PATENT APPLICATIONSA Tool for Identifying Advances in

Polymer Chemistry R & D

THOMAS F. DEROSA

InnodataFile Attachment9780470507308.jpg

PATENT APPLICATIONS

PATENT APPLICATIONSA Tool for Identifying Advances in

Polymer Chemistry R & D

THOMAS F. DEROSA

Copyright # 2009 by John Wiley & Sons, Inc. All rights reserved

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Library of Congress Cataloging-in-Publication Data

DeRosa, Thomas F.Patent applications : a tool for identifying advances in polymer chemistry R & D / Thomas F. DeRosa.p. cm.

Includes index.ISBN 978-0-470-47228-6 (cloth)1. Polymers–Research. 2. Patents. I. Title.QD381.D474 2009668.9072–dc22

2009005634

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

http://www.copyright.comhttp://www.wiley.com/go/permissionhttp://www.wiley.com

Dedicated to my wife,

Barbara

for her patience and emotional support

in the preparation of this book

CONTENTS

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii

I. ADDITIVES

A. Ink Dispersants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1B. Ink Dispersants and Colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4C. Oil Dispersants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8D. Oil Drilling Dispersants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12E. Fabric Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17F. Paint Additives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37G. Paint Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46H. Paper Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49I. Polymeric Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

II. ADHESIVES

A. Pressure Sensitive Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59B. Surface Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67C. Thermally Stable Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

III. COSMETICS

A. Topical. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

IV. CRYSTALLINE MATERIALS

A. Liquid-Crystal Displays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

V. DYES

A. Jet Printer Ink . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

vii

VI. ELECTRICALLY ACTIVE POLYMERS

A. Battery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121B. Conducting Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125C. Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129D. Photovoltaic Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145E. Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163F. Transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185

VII. ENERGETIC POLYMERS

A. Explosive Binder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191

VIII. ENGINEERED PLASTICS

A. Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197B. Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200C. Crosslinking Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205D. High-Performance Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215

IX. FIBERS

A. High Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251

X. FUEL CELLS

A. Fuel Cell Membranes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259B. Proton Conducting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262

XI. IMPROVED SYNTHETIC METHODS

A. Isocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281B. Organometallic Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285

XII. INITIATORS/MODIFIERS

A. Free Radical Initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317B. Free Radical Initiator Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322C. Photoinitiators. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325

viii Contents

XIII. LIGHT-EMITTING POLYMERS

A. Diodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335

XIV. MEDICAL POLYMERS

A. Biodegradable. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409B. Biomaterials for Dental Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421C. Biomaterials for Diagnostics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447D. Biomaterials for Drug Delivery Devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . 455E. Biomaterials for Gene Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489F. Biomaterials for Membranes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494

XV. NITRIC-OXIDE-RELEASING AGENTS

A. Antirestenosis Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499

XVI. OPTICAL

A. Intraocular Lenses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507B. Optical Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533C. Optical Waveguides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536

XVII. PHARMACEUTICALS

A. Polypeptides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541B. Radiopharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544

XVIII. PHOTORESISTS

A. Resists . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551

XIX. PHOTOTHERAPY

A. Oxygen Generators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599

XX. RECORDING MATERIALS

A. Anisotropic Films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607

Contents ix

XXI. STENTS

A. Cardiovascular . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613

XXII. SUTURES

A. Adsorbable . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617

XXIII. TISSUE REPLACEMENT

A. Tissue Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621

XXIV. VISCOELASTIC POLYMERS

A. High Viscoelastic Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635

Contributors

Academic Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641

Government Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641

Industrial Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645

x Contents

PREFACE

There has never been a doubt that the US Patent and Trademark office consisting of adb of well over 7,500,000 records is one of the lesser utilized scientific resources. It isin this domain that the most commercially viable chemical/scientific inventions aredescribed. In purely academic circles this db is shunned.

From the moment a US Patent is filed, it may require two to five years before thedocument is issued as a Patent. Moreover, while only 70% of filed Applicationsissue as patents, the dominant reason is the chemistry of the Application is too currentto that of the existing Patent.

Nevertheless, the objective of this treatise is to provide the chemical researcher witha two to five “window” to assess the direction that industry/academia are pursuing.This work is further intended to allow chemical researchers the opportunity to avoidinfringing on Applications and Patents.

It is my intentions that the text of US Patent Application is easily followed andprovides fruitful chemical leads and ideas.

THOMAS F. DEROSA

xi

INTRODUCTION

The objective of this book is to identify and highlight significant state-of-the-artresearch in 24 active areas of polymer chemistry reported in current U.S. patent appli-cations occurring in academic, government, and industrial centers. A further objectiveis to provide chemical researchers with descriptions of advances in these areas as wellas detailing synthetic methods for preparing key intermediates and products providedfrom these technical centers. Wherever possible key references associated with eachentry have been supplied to provide a chemical and evolutionary context for the reader.

From its initial filing with the U.S. Patent and Trademark Office, a U.S. patentapplication issuing period is from 18 months to 5 years. Thirty percent of filedapplications, however, do not issue as U.S. patents. While there are many reasonsfor this, the most cogent reason is that the application chemistry too closely resembleschemical material already described in an issued patent. U.S. patent applications thatdo not issue as U.S. patents are doomed to oblivion.

In this book 24 academic and industrial subject areas of active research reportedin U.S. patent applications are reviewed and summarized so that essential informationis readily available to the researcher. The 24 polymeric categories include:

AdditivesCosmeticsDyesEnergetic PolymersFibersImproved Synthetic MethodsLight-Emitting PolymersNitric-Oxide-Releasing AgentsPharmaceuticalsPhototherapyStentsTissue Replacement

AdhesivesCrystalline MaterialsElectrically Active PolymersEngineered PlasticsFuel CellsInitiators/ModifiersMedical PolymersOpticalPhotoresistsRecording MaterialsSuturesViscoelastic Polymers

It is impossible to determine with certainty whether a U.S. patent application willissue as a U.S. patent. Nevertheless relevant subject matter appearing in U.S. patentshave been identified and reviewed to qualitatively gauge the patentability of U.S.patent applications contained in this book.

The text format has been designed to be used as a reference and synthetic guide forpolymer and organic chemists as well as for graduate students. The material describedherein is not limited to polymer chemistry, however. In many instances—and withonly marginal synthetic modifications—intermediates and products are readily

xiii

convertible into agents outside the scope of this book. Extensive structural depictionsof intermediates, products, and derivatives have been provided to allow the researcherto more easily visualize other material applications.

Finally, I thoroughly enjoyed compiling this text and hope the reader finds it useful.

THOMAS F. DEROSA

xiv Introduction

I. ADDITIVES

A. Ink Dispersants

a. Hyperbranched esters

Title: Method for the Production of HyperbranchedWater-Soluble PolyestersAuthor: Jean-Francois Stumbe et al.Assignee: BASF Aktiengesellschaft (Ludwigshafen, DE)

U.S. Patent Application: 20070293634 (December 20, 2007)Material Patentability: MediumAnticipated Issuing Data: Mid-2010

Research Focus: Preparation of nondentrimeric hyperbranched polyesters that are water-soluble or water-dispersible from dicarboxylic acids and polyetherpolyols.

Originality: Although dentrimeric hyperbranched polyesters have been reported in thepatent literature, the agents in this application are novel.

Application: Ink dispersant

Observations: This group has developed a single-step method for preparing ester-graftedhyperbranched polymers. These materials are not dentrimeric analogs,however. Although hyperbranched ureas, carbonates, and polyestershave previously been prepared, in this application water-dispersible orsoluble linear polyesters containing pendant alcohols having acidnumbers from 9 to 117 were produced. The single-step method for prepar-ing these agents entailed condensing the oligomeric glycerol with selecteddicarboxylic acids in the presence of either enzyme catalyst Novozymw-435 or acid catalyst Fascatw.

Patent Applications: A Tool for Identifying Advances in Polymer Chemistry R & D. By Thomas F. DeRosaCopyright # 2009 John Wiley & Sons, Inc.

1

REACTION

i. Adipic acid, Novozymw-435, toluene

1. Preparation of linear hyperbranched polyester using Novozymw-435

Adipic acid (0.60 mol) and an oligomeric glycerol having a repeat unit of three, PG-3(0.44 mol), were dissolved at 708C in 80 ml of toluene and then treated with enzymecatalyst Novozymw-435 (14 g). The mixture was polymerized for 9 hours at 708C at300 mbar to remove water formed during the reaction. The mixture was then concen-trated and the product isolated as a honey-like, viscous, colorless to slightly yellowishpolyester. The polyester was readily soluble in water.

DERIVATIVES

A summary of water-dispersible or water-soluble linear polyesters prepared in thisapplication containing hyperbranched alcohols and having acid numbers from 9 to117 is provided in Table 1. Ester reactions were performed using either enzyme cata-lyst Novozymw-435 or acid catalyst Fascatw.

TABLE 1. Physical Properties of Selected Water-Soluble or Water-DispersablePolyesters Prepared Using Enzyme Catalyst Novozymw-435 or Acid Catalyst Fascatw

Entry ReagentsAcid

NumberMw(Da)

Mn(Da)

WaterSolubility

2 Adipic acid, PG-3, Fascatw 117 2220 1450 Very good3 Adipic acid, TMPEOa,

Novozymw-4359 8000 24,000 Good

4 Adipic acid, TMPEO, Fascatw 50 2340 5860 Good7 Adipic acid, PG-3, stearic acid 104 2300 3330 Dispersable10 Phthalic anhydride, PG-3, Fascatw n.d. n.d. n.d. Dispersable

aEthoxylated trishydroxymethylpropane.

2 Method for the Production of Hyperbranched Water-Soluble Polyesters

NOTES

1. Additional hyperbranched polyesters based on either di-, tri-, or polycarboxylicacids or di-, tri-, or polyols are described by Bruchman et al. (1). For example,the reaction product of adipic acid, pentaerythritol and 1,4-cyclohexanedi-methanol, was prepared using di-n-butyltin oxide as catalyst and then post-reacted with selected diisocyanates and used as a paint additive.

2. By reacting hyperbranched polyesters with diethyl carbonate, Eipper et al.(2) prepared impact-modifing hyperbranched polyester–polycarbonates resins.

3. In an earlier investigation by the authors (3) hyperbranched polyamides wereprepared by condensing adipic acid with polyamines at 1508C.

4. In related investigations hyperbranched polyureas and polycarbonates wereprepared by Bruchmann et al. (4,5), respectively, while hyperbranchedanalogs containing ethylenically unsaturated substituents were prepared bythe authors (6).

References

1. B. Bruchmann et al., U.S. Patent Application 20070213501 (September 13, 2007).

2. A. Eipper et al., U.S. Patent Application 20070244227 (October 18, 2007).

3. J.-F. Stumbe et al., U.S. Patent Application 20070191586 (August 16, 2007).

4. B. Bruchmann et al., U.S. Patent Application 20070083030 (April 12, 2007).

5. B. Bruchmann et al., U.S. Patent Application 20060093885 (February 15, 2007).

6. J.-F. Stumbe et al., U.S. Patent Application 20070027269 (February 1, 2007).

Notes 3

B. Ink Dispersants and Colorants

a. Azo-benzothiazole polyethers

Title: Aqueous Inks Containing Colored PolymersAuthor: Jeffery H. Banning et al.Assignee: Xerox Corporation (Rochester, NY)

Patent Application: 20060074142 (April 6, 2006)Material Patentability: HighAnticipated Issuing Date: Mid-2008

Research Focus: Preparation of water-soluble organic ink colorants by incorporating chro-mophores onto oligomeric alkoxyethers.

Originality: Very versatile synthetic design for water-solubilizing ink colorants.Application: Jet printing ink

Thermal ink jet process

Observations: Two separate methods were used to solubilize colorants in an aqueousmedium:

a. Graft incorporation of the colorant onto a homophilic polymersubstrate

b. Incorporation of oligomeric hydrophilic substituents directly into thecolorants

The first method in this application, however, was limited to modifyingalcohol-containing colorants onto polymers containing grafted succinicanhydride transesterification, and transaminated reactions were alsoreported. In the second method water-soluble colorants were preparedby azo coupling of colorants with alkoxyether functionalized aniline.

4

REACTION

i. Phosphoric acid, sulfuric acid, 2-ethylhexanol, 2-amino-4-methylbenzothiazole,nitrosyl sulfuric acid, sulfamic acid, POE(10)-N-ethyl aniline, urea, sodiumhydroxide, CH2Cl2

EXPERIMENTAL

1. Preparation of water-soluble 4-methylbenzothiazole with alkoxyetherfunctionalized aniline

A vessel was charged with 85% H3PO4 (115 g), 95% H2SO4 (31 g), and 2 drops of2-ethylhexanol. Stirring was then initiated and the kettle was placed in an ice/saltbath to cool the mixture to about 08C. This mixture was then treated with 2-amino-4-methylbenzothiazole (10.2 g). A constant-pressure addition funnel was used toadd nitrosyl sulfuric acid (21.7 g) dropwise over a period of about 1.5 hours andthe mixture stirred an additional 90 minutes to ensure complete diazotization.Thereafter sulfamic acid (0.7 g) was added with stirring to neutralize any excessNOþ. The diazo mixture was then slowly added over 45 minutes to a 1-liter beakercontaining ice, POE(10)-N-ethyl aniline (36.0 g), 150 ml water, and 2.0 g of urea.The mixture was then stirred at 08C for 2 hours followed by stirring at ambient temp-erature overnight. The diazo colorant was then neutralized to a pH of 7 using 50%aqueous NaOH while keeping the reaction temperature below 608C. Followingneutralization, the colorant was poured into a 1-liter separatory funnel and allowedto phase separate. The bottom water/salt layer was discarded, and the colored organicproduct layer was isolated and dissolved in CH2Cl2 and then passed through a smallplug of silica gel to remove any polar impurities. The methylene chloride layer wasconcentrated yielding a viscous red liquid.

DERIVATIVES

Derivatives 5

NOTES

1. An alternative method for solubilizing a colorant through chemical graftingonto a functional polymer as indicated in Eq. (1) was also described in thisapplication.

(1)

2. Additional colorant agents were previously prepared by the authors (1) and aredescribed.

3. Beginning with quinizarin, Jaeger et al. (2) developed methods of makingdimeric colorant agents as illustrated in Eq. (2).

(2)

i. 1,36-Hexatriacontane diisocyanate

6 Aqueous Inks Containing Colored Polymers

4. An azo dye-colored composition, (I ), was prepared by Fujie et al. (3) in twosynthetic steps and used as a heat-sensitive recording ink sheet.

5. A colorant containing a curable sulfonamide composition, (II), was prepared byAraki (4) and used on a support as a color filter.

References

1. J.H. Banning et al., U.S. Patent Application 20070123701 (May 31, 2007) and U.S. Patent Application20060264674 (November 23, 2006).

2. C.W. Jaeger et al., U.S. Patent Application 20060178458 (August 10, 2006).

3. Y. Fujie et al., U.S. Patent Application 20080012930 (January 17, 2008).

4. K. Araki, U.S. Patent Application 20080014536 (January 17, 2008).

Notes 7

C. Oil Dispersants

a. Polyacrylate amino succimides

Title: Alkyl Acrylate Copolymer VI Modifiers andUses ThereofAuthor: Sanjay Srinivansan et al.Assignee: Afton Chemical Corporation (Richmond, VA)

Patent Application: 20080026964 (January 31, 2008)Material Patentability: HighAnticipated Issuing Date: Mid-2010

Research Focus: Preparation of polyacrylate viscosity improvers containing graftedN-phenyl-p-phenylenediamine as an antioxidant.

Originality: Departure from using oil viscosity improvers based on poly(ethylene-co-propylene)-g-succinic anhydride.

Application: Automotive oil viscosity improver

Observations: Most automotive oil viscosity improvers are based on shear stablepoly(ethylene-co-propylene) having Mn’s , 100,000 Da. Poly(ethylene-co-propylene) multifunctional viscosity improvers are prepared by freeradical grafting of maleic anhydride and then imidizing with N-phenyl-p-phenylenediamine. While polymethacrylate viscosity index improversare known, attempts to prepare them having a desirable balance ofantioxidancy and high- and low-temperature viscometric shear stabilityhave been elusive. This application has addressed that requirement.

8

REACTION

i. Butyl methacrylate, lauryl methacrylate, maleic anhydride, lauryl mercaptan, 2,20-azoisobutyronitrile

ii. N-Phenyl-p-phenylenediamine, ethoxylated lauryl alcohol

EXPERIMENTAL

1. Preparation of anhydride

Butyl methacrylate, lauryl methacrylate, and cetyl methacrylate were combined withmaleic anhydride, lauryl mercaptan, and process oil and then charged into a 2-literreaction vessel equipped with twomixing impellers rotated at 300 rpm during the reac-tion. The mixture was preheated to 858C and then treated with 2,20-azoisobutyronitrileand heated for 4 hours at 858C followed by 1 hour at 1008C. In some cases additionaloil was added to make the product more easily pourable. Unreacted maleic anhy-dride and other low-molecular-weight products were removed by heating the reactionmass to 1208C while applying a vacuum. Reaction scoping results are provided inTable 1.

2. Preparation of imide

The step 1 product was dissolved in process oil at 1358C and then treated with amixture of N-phenyl-p-phenylenediamine and ethoxylated lauryl alcohol andfurther heated to 160–1708C for 3 hours. The reaction mixture containing the multi-functionalized polymer reaction product was filtered where the nitrogen contentwas 0.36%.

Experimental 9

REACTION SCOPING

TESTING

High-Frequency Reciprocating Rig

Film formation properties of lubricating fluids containing selected experimental VIimprovers was determined using a high-frequency reciprocating rig (HFRR) accordingto the procedure outlined in SAE 2002-01-2793. Testing results are provided inTable 2.

NOTES

1. In subsequent investigations by Loper et al. (1) and Mathur et al. (2) oil disper-sant additives were prepared by reacting the step 1 product with triethylenetetra-mine, tetraethylenepentamine, pentaethylenehexamine, and bis-aminopropylpiperazine.

2. Vinci et al. (3) prepared automotive oil viscosity index improvers that consistedof copolymers of C12–C15 methacrylates with 2-ethylhexyl methacrylate andpoly(ethylene-co-propylene) with 2-ethylhexyl methacrylate, then blended in94.5 parts mineral oil.

TABLE 2. HFRR Testing Results Reflecting Film FormationProperties of Polymers in the Presence of Abrasive Contaminantsa

Carbon Black(%)

Comparative Example(%)

Imidized Entry 1(%)

0 87 915 37 608 12 50

aHigher results are preferred since it reflects a greater boundary film.

TABLE 1. Scoping Reaction for Preparation of Step 1 Producta

Reagentsb

EntryAIBN(wt%)

LSH(wt%)

MA(wt%)

BMA(wt%)

LMA(wt%)

CMA(wt%)

Mw(Da)

Mn(Da)

1 0.1 0.12 5.00 11.0 57.0 0.3 199,330 86,0033 0.1 0.16 5.00 11.0 57.0 0.3 142,055 66,8345 0.1 0.09 5.00 11.0 57.0 0.3 281,162 107,1796 0.04 0.04 4.42 9.73 50.47 0.3 578,520 195,858

a The viscosity index improver was prepared after reacting with N-phenyl-p-phenylenediamine.bAIBN ¼ 2,20-Azoisobutyronitrile, BMA ¼ butyl methacrylate, CMA ¼ cetyl methacrylate, LMA ¼lauryl methacrylate, LSH ¼ lauryl mercaptan, and MA ¼ maleic anhydride.

10 Alkyl Acrylate Copolymer VI Modifiers and Uses Thereof

3. Nanomaterials were used by Zhang et al. (4) as a replacement for polymer-basedviscosity modifiers for automotive lubricants. Compared with traditionalpolymer-based viscosity modifiers, nanomaterials induce a more even viscosityincrease across engine operating temperature ranges. In addition, nanomaterialsprovide a viscosity modifier that exhibits temporary shear loss that can contrib-ute to fuel economy.

References

1. J.T. Loper et al., U.S. Patent Application 20080027181 (January 31, 2008).

2. N.C. Mathur et al., U.S. Patent Application 20080026972 (January 31, 2008).

3. J.N. Vinci et al., U.S. Patent Application 20080015131 (January 17, 2008).

4. Z. Zhang et al., U.S. Patent Application 20070293405 (December 20, 2007).

Notes 11

D. Oil Drilling Dispersants

a. Polymethacrylate betaines

Title: Zwitterionic Polymers Comprising Betaine-TypeUnits and Use of Zwitterionic Polymers in Drilling FluidsAuthor: Katerina Karagianni et al.Assignee: Toyo Seikan Kaisha, Ltd. (Tokyo, JP)

Patent Application: 20080045420 (February 21, 2008)Material Patentability: LowAnticipated Issuing Date: 2010

Observations: The current application addresses the need for mineral agent inhibitors thatprevent the aggregation of argillaceous rocks and prevent the swelling ofclays during subterranean drilling. While acrylamide copolymers containingsulfobetaines or phosphobetaines are effective in addressing this problem,pollution concerns limit their application. Although this application haslimited novelty since both (a) co-methacrylates and (b) betainelike materialsterpolymer have previously been prepared, the use of these materials asdrilling dispersants is novel.

12

REACTION

i. a-Methoxy-v-methacrylate polyethylene glycol 1000, water, ethanol, ammoniumpersulfate

EXPERIMENTAL

1. Preparation of poly(sulfopropyldimethylammoniumethylmethacrylate-co-a-methoxy-v-methacrylate-polyethylene glycol)

A reactor charged with sulfopropyldimethylammoniumethyl methacrylate (0.020 mol),a-methoxy-v-methacrylate polyethylene glycol 1000 (0.009mol), water (398 g),and ethanol (261.90 g) was heated to 788C. The mixture was then simultaneouslytreated with ammonium persulfate (0.004 mol) dissolved in water (20 g) over 150minutes, ammonium persulfate (2.5 g) dissolved in water (60 g) continuously over120 minutes, sulfopropyldimethyl-ammoniumethyl methacrylate (0.182 mol) over120 minutes, and a-methoxy-v-methacrylate polyethylene glycol (0.078 mol), andwater (205.80 g). Thereafter the reaction was maintained at 708C for 90 minutesand then cooled. The solution was then treated with water and ethanol removed bydistillation. The product was isolated with a solids content of 27.3%, a pH of 2, aBrookfield viscosity of 36 mPa . s, and an Mw of 65,000 Da with an Mn of 8000 Da.

Experimental 13

DERIVATIVES

TABLE 1. Selected Zwitterionic Polymers Containing Betaine-Type Units Used asDrilling Fluid Component

Entry Repeat Unit Mw (Da) Mn (Da)

BrookfieldViscosity(mPa . s)

2 57,500 6500 31

4 30,000 4000 30

5 2,000,000 900,000 —

7 800,000 300,000 —

14 Zwitterionic Polymers Comprising Betaine-Type Units and Use of Zwitterionic Polymers