IL110136A - Process for producing functionalized polymers via enamine of acetoacetate - Google Patents

Process for producing functionalized polymers via enamine of acetoacetate

Info

Publication number
IL110136A
IL110136A IL11013694A IL11013694A IL110136A IL 110136 A IL110136 A IL 110136A IL 11013694 A IL11013694 A IL 11013694A IL 11013694 A IL11013694 A IL 11013694A IL 110136 A IL110136 A IL 110136A
Authority
IL
Israel
Prior art keywords
acetoacetate
polymer
monomer
functionalized polymers
producing functionalized
Prior art date
Application number
IL11013694A
Other languages
English (en)
Other versions
IL110136A0 (en
Original Assignee
Rohm & Haas
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm & Haas filed Critical Rohm & Haas
Publication of IL110136A0 publication Critical patent/IL110136A0/xx
Publication of IL110136A publication Critical patent/IL110136A/xx

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/12—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/30—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and unsaturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)
IL11013694A 1993-07-14 1994-06-27 Process for producing functionalized polymers via enamine of acetoacetate IL110136A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/091,489 US5525662A (en) 1993-07-14 1993-07-14 Functionalization of polymers via enamine of acetoacetate

Publications (2)

Publication Number Publication Date
IL110136A0 IL110136A0 (en) 1994-10-07
IL110136A true IL110136A (en) 1999-09-22

Family

ID=22228053

Family Applications (1)

Application Number Title Priority Date Filing Date
IL11013694A IL110136A (en) 1993-07-14 1994-06-27 Process for producing functionalized polymers via enamine of acetoacetate

Country Status (12)

Country Link
US (5) US5525662A (fr)
EP (1) EP0634425B1 (fr)
JP (1) JP3787168B2 (fr)
KR (2) KR100365104B1 (fr)
CN (2) CN1051319C (fr)
AU (1) AU687398B2 (fr)
BR (1) BR9402671A (fr)
CA (1) CA2127570A1 (fr)
DE (1) DE69426659T2 (fr)
IL (1) IL110136A (fr)
RU (1) RU94026093A (fr)
ZA (1) ZA944717B (fr)

Families Citing this family (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5783626A (en) * 1995-04-12 1998-07-21 Taylor; James Wayne Waterborne polymers with pendant crosslinkable groups
US5539073A (en) * 1995-04-12 1996-07-23 Eastman Chemical Company Waterborne polymers having pendant allyl groups
US5772988A (en) * 1996-05-10 1998-06-30 Revlon Consumer Products Corporation Nail enamel compositions from acetoacetoxy methacrylate copolymer
US6028155A (en) * 1997-05-21 2000-02-22 Eastman Chemical Company Surfactant-containing acetoacetoxy-functional and enamine-functional polymers
US5998543A (en) * 1996-05-28 1999-12-07 Eastman Chemical Company Stable amino-containing polymer latex blends
CN1226260A (zh) 1996-05-28 1999-08-18 伊斯曼化学公司 含有表面活性剂的乙酰乙酰氧基－官能和烯胺－官能聚合物
US5891950A (en) * 1996-05-28 1999-04-06 Eastman Chemical Company Use of stable amino-functional latexes in water-based inks
US6417267B1 (en) 1996-05-28 2002-07-09 Eastman Chemical Company Adhesive compositions containing stable amino-containing polymer latex blends
US5962556A (en) * 1996-10-22 1999-10-05 Eastman Chemical Company Functional latexes resistant to hydrolysis
US6512042B1 (en) 1996-12-18 2003-01-28 Rohm And Haas Company Waterborne crosslinkable coating compositions
US5922790A (en) 1997-01-09 1999-07-13 Eastman Chemical Company Non-polymeric acetoacetates as adhesion promoting coalescing agents
US5913970A (en) * 1997-01-16 1999-06-22 Eastman Chemical Company Stabilized non-polymeric acetoacetate esters that promote adhesion to metallic and oxidized substrates
GB2323599A (en) * 1997-03-18 1998-09-30 Courtaulds Plc Compositions curable by a Michael reaction
JP4242930B2 (ja) * 1997-05-21 2009-03-25 イーストマン ケミカル カンパニー フィルム形成まで化学的及び物理的に安定な反応性ラテックスブレンドを調製する方法
US6333378B1 (en) 1997-08-12 2001-12-25 Eastman Chemical Company Acrylic modified waterborne alkyd or uralkyd dispersions
CN1174060C (zh) 1997-08-12 2004-11-03 伊斯曼化学公司 丙烯酸改性水性醇酸分散液
US5990224A (en) * 1997-09-18 1999-11-23 Eastman Chemical Company Stable low foam waterborne polymer compositions containing poly(alkyleneimines)
US6201048B1 (en) 1997-09-18 2001-03-13 Eastman Chemical Company Stable waterborne polymer compositions containing poly(alkyleneimines)
US6649679B1 (en) 1997-09-18 2003-11-18 Eastman Chemical Company Stable waterborne polymer compositions containing poly(alkylenimines)
US6005035A (en) * 1997-09-18 1999-12-21 Eastman Chemical Company Stable waterborne polymer compositions containing poly(alkylenimines)
US6121399A (en) * 1997-10-23 2000-09-19 Eastman Chemical Company Polymers of 3-butene esters, their preparation and use
US6348623B2 (en) 1997-10-23 2002-02-19 Eastman Chemical Company Polymers of 3-butene esters, their preparation and use
US6121400A (en) * 1997-10-23 2000-09-19 Eastman Chemical Company Polymers of 3-butene esters, their preparation and use
US6277358B1 (en) 1997-12-15 2001-08-21 Revlon Consumer Products Corporation Cosmetic compositions containing crosslinkable polymers
US6037390A (en) * 1997-12-31 2000-03-14 E. I. Du Pont De Nemours And Company Smear resistant pigmented ink jet inks containing β-diketone or ureido dispersants
CA2348895C (fr) 1998-11-20 2005-04-12 The Sherwin-Williams Company Compositions durcissables a fonction acetoacetoxy et imine
US6221976B1 (en) 1999-01-25 2001-04-24 The Dow Chemical Company Polymers containing partially neutralized silanols
US6337106B1 (en) 1999-06-01 2002-01-08 Rohm And Haas Method of producing a two-pack fast-setting waterborne paint composition and the paint composition therefrom
JP3816697B2 (ja) * 1999-07-07 2006-08-30 大日精化工業株式会社 重合体が結合した機能剤、その製造方法、それらの使用方法及びそれらを使用した物品
US6229007B1 (en) * 1999-09-30 2001-05-08 Basf Corporation Amine functional cellulose ester compounds and methods of making the same
ES2252222T3 (es) * 2000-04-12 2006-05-16 Akzo Nobel Coatings International B.V. Composicion acuosa de dos componentes reticulable.
GB0015245D0 (en) * 2000-06-22 2000-08-16 Avecia Ltd Composition and process
US6521715B1 (en) 2000-08-22 2003-02-18 E. I. Du Pont De Nemours And Company Graft copolymer pigment dispersants
US6524656B2 (en) * 2001-02-23 2003-02-25 Rohm And Haas Company Coating method
US7396871B2 (en) * 2002-01-14 2008-07-08 Eastman Chemical Comapny Rubber modified acrylic and/or vinyl hybrid resins
US6893722B2 (en) 2002-04-29 2005-05-17 Exxonmobil Oil Corporation Cationic, amino-functional, adhesion-promoting polymer for curable inks and other plastic film coatings, and plastic film comprising such polymer
US7195818B2 (en) * 2002-05-01 2007-03-27 Exxonmobil Oil Corporation Sealable multi-layer opaque film
US20040105994A1 (en) * 2002-12-03 2004-06-03 Pang-Chia Lu Thermoplastic film structures with a low melting point outer layer
EP1431328A1 (fr) * 2002-12-19 2004-06-23 Sika Technology AG Polymères contenant 3-(N-Silyalkyl)-amino-propenate et leur production
WO2005056700A1 (fr) 2003-12-06 2005-06-23 Fujifilm Imaging Colorants Limited Procede de preparation de matieres solides particulaires modifiees, encres comprenant ces dernieres
US20050131176A1 (en) * 2003-12-10 2005-06-16 Cheng-Le Zhao Process for production of polymer dispersions containing an acetoacetate moiety
GB0413630D0 (en) 2004-06-18 2004-07-21 Avecia Ltd Process
US20060046005A1 (en) * 2004-08-24 2006-03-02 Mcgee Dennis E Coating for polymeric labels
US7402624B2 (en) * 2004-11-08 2008-07-22 E.I. Du Pont De Nemours & Company Graft copolymers with segmented arms and their preparation and use
AU2007201184B8 (en) * 2006-04-11 2013-02-07 Rohm And Haas Company Dirt pickup resistant coating binder having high adhesion to substrates
TW200815556A (en) * 2006-06-01 2008-04-01 Akzo Nobel Coatings Int Bv Adhesive system
US7855261B2 (en) 2006-12-08 2010-12-21 Eastman Chemical Company Aldehyde removal
US20080135058A1 (en) * 2006-12-08 2008-06-12 Ted Calvin Germroth Tobacco smoke filter and method for removal of aldehydes from tobacco smoke
US20080134893A1 (en) * 2006-12-08 2008-06-12 Thauming Kuo Particulate filter media
US8357540B2 (en) * 2006-12-21 2013-01-22 3M Innovative Properties Company Polymeric substrates with fluoroalkoxycarbonyl groups for amine capture
US8906703B2 (en) * 2006-12-21 2014-12-09 3M Innovative Properties Company Surface-bound fluorinated esters for amine capture
US20090163635A1 (en) * 2007-12-19 2009-06-25 Eastman Chemical Company Aqueous dispersions of adhesion promoters
US20100081752A1 (en) * 2008-09-26 2010-04-01 E. I. Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
WO2010085631A2 (fr) * 2009-01-23 2010-07-29 Bridgestone Corporation Polymères fonctionnalisés avec des composés polycyano
JP2013508318A (ja) 2009-10-21 2013-03-07 バイエル・ファルマ・アクチェンゲゼルシャフト 置換されたベンゾスルホンアミド誘導体
EP2526149B1 (fr) * 2010-01-22 2017-03-01 Bridgestone Corporation Polymères fonctionnalisés par des composés nitrile contenant un groupe amino protégé
US8809446B2 (en) 2010-12-15 2014-08-19 Eastman Chemical Company Substituted 3-oxopentanoates and their uses in coating compositions
US8809447B2 (en) 2010-12-15 2014-08-19 Eastman Chemical Company Acetoacetate-functional monomers and their uses in coating compositions
US9029451B2 (en) 2010-12-15 2015-05-12 Eastman Chemical Company Waterborne coating compositions that include 2,2,4-trimethyl-3-oxopentanoate esters as reactive coalescents
WO2012134695A1 (fr) 2011-03-29 2012-10-04 Exxonmobil Oil Corporation Revêtements de film à base de polymères de condensation de polyalkylamine
US20140141262A1 (en) * 2011-06-29 2014-05-22 Sun Chemical Corporation Vinyl alcohol polymers with silane side chains and compositions comprising the same
US20130084437A1 (en) 2011-09-29 2013-04-04 Dennis E. McGee Film Coatings Based on Polyalkylimine Condensation Polymers
AU2011379106B2 (en) * 2011-10-11 2015-12-24 Rohm And Haas Company Aqueous polymer dispersion
US20130224404A1 (en) * 2012-02-28 2013-08-29 Cray Valley Usa, Llc Isocyanate-free insulated glass sealant and insulated glass units using the same
EP2748237A1 (fr) 2012-05-01 2014-07-02 Jindal Films Americas, LLC Revêtements de film de polyalkylèneimine époxylée
EP2945994B1 (fr) 2013-01-18 2018-07-11 Basf Se Compositions de revêtement à base de dispersion acrylique
KR101518504B1 (ko) 2013-10-17 2015-05-11 제일모직주식회사 편광판용 접착제 조성물, 이를 포함하는 편광판용 접착 필름, 이를 포함하는 편광판 및 이를 포함하는 광학 표시 장치
CA2983239A1 (fr) 2015-04-24 2016-10-27 The Penn State Research Foundation Polymeres a base d'eau aptes a la chimie clic et polymeres a base d'eau reticules par chimie clic
ES2930250T3 (es) 2018-10-10 2022-12-09 Dow Global Technologies Llc Composición a base de agua
JP7407270B2 (ja) * 2019-08-09 2023-12-28 シントマー スンディリアン ブルハド 自己回復特性を有するエラストマーフィルムの調製のためのポリマーラテックス組成物
CN111349393A (zh) * 2020-02-25 2020-06-30 江西科技师范大学 一种新型植物油基的有机-无机杂化涂层材料的制备方法
CN113372479B (zh) * 2021-07-20 2023-04-28 安徽工程大学 利用可功能化酰胺动态共价键制备的交联乙酰乙酸基甲基丙烯酸乙酯共聚物及制备方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328325A (en) * 1966-03-09 1967-06-27 Rohm & Haas Floor polish and method of use
GB1185216A (en) * 1966-05-28 1970-03-25 Basf Ag Production of coated, impregnated or bonded articles
US3467610A (en) * 1967-11-29 1969-09-16 Rohm & Haas Aqueous floor polish compositions containing a water-insoluble addition polymer and a polyvalent metal chelate
US4150005A (en) * 1977-03-17 1979-04-17 Rohm And Haas Company Internally plasticized polymer latex
US4254279A (en) * 1979-09-24 1981-03-03 Fmc Corporation Ester resolution process
JPS6121171A (ja) * 1984-07-09 1986-01-29 Hoechst Gosei Kk 速硬化水性接着剤と接着方法
US4626567A (en) * 1985-10-25 1986-12-02 Beecham Home Improvement Products Inc. Water-resistant clear and colored acrylic latex sealant
US4908403A (en) * 1986-05-02 1990-03-13 Union Oil Of California Pressure sensitive adhesives of acetoacetoxy-alkyl acrylate polymers
JPH0757863B2 (ja) * 1987-12-29 1995-06-21 日本合成化学工業株式会社 感圧性接着剤組成物
GB8811436D0 (en) * 1988-05-13 1988-06-15 Polyvinyl Chemie Holland Bv Aqueous coating compositions
ES2067547T3 (es) * 1988-08-26 1995-04-01 Nippon Oils & Fats Co Ltd Agente dispersante de pigmento.
US4960924A (en) * 1988-10-31 1990-10-02 Rohm And Haas Company Mercaptoalkyl acetoacetates
US5055506A (en) * 1988-12-30 1991-10-08 Union Oil Company Of California Polymer systems and methods for their production
GB9005838D0 (en) * 1989-03-29 1990-05-09 Ici Plc Aqueous coating compositions
JPH036236A (ja) * 1989-06-01 1991-01-11 Nippon Oil & Fats Co Ltd 反応性樹脂粒子
US5017676A (en) * 1989-12-18 1991-05-21 Texaco Chemical Company Acetoacetoxyethyl methacrylate in the cure of epoxy resins
GB9101205D0 (en) * 1990-02-14 1991-02-27 Ici Plc Incorporation of desired groups into polymers,the polymers so produced and composition containing them
DE4034279A1 (de) * 1990-10-27 1992-04-30 Bayer Ag Verwendung von alkoxysilylaminen als haerter fuer acetoacetat- oder acetoacetamidgruppen aufweisende kunststoffvorlaeufer
NL9002380A (nl) * 1990-11-01 1992-06-01 Stamicarbon Bindmiddelsamenstelling op basis van een acrylaatpolymeer en een kruisvernetter op basis van een acetoacetaatverbinding.
US5124384A (en) * 1990-11-16 1992-06-23 Air Products And Chemicals, Inc. Transparent caulks containing fumed silica
JPH04189874A (ja) * 1990-11-22 1992-07-08 Nippon Oil & Fats Co Ltd 塗料用樹脂組成物
ATE148146T1 (de) * 1990-12-21 1997-02-15 Rohm & Haas Lufthärtende polymerzusammensetzung
US5391624A (en) * 1992-02-10 1995-02-21 S. C. Johnson & Son, Inc. Thermosettable compositions
AT396934B (de) * 1992-02-14 1993-12-27 Vianova Kunstharz Ag Verfahren zur herstellung von wässrigen, selbstvernetzenden polymerdispersionen und ihre verwendung als bindemittel für lagerstabile einkomponentenlacke
US5362816A (en) * 1992-06-04 1994-11-08 Rohm And Haas Company High cohesive strength pressure-sensitive adhesives incorporating acetoacetate
US5349026A (en) * 1992-11-20 1994-09-20 Rohm And Haas Company Reactive coalescents

Also Published As

Publication number Publication date
US5494975A (en) 1996-02-27
JP3787168B2 (ja) 2006-06-21
US5494961A (en) 1996-02-27
US5548024A (en) 1996-08-20
JPH07138317A (ja) 1995-05-30
CA2127570A1 (fr) 1995-01-15
BR9402671A (pt) 1995-05-02
US5616764A (en) 1997-04-01
EP0634425B1 (fr) 2001-02-07
CN1238342A (zh) 1999-12-15
ZA944717B (en) 1995-01-18
RU94026093A (ru) 1996-05-27
EP0634425A1 (fr) 1995-01-18
DE69426659D1 (de) 2001-03-15
KR960014165A (ko) 1996-05-22
KR100365104B1 (ko) 2003-03-03
KR100393405B1 (ko) 2003-07-31
US5525662A (en) 1996-06-11
DE69426659T2 (de) 2001-06-21
AU6731894A (en) 1995-01-27
AU687398B2 (en) 1998-02-26
IL110136A0 (en) 1994-10-07
CN1102414A (zh) 1995-05-10
CN1051319C (zh) 2000-04-12

Similar Documents

Publication Publication Date Title
IL110136A (en) Process for producing functionalized polymers via enamine of acetoacetate
CA2039953A1 (fr) Polymeres et copolymeres dieniques termines par reaction avec des n-alkylimines et des n-arylimines
US4169924A (en) Preparation of linear cyclic polyimides from latices
AU1272200A (en) Functionalized polyallylamines and process for producing the same
ATE195328T1 (de) Geschützte funktionelle initiatoren zur herstellung von am kettenende funktionalisierte polymeren
AU1923200A (en) Surface modified divinylbenzene resin having a hemocompatible coating
MY120719A (en) Polymeric compositions and their production and uses
EP0735186A3 (fr) Adjuvant pour la papeterie et procédé papetier
DE3472243D1 (en) A flocculating agent and a process for its production
DE59106705D1 (de) Verfahren zur Herstellung von Homopolymerisaten des Propylens mit breitem Molmassenverhältnis.
EP0481345A3 (en) Liquid coating composition
KR950032353A (ko) 분산제로서 적합한 중합물질
ES2074196T3 (es) Peroxidos funcionalizados para reacciones de polimerizacion.
KR910000914A (ko) 폴리머/폴리올용 안정화제
MX9702773A (es) Sintesis de polimeros.
EP0041651B1 (fr) Procédé de fabrication d'agents de resistence à l'humidite pour le papier
DE60007664D1 (de) Elektroabscheidbare tauchlack zusammensetzung enthaltend ein carbamathaltiges harz mit mindestens einer quaternären ammoniumgruppe und mindestens einer carbamatgruppe
AU581911B2 (en) Aldehyde or imine oxygen scavengers for vinyl polymerizations
CA2033740A1 (fr) Melanges de dispersions aqueuses de polymeres
ATE134660T1 (de) Herstellung von schmelzverarbeitbaren acrylonitril/methacrylonitril-copolymeren
ATE183540T1 (de) Verwendung von wässrigen dispersionen als heisssiegellack
CA2195346A1 (fr) Benzocyclobutenones et polymeres derives
EP0246875A3 (fr) Polymères liquides
DE3278281D1 (en) Quaternary ammonium compounds containing surfactant anions, polymers thereof, polymerisable compositions containing them, methods of making the monomers and polymers and articles containing polymer
JPS6485398A (en) Production of paper

Legal Events

Date Code Title Description
FF Patent granted
RH Patent void