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    • 3. 发明授权
    • Method using fluoropolymer emulsions
    • 使用氟聚合物乳液的方法
    • US08507601B2
    • 2013-08-13
    • US12614482
    • 2009-11-09
    • Gerald Oronde BrownVictoria A. Helinski
    • Gerald Oronde BrownVictoria A. Helinski
    • C08F220/24C08F220/22C08L27/00C08K3/22
    • C09D133/066C08F2220/1858C08L33/24C09D133/14Y10T428/3154Y10T442/227C08L33/16C08L2666/04C08F220/24C08F2220/286C08F220/58
    • A method of providing oil repellency, water repellency, and dynamic water repellency to a substrate comprising contacting the substrate with a polymer composition comprising A) a first polymer comprising (a) hydrophobized nanoparticle; (b) C1 to C18, straight, branched, or cyclic alkyl (meth)acrylate; (c) N-methylol (meth)acrylamide or a monomer of formula (I) R—(OCH2CH2)a—O—C(O)—C(R1)═CH2  (I) wherein R is hydrogen, C1-C4 alkyl, or —C(O)—C(R1)═CH2, and R1 is H or —CH3; said first polymer in contact with B) a second polymer comprising (d) a fluorinated monomer of formula (II) Rf1-L-X—C(O)—C(R)═CH2  (II) wherein Rf1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having 2 to about 100 carbon atoms; optionally interrupted by 1 to about 50 oxygen atoms; wherein the ratio of carbon atoms to oxygen atoms is at least 2:1 and no oxygen atoms are bonded to each other; L is a bond or a linear or branched divalent linking group having 1 to about 20 carbon atoms, said linking group optionally interrupted by 1 to about 4 hetero-radicals selected from the group consisting of —O—, —NR6—, —S—, —SO—, —SO2—, and —N(R6)C(O)— wherein R6 is H or C1 to C6 alkyl, and said linking group optionally substituted with CH2Cl; X is —O—, —N(R)—, or —S—, wherein R is H or CH3; (e) a monomer as described in (b) above; and (f) a monomer as described in (c) above; provided that the first polymer comprises from about 50% to about 70% by weight of the polymer composition.
    • 提供对基材提供拒油性,拒水性和动态拒水性的方法,包括使基材与聚合物组合物接触,所述聚合物组合物包含A)包含(a)疏水化纳米颗粒的第一聚合物; (b)C1至C18,直链,支链或环状(甲基)丙烯酸烷基酯; (C)N-羟甲基(甲基)丙烯酰胺或式(I)的单体R-(OCH2CH2)aOC(O)-C(R1)= CH2(I)其中R是氢,C1-C4烷基或-C (O)-C(R 1)= CH 2,并且R 1是H或-CH 3; 所述第一聚合物与B)接触的第二聚合物包含(d)式(II)的氟化单体的第二聚合物Rf1-LXC(O)-C(R)= CH2(II)其中Rf1是单价,部分或完全氟化的, 具有2至约100个碳原子的直链或支链的烷基; 任选地被1至约50个氧原子中断; 其中碳原子与氧原子的比例为至少2:1,并且没有氧原子彼此键合; L是具有1至约20个碳原子的键或直链或支链二价连接基团,所述连接基团任选被1至约4个选自-O - , - NR 6 - , - S - ,-SO - , - SO 2 - 和-N(R 6)C(O) - ,其中R 6为H或C 1至C 6烷基,所述连接基团任选被CH 2 Cl取代; X是-O - , - N(R) - 或-S-,其中R是H或CH 3; (e)如上述(b)所述的单体; 和(f)如上述(c)所述的单体; 条件是第一聚合物占聚合物组合物重量的约50%至约70%。
    • 5. 发明授权
    • Fluorosilanes
    • 氟硅烷
    • US08058463B2
    • 2011-11-15
    • US12323593
    • 2008-11-26
    • Axel Hans-Joachim HerzogGerald Oronde Brown
    • Axel Hans-Joachim HerzogGerald Oronde Brown
    • C07F7/10C07D231/00
    • C07F7/1804
    • Fluoroalkyl silanes are a class of compounds useful for various industrial purposes. For example, fluoroalkyl silanes which have hydrolysable groups (called hydrolysable fluoroalkyl silanes), are compounds useful as surface treatment agents which provide durable hydrophobic and oleophobic coatings. In general, hydrolysable fluoroalkyl silanes can be represented with the following formula: (RO—)3Si—RT wherein R is H or an alkyl; and RT is a monovalent organic compound terminated by a perfluoroalkyl group. When used to coat a surface, the (RO—)3 moiety reacts (via hydrolysis) with various chemical groups of the surface (e.g., hydroxyl, amine, or other reactive groups) thereby bonding the fluoroalkyl silane to the surface The RT moiety comprises a divalent organic linking group which links the silicon atom to a terminal group rich in fluorine atoms whose unique electronic properties impart desirable hydrophobic and oleophobic properties in a surface coating. Modification of the RT moiety is useful in the engineering of fluoroalkyl silanes. The present invention provides for fluoroalkyl silanes having RT moieties which have not been heretofore considered.
    • 氟烷基硅烷是一类可用于各种工业目的的化合物。 例如,具有可水解基团的氟代烷基硅烷(称为可水解氟烷基硅烷)是可用作表面处理剂的化合物,其提供耐久的疏水和疏油涂层。 通常,可水解的氟烷基硅烷可用下式表示:(RO-)3Si-RT其中R是H或烷基; RT是由全氟烷基封端的一价有机化合物。 当用于涂覆表面时,(RO-)3部分(通过水解)与表面的各种化学基团(例如羟基,胺或其它反应性基团)反应,从而将氟代烷基硅烷键合到表面。RT部分包含 将硅原子连接到富含氟原子的末端基团的二价有机连接基团,其独特的电子性质在表面涂层中赋予所需的疏水性和疏油性。 RT部分的修饰可用于氟烷基硅烷的工程化。 本发明提供了具有迄今尚未考虑的RT部分的氟代烷基硅烷。
    • 6. 发明申请
    • FLUOROPOLYMER COMPOSITIONS AND TREATED SUBSTRATES
    • 氟聚合物组合物和处理的基材
    • US20110084227A1
    • 2011-04-14
    • US12577334
    • 2009-10-12
    • Gerald Oronde BrownMichael Henry Ober
    • Gerald Oronde BrownMichael Henry Ober
    • D06M15/564
    • D06M15/564D06M15/576D06M2200/11D06M2200/12Y10T428/31551Y10T442/198Y10T442/2164Y10T442/2172Y10T442/218Y10T442/2197Y10T442/2213Y10T442/2221Y10T442/2246Y10T442/227Y10T442/2279Y10T442/2287Y10T442/2385Y10T442/2459Y10T442/2533Y10T442/259Y10T442/30Y10T442/3301Y10T442/3764Y10T442/3805Y10T442/3813
    • A composition for imparting surface properties to substrates comprising a polymer of at least one polyurethane having at least one urea linkage prepared by: (i) reacting (a) at least one diisocyanate, polyisocyanate, or mixture thereof, having isocyanate groups, and (b) at least one fluorinated compound selected from the formula (I): Rf1-L-X  (I) wherein Rf1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having 2 to 100 carbon atoms; optionally interrupted by 1 to 50 oxygen atoms; wherein the ratio of carbon atoms to oxygen atoms is at least 2:1 and no oxygen atoms are bonded to each other; L is a bond or a linear or branched divalent linking group having 1 to about 20 carbon atoms, said linking group optionally interrupted by 1 to about 4 hetero-radicals selected from the group consisting of —O—, —NR1—, —S—, —SO—, —SO2—, and —N(R1)C(O)— wherein R1 is H or C1 to C6 alkyl, and said linking group optionally substituted with CH2Cl; X is an isocyanate-reactive group selected from the group consisting of —OH, —N(R)H, and —SH; and thereafter (ii) reacting with (c) water and (d) 0.05 to about 2.0 % by weight of an isocyanate-reactive fluorinated particulate component, based on a total dry weight of the composition.
    • 使具有至少一种具有至少一个脲键的聚氨酯的聚合物的表面性能赋予基材的组合物,其通过以下步骤制备:(i)使(a)至少一种具有异氰酸酯基团的二异氰酸酯,多异氰酸酯或其混合物与(b )至少一种选自式(I)的氟化化合物:Rf1-LX(I)其中Rf1是具有2至100个碳原子的一价,部分或完全氟化的直链或支链烷基; 任选地被1至50个氧原子中断; 其中碳原子与氧原子的比例为至少2:1,并且没有氧原子彼此键合; L是具有1至约20个碳原子的键或直链或支链二价连接基团,所述连接基团任选被1至约4个选自-O - , - NR 1 - , - ,-SO-,-SO 2 - 和-N(R 1)C(O) - ,其中R 1为H或C 1至C 6烷基,所述连接基团任选被CH 2 Cl取代; X是选自-OH,-N(R)H和-SH的异氰酸酯反应性基团; 然后(ii)基于组合物的总干重与(c)水和(d)0.05至约2.0重量%的异氰酸酯反应性氟化颗粒组分反应。
    • 7. 发明申请
    • SURFACE MODIFIED INORGANIC PARTICLES
    • 表面改性无机颗粒
    • US20090176097A1
    • 2009-07-09
    • US12328122
    • 2008-12-04
    • Gerald Oronde BrownAxel Hans-Joachim Herzog
    • Gerald Oronde BrownAxel Hans-Joachim Herzog
    • B32B9/04C07F7/10
    • C09C3/12C01P2002/86C09C1/043C09C1/3081C09C1/3684C09C1/407Y10T428/2991
    • Inorganic particles hydrophobized with fluorosilanes have been used to impart hydrophobic as well as oleophobic properties as exemplified by U.S. Patent Application, US2006/0222815, filed by Oles et al. which teaches making such hydrophobized particles by the covalent bonding (i.e. grafting) of fluorosilanes upon the surface of inorganic particles (e.g. silica). The fluorosilanes employed by Oles et al. consist of a silicon atom having four bonds, three of which are direct bonds to hydrolysable groups which can react with the surface of an inorganic particle thereby covalently bonding the fluorosilane to particle. The remaining bond is a direct bond from the silicon atom to a perfluoroalkyl group. In contrast, the hydrophobized inorganic particles of the present invention comprise residues from fluorosilanes wherein the silicon atom is first bonded to a divalent organic linking group which in turn is bonded to a perfluoroalkyl group. It has been discovered that incorporation of the aforementioned divalent organic linking group can improve the ability of resulting hydrophobized inorganic particles to impart hydrophobic as well as oleophobic properties.
    • 用氟硅烷疏水化的无机颗粒已被用于赋予疏水性以及疏油性,如Oles等人提交的美国专利申请US2006 / 0222815所示。 其教导通过在无机颗粒(例如二氧化硅)的表面上共价键合(即接枝)氟硅烷来制造这种疏水化颗粒。 Oles等人采用的氟硅烷 由具有四个键的硅原子组成,其中三个直接键合到可水解基团,其可与无机颗粒的表面反应,从而共价键合氟硅烷至颗粒。 剩余的键是从硅原子到全氟烷基的直接键合。 相比之下,本发明的疏水化无机颗粒包含氟硅烷的残基,其中硅原子首先与二价有机连接基团键合,二价有机连接基团又与全氟烷基键合。 已经发现,上述二价有机连接基团的引入可以提高所得疏水化无机颗粒赋予疏水性和疏油性能的能力。
    • 10. 发明授权
    • Fluoroalkyl silanes
    • 氟烷基硅烷
    • US08501952B2
    • 2013-08-06
    • US13242434
    • 2011-09-23
    • Axel Hans-Joachim HerzogGerald Oronde Brown
    • Axel Hans-Joachim HerzogGerald Oronde Brown
    • C07D231/00
    • C07F7/1804
    • The present invention is directed to a fluorosilane represented by (L)3-Si—(CH2)n—N(-Q3-Rf)-Q1-Rf where each n is independently an integer from 1 to 12; L is independently chosen from a hydrolysable or non-hydrolysable monovalent group Rf is chosen from a C2-C12 perfluoroalkyl provided that: i) one fluorine atom of the perfluoroalkyl can be optionally replaced by hydrogen, and/or ii) the perfluoroalkyl can be optionally interrupted by at least one oxygen, methylene, or ethylene; Q1 is chosen from the group consisting of a C2-C12 hydrocarbylene optionally interrupted by at least one divalent organic group; X1 is chosen from O or S; and b) Q1 and Q3 are independently chosen from the group consisting of a C2-C12 hydrocarbylene interrupted by at least one of —C(O)—O— or —O—C(O)—, and optionally further interrupted by at least one divalent organic group.
    • 本发明涉及由(L)3-Si-(CH2)n-N(-Q3-Rf)-Q1-Rf表示的氟硅烷,其中每个n独立地为1至12的整数; L独立地选自可水解或不可水解的一价基团,Rf选自C 2 -C 12全氟烷基,条件是:i)全氟烷基的一个氟原子可任选被氢替代,和/或ii)全氟烷基可任选地 被至少一个氧,亚甲基或乙烯中断; Q1选自任选被至少一个二价有机基团中断的C 2 -C 12亚烃基; X1选自O或S; 和b)Q1和Q3独立地选自被-C(O)-O-或-OC(O) - 中的至少一个间隔的C 2 -C 12亚烃基,并任选进一步被至少一个二价 有机组。