® Usage: range of colorants for a wide range of different applications. Y ellow 6G, others like Macrolex® Red EG show very low Macrolex® dyes are suitable for coloring amorphous thermo- solubility. In all cases Macrolex® dyes are fully soluble in hot plastics such as: Outstanding product quality, long-established technical ex- engineering plastics. PS, EPS, SB*, SAN*, ABS and their blends pertise and the satisfaction of a wide range of essential regu- (*not block copolymers); latory requirements – these are the defining features of our In contrast to standard disperse dyes, Macrolex® dyes are PMMA, PC, PPO and their blends; product portfolio. extremely pure and have a very low amount of impurities. PVC-U, PET, (PBT); (PA-6, PA-12), CA, CAB. The following pages give technical information on Lanxess As early as in the 1960s Macrolex® dyes were devel oped for colorants used for plastics. the special needs of plastics coloration. Process conditions The Macrolex® range contains soluble dyes with Macrolex® soluble dyestuffs are used for engineering for engineering plastics like polystyrene, ABS, PC, PMMA, PA high heat stability; plastics. and others are quite severe. During extrusion and injection good light fastness and weather resistance; Bayplast® organic pigments are used for standard molding of PC, the dyes have to withstand temperatures up to high color strength; plastics. over 350 °C for some minutes.
    [Show full text]
  • ANNEX II, Last Update: 06/07/2021 LIST of SUBSTANCES PROHIBITED in COSMETIC PRODUCTS
    File creation date: 25/09/2021 ANNEX II, Last update: 06/07/2021 LIST OF SUBSTANCES PROHIBITED IN COSMETIC PRODUCTS Reference Substance identification number Chemical name / INN CAS Number EC Number Update Date 1 N-(5-Chlorobenzoxazol-2-yl)acetamide 35783-57-4 - 17/10/2010 2 (2-Acetoxyethyl)trimethylammonium hydroxide (Acetylcholine) and its salts 51-84-3 200-128-9 17/10/2010 3 Deanol aceglumate (INN) 3342-61-8 222-085-5 15/10/2010 4 Spironolactone (INN) 52-01-7 200-133-6 15/10/2010 5 [4-(4-Hydroxy-3-iodophenoxy)-3,5-diiodophenyl]acetic acid (Tiratricol (INN)) and its salts 51-24-1 200-086-1 17/10/2010 6 Methotrexate (INN) 59-05-2 200-413-8 15/10/2010 7 Aminocaproic acid (INN) and its salts 60-32-2 200-469-3 17/10/2010 8 Cinchophen (INN), its salts, derivatives and salts of these derivatives 132-60-5 / 205-067-1 / 17/10/2010 5949-18-8 227-710-5 9 Thyropropic acid (INN) and its salts 51-26-3 - 17/10/2010 10 Trichloroacetic acid 76-03-9 200-927-2 15/10/2010 11 Aconitum napellus L. (leaves, roots and galenical preparations) 84603-50-9 283-252-6 15/10/2010 12 Aconitine (principal alkaloid of Aconitum napellus L.) and its salts 302-27-2 206-121-7 15/10/2010 13 Adonis vernalis L. and its preparations 84649-73-0 283-458-6 15/10/2010 14 Epinephrine (INN) 51-43-4 200-098-7 15/10/2010 15 Rauwolfia serpentia L., alkaloids and their salts 90106-13-1 290-234-1 17/10/2010 16 Alkyne alcohols, their esters, ethers and salts - - 17/10/2010 17 Isoprenaline (INN) 7683-59-2 231-687-7 15/10/2010 18 Allyl isothiocyanate 57-06-7 200-309-2 15/10/2010 19 Alloclamide
    [Show full text]
  • (19) United States (12) Patent Application Publication (10) Pub
    US 20110124837Al (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0124837 A1 Hong et al. (43) Pub. Date: May 26, 2011 (54) POLYMERIC VIOLET ANTHRAQUINONE (52) US. Cl. ....................................... .. 528/226; 528/220 COLORANT COMPOSITIONS AND METHODS FOR PRODUCING THE SAME (57) ABSTRACT (76) Inventors: Xiaoyong Michael Hong, Greer, This invention relates to polymeric violet anthraquinone SC (US); Robert L. Mahaffey, colorants having at least one poly(oxyalkylene) chain Spartanburg, SC (U S) attached to an anthraquinone structure. Such colorants exhibit bright violet shade, excellent compatibility With organic (21) Appl. No.: 12/624,646 media or aqueous systems, good lightfastness, and excellent thermal stability. The Water soluble poly(oxyalkylene) sub (22) Filed: Nov. 24, 2009 stituted polymeric violet anthraquinone colorants also pos sess high Water solubility, high color strength, non-staining Publication Classi?cation properties, and high pH stability. The processes and methods (51) Int. Cl. for making such polymeric violet anthraquinone colorants C08G 16/00 (2006.01) and their use for coloring consumer products are also pro C08G 75/00 (2006.01) vided. US 2011/0124837 A1 May 26, 2011 POLYMERIC VIOLET ANTHRAQUINONE creams or pastes. Similar to the acid dyes described above, COLORANT COMPOSITIONS AND these compositions cause staining to the substances to Which METHODS FOR PRODUCING THE SAME they are applied. In this instance, it is desirable to use staining anthraquinone colorants for dyeing human hair. Thus, the FIELD OF THE INVENTION colorants taught by Kaiser et al. are not polymeric in nature, and they are not non-staining. Additionally, the colorants [0001] This invention relates to compositions of polymeric taught by Kaiser et al.
    [Show full text]
  • The Coloration of Plastics and Rubber
    Pigments & Additives Division Plastic Business Exactly your chemistry. The Coloration of Plastics and Rubber The Coloration of Plastics and Rubber Foreword Note on the thermal stability of diarylide pigments The coloration of plastics is an area of technology in which Pigments indicated with the symbol ❖ throughout this bro- everyone has an opinion, everyone else can do it better and chure are collectively identified chemically as diarylide pig- cheaper and where the mistakes are highly visible and ments. Due to the potential for thermal decomposition (refer usually expensive. to the relevant material safety data sheets) from these pig- ments, a heat stability of 200 °C is given, even when the This brochure sets out to provide the reader with a practical coloring attributes of the pigment would remain stable at insight in to the polymers, processes and applications app- higher temperatures. lying to the plastics industry and the coloring solutions avai- lable from the Clariant ranges of organic colorants. Further information can be found in ETAD INFORMATION NOTICE No. 2 “Thermal Decomposition of Diarylide Section 1 of this brochure is an introduction and guide to Pigments” - September 1990. the coloration of plastics and includes chapters covering colorant classification, colorant selection criteria and an overview of the Clariant product ranges for plastics colora- Clariant shade cards and technical brochures tion. This is followed by a product by product guide to the main areas of application using the following key: The Business; Marketing Plastics of Clariant strives to pro- vide a high level of technical information regarding its pro- ■ suitable ducts. Technical brochures and shade cards are continually ● limited suitability (preliminary testing required) being updated to include new products, cater for new appli- − not suitable cations and to provide customers with the relevant techni- cal data in order to meet the demands of a fast changing Section 2 provides a concise guide; polymer by polymer to industry.
    [Show full text]