KR20050016482A - Fluorochemical Treatment for Silicon Articles - Google Patents

Abstract

Silicon substrates having Si—H bonds are chemically modified using fluorinated olefins of the formula:

Where

m is an integer of 1 or more,

n is an integer of 0 or more,

Z is a divalent linking group,

R _f is a highly fluorinated organic group.

Description

Fluorochemical Treatment for Silicon Articles

The present invention generally relates to chemical modification of silicon substrates, and more particularly to chemical modification of silicon-based microelectromechanical systems (ie MEMS) devices.

MEMS devices are used, for example, as airbag accelerometers, microengines, optical switches, rotary motion devices, sensors and movers. MEMS devices are typically fabricated from silicon wafers using microlithography and are independently positioned active silicon elements (eg gears, hinges, levers, slides) that must be free to move and rotate, etc. And mirrors). The inherent mechanical nature of a MEMS device causes high and increased levels of complexity for its production and reliability.

Since MEMS devices generally have a large surface area-to-volume ratio, their performance is often governed by the strong adhesion (ie, stiction) of active silicon elements to each other and / or to a supporting silicon substrate. Adhesion is caused by capillary forces (e.g., caused by high critical surface tension of the silicon surface of the MEMS device), electrostatic forces, van der Waals forces, and / or "chemical" forces such as hydrogen bonding and solid bridging May be induced. Sticking may occur, for example, during or after the release of the MEMS device via etching (eg during use).

Sticking, friction, and abrasion are major problems that limit both the production yield and useful life of many MEMS devices, and are damaging to the MEMS industry from the outset.

To solve the problem of sticking, various treatments that reduce sticking (ie, anti-sticking treatments) are commonly used. Such treatment typically reduces capillary forces by reducing the surface energy of the MEMS surface (which causes, for example, high forward and / or backward contact angles with water). Ideally, the anti-sticking treatment is stable at typical operating temperatures of the MEMS device (eg in the range of -40 to + 130 ° C). In some cases, the anti-stick treatment may also function to lubricate MEMS device movements to ensure proper functioning and to reduce wear rates.

Many anti-stick and / or lubricating treatments are simple liquid coatings and therefore tend to be lost or eliminated over time. Other anti-sticking treatments use various graft techniques to chemically bond the anti-stick coating to the silicon surface of the MEMS device. However, although fixation reduction can be achieved in this way, there is a continuing need for further improvements in anti-sticking treatments.

Summary of the Invention

In one embodiment, the present invention

Providing a silicon substrate having a plurality of Si—H bonds;

Providing a composition comprising a fluorinated olefin of formula: And

Contacting the composition with the silicon substrate under conditions such that the fluorinated olefin will covalently adhere to the surface of the silicon substrate

It provides a method of modifying a silicon substrate comprising:

Where

m is an integer of 1 or more,

n is an integer of 0 or more,

Z is a divalent linking group,

R _f is a highly fluorinated organic group.

In another aspect, the invention

Providing a silicon substrate;

Etching the silicon substrate to form a plurality of Si—H bonds;

Providing a composition comprising a fluorinated olefin of formula: And

Contacting the composition with the silicon substrate under conditions such that the fluorinated olefin will covalently adhere to the silicon substrate

It provides an article comprising a chemically modified silicon substrate prepared according to a method comprising:

Where

m is an integer of 1 or more,

n is an integer of 0 or more,

Z is a divalent linking group,

R _f is a highly fluorinated organic group.

In another aspect, the present invention provides an article comprising a chemically modified silicon substrate, wherein the chemically modified substrate comprises one or more silicon atoms covalently bonded to an organic group of the formula:

Where

m is an integer of 1 or more,

n is an integer of 0 or more,

Z is a divalent linking group,

R _f is a highly fluorinated organic group,

Si _sub is a substrate silicon atom directly bonded to one or more additional substrate silicon atoms.

Surface-modified silicon substrates made in accordance with the present invention exhibit good properties (eg, hydrophobicity and / or oleophobicity). The methods and materials of the present invention are available in MEMS devices that provide anti-stick coatings that are particularly useful in the manufacture of a wide variety of silicon-based articles.

The present invention relates to materials and methods for modifying silicon substrates having chemically accessible Si-H bonds. The modification is accomplished by hydrosilylation of the Si—H bond with one or more fluorinated olefins. In hydrosilylation, Si—H bonds are added across the terminal carbon-carbon double bonds of the olefin, so that silicon atoms are typically attached to the terminal carbon atoms of the olefin. Modifications can also occur within the body of the silicon substrate in chemically accessible zone (s) (such as, for example, in the case of porous silicon substrates), but typically the modification of the silicon substrate occurs on its surface.

Silicon-hydride (ie, Si-H) bonds can be formed on silicon substrates, for example, by treating the oxidized silicon surface with an etchant. Suitable etchantes that are acidic or basic are well known and have hydrogenated silicon surfaces suitable for use in practicing the present invention having up to 3 hydrides per silicon atom, depending on the etchant (s) used. It can be used to prepare.

Examples of acidic etching agents that cause various silicon hydrides on the silicon substrate surface are, for example, 40 wt% aqueous ammonium fluoride, aqueous hydrofluoric acid and anhydrous, such as those described in US Pat. No. 6,310,018 to Behr et al. Hydrofluoric acid etching cleaning compositions are included.

In an exemplary basic method, an aqueous base (eg sodium hydroxide) can be used as an etchant to provide a hydrogenated silicon surface.

Etch duration, etchant concentration and temperature are generally correlated. While other concentrations, temperatures and etch durations may be used, typically the etchant concentration ranges from 27 molar to 12 molar concentrations, the temperature of the etch process ranges from 18 to 30 ° C. and the duration of the etch is from 1 to 5 minutes.

In order to prevent the Si-H bonds from being converted to Si-O bonds, it is preferable to treat the substrates under an inert atmosphere (eg nitrogen or argon) after etching.

Once the silicon substrate is etched to form a surface with Si—H bonds, the fluorinated olefins may be brought into contact with the Si—H bonds (whether present as a mixture, in solution or in pure form). For example, on the exposed surface of the silicon substrate).

Useful silicon substrates include any form of solid silicon. Examples of silicon substrates include polycrystalline silicon (ie, polysilicon), silicon nanocrystals, amorphous silicon, porous silicon, thin films of any of these types of solid silicon, and / or combinations thereof. The silicon substrate can have any shape. Preferably, the silicon substrate is planar. More preferably, the substrate has the form of a wafer or chip.

In some embodiments, the silicon substrate can include one or more microelectromechanical elements (eg, MEMS devices). Examples of MEMS devices include accelerometers; Pressure, mass flow, and yaw rate sensors; display; Optical scanners; Adaptive optics; Optical regulators; Optical attenuator; Dynamic gain balancer; Optical, microwave, and radio frequency switches; Variable capacitors and derivatives; Micro-relays; Chemical sensors; And micro-valve.

MEMS devices include, for example, JDS Uniphase MEMS Business Unit (Cronos), Research Triangle Park, North Carolina; Sandia National Laboratories, Albuquerque, NM, USA; Or commercially known methods such as those available from Tronic's Microsystems, Grenoble, France. Exemplary assembly methods are described in the "MUMPs Design Handbook", Revision 7.0 (2001) available from JDS Uniface MEMS Business Unit (Chronos).

The methods and articles according to the present invention are in addition to MEMS device anti-sticking treatments (e.g., stabilization of porous silicon, preparation of stable Si electrodes, silicon surface passivation, preparation of DNA on Si and microfluidic devices). It is useful for a range of applications.

Fluorinated olefins useful in the practice of the present invention include one or more materials of the formula:

Wherein m, n, Z and R _f are defined as follows:

m is 1 or more, Preferably it is the range of 1-20, More preferably, it is an integer of the range of 1-10. In some desired embodiments m is 1. Without wishing to be bound by theory, the presence of one or more methylene groups (ie, m is one or more) provides enhanced reactivity to fluorinated olefins compared to electron withdrawing groups such as perfluoroalkyl or perfluoroalkylene, and alkoxy Strong electron donors, such as dialkylamino and the like, are believed to provide improved chemical and environmental stability compared to groups.

n is 0 or more, Preferably it is the range of 0-20, More preferably, it is an integer of the range of 0-3.

Z is a covalent bond or for example straight, branched or cyclic alkylene; Arylene; Straight chain, branched or cyclic aralkylene; Oxygen; Carbonyl; sulfur; Sulfonyl; Amino (including substituted amino such as alkylamino); And combinations thereof, such as sulfonamido, carboxamido, carbonyloxy, oxycarbonyl, alkyleneoxy, sulfonamidoalkylene, carboxamidoalkylene, or poly (oxyalkylene) And bivalent couplers. Preferably, Z is a covalent bond, -O- or Wherein R ¹ is alkyl (eg methyl, ethyl) or H). More preferably, Z is -O- or to be.

R _f is a highly fluorinated organic group. As used herein, the term "highly fluorinated organic group" means an organic group containing at least 3 carbon atoms and containing fluorine in an amount of at least 40% by weight. Preferably, R _f contains fluorine in an amount of at least 50% by weight, more preferably at least 60% by weight. R _f may, for example, be branched, straight chain (ie unbranched) and / or cyclic. R _f may be for example a fluorine-substituted alkyl, alkaryl, aralkyl or aryl group optionally substituted with one or more additional groups including, for example, oxa, alkoxy and allyloxy groups.

In some embodiments, R _f can include alkyl, alkylene, alkoxyalkyl groups and / or derivatives thereof at least partially fluorinated. In some embodiments, R _f has 4 to 30 carbon atoms, although other numbers of carbon atoms are also useful. Preferably, R _f comprises one or more perfluoroalkyl and / or perfluoroalkylene groups. Examples of perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, perfluoropropyl (eg perfluoroisopropyl), perfluorobutyl (eg perfluoro-n-butyl, Perfluoroisobutyl, perfluoro-tert-butyl), perfluorooctyl (eg, perfluoro-n-octyl, perfluoroisoctyl), and perfluorodecyl. Preferably, the perfluoroalkyl group has 4 to 12 carbon atoms. Examples of perfluoroalkylene groups include hexafluoropropylene, octafluorobutylene, and dodecafluorohexylene.

In some embodiments, R _f can include poly (alkyleneoxy) groups and / or derivatives thereof partially or fully fluorinated. Examples of the perfluorinated polyalkyleneoxy group include poly (tetrafluoroethyleneoxy) groups; Monovalent and divalent poly (hexafluoropropyleneoxy) groups; And block or randomly aligned difluoromethyleneoxy, tetrafluoroethyleneoxy and hexafluoropropyleneoxy groups (eg, poly (tetrafluoroethyleneoxy-co-hexafluoropropyleneoxy) groups). Groups are included.

Fluorinated olefins useful in the practice of the present invention are obtained, for example, directly from commercial sources and / or by known method (s) (selection typically depends on the particular nature of m, n, Z and R _f ). It can manufacture.

In some embodiments of the invention, the fluorinated olefin is one or more fluorinated allyl amides, preferably of formula Fluorinated allyl amide, wherein R _f and R ¹ are as defined above. Such compounds are typically reacted with an excess of allylamine, for example, by reacting the fluorinated ester of formula R _f C (O) OCH ₃ with an excess of allylamine in the same manner as described in the Examples set forth below. It can manufacture by forming.

In some embodiments of the invention, the fluorinated olefin is one or more fluorinated allyl ethers, preferably of formula Fluorinated allyl ethers, wherein R _f is a highly fluorinated organic group as defined above. Such compounds can be prepared, for example, by allylating fluorinated alcohols of the formula R _f CH ₂ OH or R _f CH ₂ CH ₂ OH. Typically, such fluorinated alcohols can be allylated (eg, with excess allyl bromide) to form the corresponding allyl ether, in the same manner as described, for example, in the examples set forth below.

Typically, fluorinated alcohols (eg fluorinated alcohols of the formula R _f CH ₂ OH or R _f CH ₂ CH ₂ OH) are obtained directly from commercial sources and / or for example by lithium aluminum hydride Reduction of a carboxylic acid, or catalytic hydrogenation on a copper-chromium oxide catalyst (as described, for example, in US Pat. No. 2,666,797 to Hurst et al.); Sodium borohydride reduction of the methyl ester of the corresponding fluorinated carboxylic acid (as described, for example, in US Pat. No. 4,156,791 to Childrens); Sodium borohydride reduction of the corresponding fluorinated carboxylic acid halide (as described, for example, in US Pat. No. 3,293,306 to Bleu et al. And US Pat. No. 3,574,770 to Stump et al.); Free-radical addition of methanol to perfluoroolefins, for example as described in LaZerte and Koshar in J. Am. Chem. Soc., Vol. 77, p. 910 (1955) CF ₃ CF = CF ₂ and C ₅ F ₁₁ CF = CF ₂ ); Free-radical telomerization of tetrafluoroethylene with methanol (as described, for example, in US Pat. No. 2,559,628 to Joyce), and / or direct fluorination of the corresponding acetates of hydrocarbon alcohols (eg For example as described in US Pat. No. 5,488,142 to Fall et al.), And subsequent hydrolysis.

Examples of useful commercially available fluorinated alcohols include substituted and unsubstituted 1H, 1H-dihydroperfluoroalkane-1-ol (eg 2,2,3,3-tetrafluoro-1,4-butanediol; 1H , 1H, 3H-tetrafluoro-1-propanol; 1H, 1H-pentafluoro-1-propanol; 2,2,3,3,4,4-hexafluoro-1,5-pentanediol; 1H, 1H-heptafluoro-1-butanol; 1H, 1H, 6H, 6H-octafluorohexanediol; 1H, 1H, 5H-octafluoro-1-pentanol; undecafluorocyclohexylmethanol; 1H, 1H , 7H-dodecafluoro-1-heptanol; 1H, 1H-pentadecafluorooctan-1-ol; 1H, 1H, 9H-hexadecafluoro-1-nonanol; and 1H, 1H, 11H- Eicosafluoro-1-undecanol); Perfluoropolyetherdiol having a number average molecular weight of 1,200 to 14,000 grams / mole (g / mol), for example the trade name “FOMBLIN” available from Ausimont USA of Toropair, NJ. (For example, "Pomblin Z DOL 2000", "Pomblin Z DOL 2500", "Pomblin Z DOL 4000", "Pomblin Z DOL TX", "Pomblin Z Tetraol", "Pomblin AM 2001 "," Fomblin AM 3001 ").

In some embodiments of the invention, it is preferred that the fluorinated olefins comprise poly (perfluoroalkyleneoxy) groups.

In some embodiments of the invention, the fluorinated olefins preferably comprise a perfluoroalkanesulfonamido group, for example a perfluorobutanesulfonamido or a perfluorooctanesulfonamido group.

The fluorinated olefins can be present, for example, in mixtures (eg dispersions in solvents), solutions in solvents or in pure form, and optionally, for example, hydrosilylation catalysts and / or free-radicals described below. May be present with the initiator.

If a solvent can optionally be used with the fluorinated olefin according to the invention, it may comprise one or more compounds which are present as liquids at 20 ° C. Preferably, the solvent may be inert (ie, substantially free of functional groups that will interfere with the hydrosilylation reaction). Examples of suitable compounds which may constitute a solvent include alkanes (e.g. dodecane, hexadecane, isodecane), hydrofluoroethers (e.g. 3M Company, Engineered Fluids from 3M Company) (NOVEC ENGINEERED FLUID) HFE-7100 "," 3M Novek Engineered Fluid HFE-7500 "," 3M Novek Engineered Fluid HFE-7200 ", carbon chloride (e.g. CF ₂ ClCFCl ₂ ) and Perfluorinated trialkylamines (for example sold under the trade name “3M Fluorinert ELECTRONIC FLUID FC-70” under 3M Company). Preferably, any solvent is selected such that the fluorinated olefins and any other components are soluble at ambient temperature and use concentrations.

Suitable methods for applying fluorinated olefins and any other constituents (eg, hydrosilylation catalysts, free-radical initiators, and / or solvents) to silicon substrates include, for example, spraying, dip coating, wiping ( wiping) and spin coating. In embodiments of the invention (eg, when the silicon substrate comprises a MEMS device), hydrosilylation is preferably carried out using a solution of fluorinated olefins in a solvent. In this case, the fluorinated olefin is typically present in an amount of from 0.05 to 20% by weight, although other percentages are possible.

In some embodiments (e.g., thermal hydrosilylation of silicon substrates using volatile fluorinated olefins), in contrast to the application method described above, fluorinated olefins in vapor form are subjected to hydrosilylation under conditions in which hydrosilylation can occur. Can be contacted. In this embodiment the fluorinated olefins preferably consist essentially of a single fluorinated olefin although mixtures may be used. This technique may be particularly desirable when fluorinated olefins, which tend to be secondary reactions (eg polymerization), are used under hydrosilylation conditions.

After coating the silicon substrate, but prior to hydrosilylation, any solvent present may optionally be removed (eg by evaporation).

Typically, at least a portion, preferably all, of the substrate surface to be treated is applied in layers with fluorinated olefins. Preferably, the fluorinated olefins form a monolayer (eg, self-assembled monolayer) on the silicon substrate surface. As the silicon substrate is surface treated, the fluorinated olefin layer may be present in any thickness, but for MEMS device application, after reaction with the silicon substrate and removal of any solvent, the fluorinated olefin layer is typically from 0.5 to 10 It has a thickness in the range of nanometers (nm), preferably 1 to 5 nm, more preferably 1 to 2.5 nm.

Hydrosilylation of a fluorinated olefin with a substrate Si—H group (eg Si _sub —H, see below) produces a silicon substrate, typically and preferably chemically modified, wherein the chemically modified substrate is At least one silicon atom covalently bonded to an organic group of the formula:

Where

m, n, Z and R _f are as defined above,

Si _sub represents a substrate silicon atom bonded directly (eg, coordinated) to one or more, typically three additional substrate silicon atoms.

Preferably, the fluorinated olefins are hydrosilylated with Si _sub —H groups to chemically modify the entire surface of the silicon substrate (eg, by forming an organic material layer), although partial coverage may also be used. Thicker organic material layers (eg, resulting from secondary reactions of fluorinated olefins or other components) may also typically be used, but the thickness of the organic material layer corresponds to the length of the single olefin molecule (ie, monolayer). It is preferable.

Hydrosilylation may proceed spontaneously or use catalysts, free-radical initiators (eg free-radical photoinitiators) and / or energy. Examples of energy forms include thermal energy and / or electromagnetic radiation (eg, wavelengths in the range of 200 to 400 nm). Typically, silicon substrates with surface Si—H bonds are subjected to minutes to hours (hr) (eg, 3 hours) at temperatures below 180 ° C. or higher in the presence of fluorinated olefins (eg, fluorinated allyl ethers). Heating for or longer than a period of time is an effective means of carrying out the hydrosilylation reaction. Under the above conditions, it may be desirable to use a high boiling point solvent (eg, a solvent having a boiling point of at least 180 ° C.) with the fluorinated olefin. In addition, it is preferred that under these conditions the fluorinated olefin is not unstable or volatile at the temperatures used. Alternatively, it can be decomposed or evaporated, and then reacted with the surface Si—H bonds of the silicon substrate.

Although not required, in some embodiments of the present invention, one or more hydrosilylation catalysts and / or free-radical initiators (eg, free-radical photoinitiators) may be used to associate fluorinated olefins with Si—H bonds. The reaction can be facilitated. Preferably, if a hydrosilylation catalyst and / or free-radical initiator is present, these (s) are present in solution with the fluorinated olefin and any optional solvent.

Hydrosilylation catalysts include, for example, one or more precious metal-containing hydrosilylation catalysts (eg chloroplatinic acid, platinum deposited on a substrate, platinum complexed with organic ligands (eg alcohols, aldehydes), and / or ) Rhodium halide complex). In some embodiments, the hydrosilylation catalyst can be a hydrosilylation photocatalyst (ie, a hydrosilylation catalyst precursor that is activated upon exposure to electromagnetic radiation to form a hydrosilylation catalyst). Typically, useful electromagnetic radiation has at least one wavelength, for example 200 to 700 nm, although other wavelengths may be used. Useful photocatalysts include, for example, platinum azo complexes as described in US Pat. No. 4,670,531 to Eckberg; (Η ⁴ -cyclooctadiene) diarylplatinum complexes as described, for example, in US Pat. No. 4,530,879 to Drahnak; Platinum alkyne complexes as described, for example, in US Pat. No. 4,603,215 to Chandra et al .; (Η ⁵ -cyclopentadienyl) trialkylplatinum complexes as described, for example, in US Pat. No. 4,510,094 to Dreynak and US Pat. No. 4,916,169 to Boardman et al .; Platinum acetylacetonate complexes as described, for example, in US Pat. No. 5,145,886 to Oxman et al.

If hydrosilylation catalysts are used, they can be used in any amount and range but are typically from 1 to 1000 parts by weight of hydrosilylation catalyst, preferably 1 million parts by weight of fluorinated olefins per effective amount, for example 1 million parts by weight of fluorinated olefins. The hydrosilylation catalyst is present in an amount ranging from 10 to 200 parts by weight per part by weight.

Free-radical initiators generate free radicals that can extract H-atoms from silicon hydride bonds upon exposure to heat or electromagnetic radiation. The free-radical initiator may comprise one or more free-radical thermal initiators and / or one or more photoinitiators. Examples of free-radical thermal initiators include organic peroxides (eg benzoyl peroxide) and azo compounds (eg 2,2'-azobisisobutyronitrile). Examples of free-radical photoinitiators include one or more benzoins and derivatives thereof (eg, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzylbenzoin), benzoin ethers, for example Benzyl dimethyl ketal (for example available under the tradename “IRGACURE 651” from Ciba Specialty Chemicals, Tarrytown, NY), benzoin methyl ether, benzoin ethyl ether and Benzoin n-butyl ether; Acetophenones and derivatives thereof such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (for example available from Ciba Specialty Chemicals under the trade name "DAROCUR 1173") And 1-hydroxycyclohexyl phenyl ketone (for example available under the tradename "Irgacure 184" from Ciba Specialty Chemicals), 2-methyl-1- [4- (methylthio) phenyl] -2- ( 4-morpholinyl) -1-propanone (for example available under the tradename "Irgacure 907" from Ciba Specialty Chemicals), and 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone (for example available from Ciba Specialty Chemicals under the trade name “Irgacure 369”); And combinations thereof. In some embodiments, the free-radical photoinitiator may be combined with a platinum complex, such as a platinum complex in which one diolefin group is eta-bonded to a platinum atom, as described in US Pat. No. 6,046,250 to Boardman et al.

After hydrosilylation, the reaction components, including any solvents, unreacted olefins, and any catalysts or free-radical initiators may be removed from the substrate (eg evaporation and / or, for example, volatile solvents or By washing with liquid or supercritical CO ₂ ). Such removal of the reaction component is more preferred when the silicon substrate comprises a MEMS device.

The present invention will be more fully understood by reference to the following non-limiting examples, where all parts, percentages, ratios, etc., are by weight unless otherwise indicated.

"Room temperature" in the following Preparation Examples and Examples means approximately 20 to 24 ° C.

"Overnight" in the following Preparation Examples and Examples means a range of approximately 14 to 16 hours.

The contact angles reported in Tables 1 and 2 are surface modified silicon shown using a video contact angle meter (trade name "VCA-2500XE", available from AST Products, Inc., Billerica, Mass.). Deionized water was measured on the wafer using deionized water (≧ 18 megohms, using a purification system obtained under the trade name “MILLI-Q” from Millipore Corp., Bedford, Mass.) Or anhydrous hexadecane. The reported contact angle is the average value of the contact angle measurements taken from opposite sides of three different droplets. Typical uncertainties at the forward and backward contact angles of the reported values are ± 2 ° and ± 4 °, respectively.

Unless stated otherwise, all reagents used in the following preparations and examples can be obtained from, or purchased from, common chemical sources, such as Aldrich Chemical Co., Milwaukee, WI, or known Can be synthesized in a conventional manner.

Materials Used in the Examples

C ₂ F ₅ OC ₂ F ₄ OCF ₂ CH ₂ OH can be prepared as described in Example 3 of US Pat. No. 5,437,812 to Janulis et al.

“KRYTOX 157 FS (L)” has the formula CF ₃ (CF ₂ ) ₂ 0 [CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) CO ₂ H and the number average molecular weight M _n is approximately Lee, based in Wilmington, Delaware, at 2,500 g / mol. children. Trade name for fluorinated polyethers obtained from EI du Pont de Nemours & Co.

"Fomblin Z-DOL 2000" has the formula HOCH ₂ CF ₂ [(CF ₂ CF ₂ O) _q (CF ₂ O) _p ] CF ₂ CH ₂ OH with a ratio of q to p 1 and a number average molecular weight M _n This is approximately 2000 g / mol and is a trade name for fluorinated polyethers from Assymont USA.

CF ₃ (CF ₂ ) ₃ OC ₂ F ₄ OCF ₂ CH ₂ OC ₂ H ₄ OH can be prepared, for example, as described in US Pat. No. 5,437,812 (Jannulis et al.).

CF ₃ (CF ₂ ) ₇ CH═CH ₂ (99% purity) obtained from Aldrich Chemical Company was used after drying on 4A molecular sieve.

1-hexadecene (99% purity) obtained from ICN Biomedicals, Aurora, Ohio, was used after drying on 4A molecular sieves.

1-Eicocene (> 85% purity) was obtained from ICN Biomedicals and used as purchased.

C ₇ F ₁₅ CH ₂ OH (a mixture of approximately 70% linear isomers and 30% branched isomers) was obtained from 3M Company, St. Paul, MN.

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₁₀ CH ₂ OH was prepared according to the following method:

To a mixture of 199.7 g of perfluoro-n-butyl iodide and 93.7 g of 10-undec-1-ol in a mixture of 700 mL of acetonitrile and 300 mL of water, a mixture of 53.8 g of sodium bicarbonate and 106.2 g of sodium dithionite was stirred Little by little while adding. The reaction mixture was stirred at rt overnight and acidified with 1 N hydrochloric acid. The mixture was extracted with diethyl ether and the combined organic phases were washed sequentially with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. It was concentrated to give 234.4 g of crude CF ₃ (CF ₂ ) ₃ CH ₂ CHI (CH ₂ ) ₈ CH ₂ OH as a viscous light amber liquid which was used without further purification. 5.0 g of acetic acid was added to a slurry of 130.0 g of zinc powder in 500 mL of ethanol. A solution of 230.0 g of CF ₃ (CF ₂ ) ₃ CH ₂ CHI (CH ₂ ) ₈ CH ₂ OH in 100 mL of ethanol was added dropwise with stirring over 1 hour, and the reaction mixture was heated at 50 ° C. for 4 hours. The mixture is filtered, the filtrate is concentrated to a viscous light yellow liquid, and bulb-to-bulb distillation is carried out in several portions to give CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₁₀ CH ₂ OH 97.3 g were obtained as a colorless solid (boiling point: 160-200 ° C. at 0.05 torr (7 Pa)).

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ CH ₂ OH was prepared according to the following method.

To a mixture of 41.10 g of perfluoro-n-octyl iodide and 11.92 g of 10-undecen-1-ol in a mixture of 100 mL of acetonitrile and 40 mL of water, a mixture of 6.89 g of sodium bicarbonate and 13.58 g of sodium dithionite was added. It was added little by little with stirring. The reaction mixture was stirred at rt overnight and acidified with 1 N hydrochloric acid. The mixture was extracted with diethyl ether and the combined organic phases were washed sequentially with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride and dried over anhydrous magnesium sulfate. It was concentrated to give 43.2 g of crude CF ₃ (CF ₂ ) ₇ CH ₂ CHI (CH ₂ ) ₈ CH ₂ OH as a white solid, which was used without further purification. 4.0 g of acetic acid was added to a slurry of 19.6 g of Zn powder in 150 mL of ethanol. A solution of crude CF ₃ (CF ₂ ) ₇ CH ₂ CHI (CH ₂ ) ₈ CH ₂ OH prepared above in 50 mL of ethanol was added dropwise with stirring over 1 hour, and the reaction mixture was heated at 50 ° C. for 4 hours. This mixture was filtered and the filtrate was concentrated to approximately 45 g of a soft white solid. The crude CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ CH ₂ OH thus obtained was used without further purification.

C ₄ F ₉ SO ₂ NHCH ₃ was prepared according to the method described in Example 1 of PCT Publication No. WO 01/30873 to Savu et al.

N-methylperfluorooctanesulfonamide (C ₈ F ₁₇ SO ₂ NHCH ₃ ) and N-ethylperfluorooctanesulfonamide (C ₈ F ₁₇ SO ₂ NHCH ₃ ) are generally described in US Pat. No. 2,809,990 (Brown ( Brown)) can be prepared according to the method described in Example 1).

"SHFE" refers to isolated hydrofluoroethers available from 3M Company under the trade designation "3M Novbeck Engineered Fluid HFE-7100".

"FSOLV" refers to a perfluorinated solvent available under the trade designation "3M Fluorinant Electronic Liquid FC-70" from 3M Company.

C ₇ F ₁₅ CH ₂ OCH ₂ CH = CH ₂  Preparation of (E1):

To a stirred solution of 124 g of C ₇ F ₁₅ CH ₂ OH and 62 g of allyl bromide in 1240 g of dimethyl sulfoxide was added dropwise a 28.1 g solution of potassium hydroxide in 35 g of water. The mixture was stirred for 4 hours, during which time the mixture was allowed to separate into two immiscible liquid phases. The reaction mixture was poured into a separatory funnel and the lower layer was isolated and washed three times with water to remove any residual solvent. The crude product was dried over anhydrous magnesium sulfate, filtered and vacuum distilled to give 103 g of C ₇ F ₁₅ CH ₂ OCH ₂ CH = CH ₂ (E1) (boiling point: 88 to 30 torr (4 kilopascals (kPa)). 89 ° C.).

C ₂ F ₅ OC ₂ F ₄ OCF ₂ CH ₂ OCH ₂ CH = CH ₂  Preparation of (E2):

One liter (L) three-necked round bottom flask was equipped with a magnetic stirrer, ice bath and connector to a nitrogen bubbler. The flask was charged with a mixture of 100.4 g of C ₂ F ₅ OC ₂ F ₄ OCF ₂ CH ₂ OH and 500 mL of dimethyl sulfoxide. While stirring the mixture, a solution of 29.1 g of potassium hydroxide in 29.1 g of water was added, followed by 56.3 g of allyl bromide. After 10 minutes, the ice bath was removed and the mixture was allowed to warm to room temperature and the mixture was stirred overnight. Agitation was stopped and the reaction mixture was separated into two liquid phases. Using a separatory funnel, the lower layer (product) was isolated. The upper phase was diluted with 1 liter volume of water and the separated small heavier liquid phase was combined with the product layer. The product was washed four times with 200 mL portions of water, dried over anhydrous magnesium sulfate, filtered and vacuum distilled to give 83.3 g of C ₂ F ₅ OC ₂ F ₄ OCF ₂ CH ₂ OCH ₂ CH = CH ₂ (E2) ( Boiling point: 93-97 ° C. at 140 torr (18 kPa)).

CF ₃ (CF ₂ ) ₃ OC ₂ F ₄ 0CF ₂ CH ₂ OC ₂ H ₄ OCH ₂ CH = CH ₂  Preparation of (E3):

The one-liter three-neck round bottom flask was equipped with a magnetic stirrer and a connector to a nitrogen bubbler. The flask was charged with a mixture of 50.2 g of CF ₃ (CF ₂ ) ₃ OC ₂ F ₄ OCF ₂ CH ₂ OC ₂ H ₄ OH and 500 mL of dimethyl sulfoxide. While stirring the mixture rapidly, a solution of 7.8 g of potassium hydroxide in 7.4 g of water was added followed by 19.2 g of allyl bromide. The mixture was stirred for 2.75 h at which time a solution of 0.91 g of potassium hydroxide in 0.97 g of water was added and stirring continued overnight at room temperature. Then a solution of 1.1 g of potassium hydroxide in 1.1 g of water was added and stirring was continued at room temperature for an additional day. At this point, the reaction mixture consists of two liquid phases. The lower layer (product) is isolated using a separatory funnel, washed three times with 150 mL portions of water, dried over anhydrous magnesium sulfate and filtered (filter cake is washed with a few mL of 1,1,2-trichlorotrifluoroethane, The wash was combined with the product), and then the volatile components were removed using a rotary evaporator at water aspirator pressure. Analysis of the product by gas chromatography indicated that there was still a starting material, residual alcohol, which was recombined with a solution of 100 mL of dimethyl sulfoxide, 0.87 g of allyl bromide, and 0.4 g of potassium hydroxide in 0.56 g of water, This mixture was stirred overnight at room temperature (approximately 20 ° C.). The lower liquid layer was isolated, then washed with water, dried over anhydrous magnesium sulfate and filtered. 44.3 g of CF ₃ (CF ₂ ) ₃ OC ₂ F ₄ OCF ₂ CH ₂ OC ₂ H ₄ OCH ₂ CH = CH ₂ (E3) was obtained by vacuum distillation (boiling point: 110-112 at 15 torr (2 kPa)). ℃).

CH ₂ = CHCH ₂ OCH ₂ CF ₂ [(CF ₂ CF ₂ ) _q (CF ₂ O) _p ] CF ₂ CH ₂ OCH ₂ CH = CH ₂  Preparation of (E4):

To a stirred mixture of 100 g of glim, 10.5 g of potassium hydroxide, 2 g of tetrabutylammonium bromide and 100 g of perfluoropolyetherdiol (Fomblin Z-DOL 2000), 22.5 g of allyl bromide were added at 45 ° C. over 1 hour. . The mixture was heated to reflux for 15 hours (85 ° C.). Solvent and excess allyl bromide were removed by distillation and the mixture was filtered to remove solids and then washed with water to obtain the fluorocompound subphase. CH product having a number average molecular weight M _n of 2,050 g / mol as determined by fluorine nuclear magnetic resonance spectroscopy ( ¹⁹ F NMR) by heating the fluorine product at 95 ° C. under reduced pressure (15 torr (2 kPa)) to remove all volatiles. 96 g of _2- CHCH ₂ OCH ₂ CF ₂ [(CF ₂ CF ₂ O) _q (CF ₂ O) _p ] CF ₂ CH ₂ OCH ₂ CH = CH ₂ (E4) was obtained.

CF ₃ (CF ₂ ) ₂ [CF (CF ₃ CF ₂ O] _x CF ₃ ) CH ₂ OCH ₂ CH = CH ₂  Preparation of (E5):

Concentrated sulfuric acid 100 in a stirred solution containing 200 g of methanol and 200 g of CF ₃ (CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) CO ₂ H (Crytox 157 FS (L)) g was added The mixture was heated to reflux for 4 hours (74 ° C.) Water was added to afford the lower fluorocompound phase and isolated The isolated fluorocompound phase was subjected to 95 at 15 torr (2 kPa) under reduced pressure. CF ₃ (CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) having a number average molecular weight M _n of 2,515 g / mol as determined by ¹⁹ F NMR by heating to 캜. 184 g of CO ₂ CH ₃ were obtained.

A stirred solution of 300 g of glim and 28 g of sodium borohydride over 1 hour CF ₃ (CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) CO ₂ CH ₃ (166 g) And the mixture was heated to reflux for 15 hours (85 ° C.). To this mixture was added 100 g of methanol, 200 g of water and 67 g of concentrated sulfuric acid. The solvent was removed by distillation and the mixture was filtered and washed with water to give the fluorocompound subphase. The fluorine compound subphase was heated under reduced pressure at 95 ° C. and 15 torr (2 kPa) to remove volatiles, thereby yielding CF ₃ (CF ₂ ) ₂ O [with a number average molecular weight M _n of 2,485 g / mol as determined by ¹⁹ F NMR. 147 g of CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) CH ₂ OH were obtained.

Glim 100 g, potassium hydroxide 4.2 g, tetrabutylammonium bromide 2 g and CF ₃ (CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) CH ₂ OH (prepared above) 100 9 g of allyl bromide was added to 1 g of agitation solution while heating at 45 ° C. over 1 hour. This mixture was then heated to reflux (85 ° C.) for 15 hours. Solvent and excess allyl bromide were removed by distillation and the mixture was filtered and washed with water to obtain the fluorocompound subphase. The fluorine product was heated under reduced pressure at 95 ° C. and 15 torr (2 kPa) to remove volatiles, thereby yielding a CF ₃ (CF ₂ ) ₂ O [number average molecular weight M _n of 2,350 g / mol as determined by ¹⁹ F NMR. 96 g of CF (CF ₃ ) CF ₂ O] _x CF (CF ₃ ) CH ₂ OCH ₂ CH = CH ₂ (E5) were obtained.

CF ₃ O (CF ₂ CF ₂ O) _w CF ₂ CH ₂ OCH ₂ CH = CH ₂  Preparation of (E6):

Poly (ethylene glycol) methyl ether (CH ₃ O (CH ₂ CH ₂ O) _w CH ₂ CH ₂ OH (Product No. _1, obtained from Aldrich Chemical Company, Milwaukee, WI) and has a number average molecular weight M _n of 550 g / mol. 20, 248-7) 1 kg was reacted with excess acetic anhydride for 1 hour at 125 ° C. The mixture was then heated to 160 ° C. under vacuum to remove excess acetic anhydride and acetic acid, thereby proton nuclear magnetic resonance spectroscopy 1032 g of CH ₃ O (CH ₂ CH ₂ O) _w CH ₂ CH ₂ OC (O) CH ₃ was obtained having a number average molecular weight M _n of 590 g / mol measured by ( ¹ H NMR).

A solution was prepared by diluting 1032 g of CH ₃ O (CH ₂ CH ₂ O) _w CH ₂ CH ₂ OC (O) CH ₃ with CF ₂ ClCFCl ₂ to a volume of 1800 mL. The solution was fed to a 10-L reactor over 23 hours containing 6,000 mL of CF ₂ ClCFCl ₂ and 4300 g of sodium fluoride and maintaining a 10% stoichiometric excess of fluorine gas throughout the reaction. Fluorination was carried out at 20 ° C. using 20% fluorine gas. After the reaction was completed, excess methanol was added. The solution was filtered to remove solids, washed with water to remove excess methanol, and the CF ₂ ClCFCl ₂ solvent was distilled off under reduced pressure. A number average molecular weight M _n measured by ¹⁹ F NMR yielded 850 g / mol CF ₃ O (CF ₂ CF ₂ O) _w CF ₂ CO ₂ CH ₃ (2382 g). To a stirred solution of 1500 g of glim and 43 g of sodium borohydride, 800 g of CF ₃ O (CF ₂ CF ₂ O) _w CF ₂ CO ₂ CH ₃ (0.94 mole, prepared above) were added over an hour and 15 Heated to reflux (85 ° C.) for hours. To the reaction mixture was first added 400 g of methanol, then 800 g of water and 280 g of concentrated sulfuric acid were added and the solvent was distilled off by heating to 95 ° C. The fluorine compound subphase was heated to 95 ° C. under pressure of 15 torr (2 kPa) to remove all volatiles, thereby yielding CF ₃ O (CF ₂ CF ₂ O with a number average molecular weight M _n of 855 g / mol as determined by ¹⁹ F NMR). ) _w CF ₂ CH ₂ OH 650 g was obtained.

85 g of CF ₂ ClCFCl ₂ , 30 g of glim, 2.5 g of potassium hydroxide, 1 g of tetrabutylammonium bromide and 30 g of a stirred solution of CF ₃ O (CF ₂ CF ₂ O) _w CF ₂ CH ₂ OH (prepared above) 6.5 g of allyl bromide was added at 45 ° C. over 2 hours. Solvent and excess allyl bromide were removed by distillation and 170 g of CF ₂ ClCFCl ₂ were added. The mixture was washed with 100 mL of 10 wt% hydrochloric acid, then with 2 × 100 g portions of water, then dried over anhydrous magnesium sulfate and filtered. By removing the volatiles at 95 ° C. and pressure 15 torr (2 kPa), CF ₃ O (CF ₂ CF ₂ O) _w CF ₂ CH ₂ OCH _{2 with} a number average molecular weight M _n of 948 g / mol as determined by ¹⁹ F NMR 28 g of CH = CH ₂ (E6) were obtained.

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₉ CH = CH ₂  Preparation of (E7):

20 mL of concentrated sulfuric acid was slowly added to a mixture of 19.52 g of CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₁₀ CH ₂ OH and 200 mL of 48 wt.% Aqueous hydrobromic acid. The reaction mixture was heated at 100 ° C. for 24 hours and poured into 1 liter of water. The mixture was extracted with hexanes and the combined organic phases were washed with saturated aqueous sodium bicarbonate and dried over anhydrous magnesium sulfate. The solution was concentrated to give an amber liquid which was eluted with hexane through 3 inches of silica. The eluate was concentrated to give a bright amber liquid, 19.82 g of CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₁₀ CH ₂ Br by bulb-to-bulb distillation as a clear colorless liquid (boiling point: 0.06 torr (8 Pa) at 120-170 ° C.).

To a solution of 10.00 g of CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₁₀ CH ₂ Br in a mixture of 8 mL of dimethyl sulfoxide and 35 mL of tetrahydrofuran at −20 ° C., 6.5 g of potassium tert-butoxide were added in several portions. . The reaction mixture was warmed to 0 ° C. and poured into water. The mixture was extracted with diethyl ether, and the combined organic phases were washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate and concentrated to give a dark liquid. The crude product was approximately 2.5 cm eluted through silica with hexanes and the eluate was concentrated to give a light amber liquid.

Distillation through a 6 inch (15 cm) Vigreux column yielded 4.97 g of CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₉ CH = CH ₂ (E7) as a clear colorless liquid (boiling point: 0.05 torr 50 to 52 ° C. at 7 Pa).

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₉ CH = CH ₉  Preparation of (E8):

25 mL of concentrated sulfuric acid was slowly added to a mixture of 29.0 g (0.049) of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ CH ₂ OH and 250 mL of 48 wt% aqueous hydrobromic acid. The reaction mixture was heated at 100 ° C. for 18 hours and poured into 1 liter of water. The mixture was extracted with hexanes and the combined organic phases were washed with saturated aqueous sodium bicarbonate and dried over anhydrous magnesium sulfate. The solution was concentrated to give a dark liquid which was eluted with hexane through 3 inches (8 cm) of silica. The eluate was concentrated to give 20.2 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ CH ₂ Br as an almost white solid which was used without further purification.

To a solution of 9.80 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ CH ₂ Br in a mixture of 8 mL of dimethyl sulfoxide and 40 mL of tetrahydrofuran at −10 ° C., 11.2 g of potassium tert-butoxide was added in several portions. . The reaction mixture was warmed to 0 ° C. and poured into cold water. The mixture was extracted with diethyl ether and the combined organic phases were washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate and concentrated to give a dark semisolid. The crude product was eluted with hexane through 1 inch (3 cm) of silica and the eluate was concentrated to give a dark solid. 5.10 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₉ CH═CH ₂ were obtained as colorless solids by bulb-to-bulb distillation (boiling point: 110-120 ° C. at 0.10 torr (13 Pa)).

C ₄ F ₉ SO ₂ N (CH ₃ ) CH ₂ CH = CH ₂  Preparation of (E9):

A 250 mL three-necked round bottom flask equipped with thermometer, magnetic stirrer and addition funnel was charged with a solution of 75 g of C ₄ F ₉ SO ₂ NHCH _{3 in} 80 g of dimethyl sulfoxide. The solution was stirred while adding a solution of 17.1 g of potassium hydroxide in 20 g of water through a pipette in an aliquot of 2 mL. The solution turned cloudy during the addition, then further stirred and became clear. Allyl bromide (31.9 g) was charged to the addition funnel and added dropwise to the reaction mixture. It was confirmed that the temperature of the reaction mixture rose to 75 ° C. during the addition. Immediately after the start of the addition the reaction mixture turned cloudy and stirring continued at room temperature overnight. The reaction mixture was poured into a separatory funnel and left to stand until the liquid layer separated. Several mL of water was added to the mixture to facilitate phase separation. The bottom layer was removed, washed with water and brine and dried over anhydrous magnesium sulfate to give 76.0 g of a clear colorless crude liquid product which was vacuum distilled to give C ₄ F ₉ SO ₂ N (CH ₃ ) CH ₂ CH = CH ₂ 68.7 g were obtained (boiling point: 97-101 ° C. at 19 torr (2.5 kPa)).

CF ₃ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ C (O) NHCH ₂ CH = CH) Preparation of (E10):

To a 5 L flask containing 2068 g of triethylene glycol monomethyl ether (MTEG) in 500 mL of dichloromethane was added 970 mL of acetyl chloride over 4 hours. After the addition was completed, a slight excess of acetyl chloride was confirmed by infrared spectroscopy. Volatiles were removed from the resulting product (MTEG acetate). Direct fluorination using perfluoro-N-methylmorpholine (PNMM) (available from 3M Company under trade name "PF-5052") as a liquid medium in a tubular reactor such as described in US Pat. No. 5,578,278 to Paul et al. It was performed by. MTEG acetate (2647 g) was pumped to the reaction zone at 44.6 g / hr, during which the gas flow rate was maintained at 2,500 ml / min F ₂ in 10,000 mL / min N ₂ . At the end of the reaction (determined by the presence of unreacted fluorine), the addition of F ₂ was stopped, then the reactor was flushed with N ₂ and 1300 g of methanol was added over approximately 2.5 hours. The mixture was stirred for approximately 0.5 hours or more. The resulting mixture was drained into approximately 60 L separatory funnel and washed twice with about 15-20 L of water introduced from the bottom valve. The fluorine compound layer was then isolated, dried over about 450 g of anhydrous magnesium sulfate, filtered and most of the PNMM was removed using a 5-plate distillation apparatus. The residue (5310 g) was distilled on a 30 cm Vibrooks column at about 740 torr (101 kPa) to give 1256 g of CF ₃ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ CO ₂ CH ₃ (boiling point: 140 To 150 ° C.). The above procedure was repeated to give 2323 g of CF ₃ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ CO ₂ CH ₃ , which was combined with 1256 g previously obtained above, and 84% pure by gas chromatography (the remaining inert). Fluorine compound) to give 3579 g of CF ₃ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ CO ₂ CH ₃ .

A 250 mL round bottom flask was charged with 46.2 g of CF ₃ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ CO ₂ CH _{3 in} 50 mL of methanol. Allylamine (7.8 g) was added in two approximately equal amounts. After 15 minutes, gas chromatographic analysis confirmed complete conversion of esters to the corresponding allyl amides. Solvent and excess allyl amine were removed by evaporation under reduced pressure. The residue was distilled off (boiling point: 90-95 ° C. at 1 torr (133 Pa)) to give 41.3 g of a pale product. This was a microfiber filter (trade name "WHATMAN GRADE GF / B-BINDER-FREE GLASS FIBER" (1.0 μm pore size) of Kent Maidstone 20/20, UK. Filtered through Redman (Whatman, PLC) and distilled to obtain 39 g of clear CF ₃ OC ₂ F ₄ OC ₂ F ₄ OCF ₂ C (O) NHCH ₂ CH = CH ₂ in 96% purity. Obtained.

C ₄ F ₉ SO ₂ N (CH ₃ ) (CH ₂ ) ₉ CH = CH ₂  Preparation of (E11):

A 500 mL three-necked round bottom flask connected with a nitrogen bubbler equipped with a magnetic stirrer and an oil bath heater was charged with 17.2 g of N-methylperfluorobutanesulfonamide (C ₄ F ₉ SO ₂ NHCH ₃ ) and 250 mL of dimethyl sulfoxide. Was charged. Agitation was started and the solids dissolved in a few minutes. A solution of 4.0 g of potassium hydroxide in 5 mL of water was added via a pipette and stirring continued for 30 minutes while the oil bath was heated to 80 ° C. After this time, most of the potassium hydroxide dissolved. Thereafter, 11-bromo-1-undecene (Aldrich Chemical Company, 95% purity, 12.3 g) was added to the flask via a pipette and the reaction mixture was stirred at 80 ° C. for 19 hours. The oil bath was then removed to cool the mixture and the flask contents were poured into a separatory funnel. The mixture was separated into two liquid phases and the bottom layer was withdrawn. The upper phase was diluted with the same volume of water to separate a small amount of the lower phase. This was also removed and combined with the first batch. The combined crude product (18.0 g) was dissolved in 150 ml of dichloromethane and washed successively with 100 ml portions of water, 10 wt% aqueous potassium hydroxide solution, water and brine. The dichloromethane solution was dried over anhydrous magnesium sulfate and filtered, and then the solvent was removed on a rotary evaporator under water inhaler pressure. This gave 17.9 g of a light pale yellow liquid product. 17.3 g of crude product was bulb-to-bulb vacuum distilled at 160 to 180 ° C. and 0.3 torr (4 Pa) to give 16.2 g of N- (10-undesenyl) -N-methylperfluorobutanesulfonamide as a clear colorless liquid distillation. Obtained as water.

C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH = CH ₂  Preparation of (E12):

A 1 liter three-necked flask equipped with a magnetic stirrer and an addition funnel was charged with 150 g of N-methylperfluorooctanesulfonamide and 570 g of dimethyl sulfoxide, and the mixture was stirred for several minutes until the solid dissolved. To this stirred solution was added a solution of 25 g of potassium hydroxide in 25 g of water. The mixture was stirred for 30 minutes and then 46 g of allyl bromide were added dropwise through an addition funnel. After a few minutes, fever was observed. The reaction mixture was stirred for 5.5 hours, during which time a white solid precipitated out of solution. This solid was isolated by filtration, washed with 350 mL of dimethyl sulfoxide and dissolved in 450 g of 1,1,2-trichlorotrifluoroethane. This solution was transferred to a separatory funnel, 200 mL of water portioned and washed four times and dried over anhydrous sodium sulfate. The solvent was removed by distillation under atmospheric pressure and the product was vacuum distilled to give 138 g of C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH = CH ₂ (boiling point: 98 ° C. to 0.4 torr (50 Pa)). 105 ° C. at 0.7 torr (90 Pa)). The product was an almost colorless clear liquid and solidified to a white waxy solid upon standing at room temperature.

C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₃ ) CH ₂ CH = CH ₂  Preparation of (E13):

A two liter three-necked flask equipped with a magnetic stirrer, addition funnel and nitrogen blanket was charged with 250 g of N-ethylperfluorooctanesulfonamide and 960 g of dimethyl sulfoxide. The mixture was stirred at room temperature until the solids dissolved. Then, a solution of 35 g of potassium hydroxide in 38 g of water was gradually added over about 1 minute. The mixture was stirred for at least several minutes and then the addition funnel was charged with 71 g of allyl bromide. Allyl bromide was added dropwise over about 30 minutes, then the mixture was stirred at rt overnight. The reaction mixture consisting of two liquid phases was poured into a separatory funnel and the bottom layer was removed and washed twice with dimethyl sulfoxide, twice with water and twice with brine. Vacuum distillation gave 216 g of C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₃ ) CH ₂ CH = CH ₂ as an almost colorless clear liquid (boiling point: 80-85 ° C. at 0.1 torr (10 Pa)).

General Method A: Preparation of Silicon Substrates Having Surface Si-H Bonds

Silicon wafers (Si (111), disks with 1 mm thickness and 10 cm diameter, WaferNet, Inc., San Jose, CA) are cut into small pieces (approximately 1 cm x 3 cm) It was. The pieces were cleaned by sequentially washing with heptane, acetone and isopropyl alcohol. Ultraviolet lamp (5 inch × 5 inch square (12.5 cm × 12.5 cm) ultraviolet lamp, available under the trade name "UV GRID LAMP" from BHK, Inc., Claremont, CA, model number In the device where the lamp is placed in the box, clean the cleaned pieces for 10 minutes so that the 88-9102-O2 is suspended 8 cm above the bottom of a small sheet metal box (13 cm wide x 14 cm deep x 15 cm high). Exposure to ultraviolet light and ozone. A small wrap jack was used to position the pieces of silicon wafer to be cleaned as close as possible without physical contact with the ultraviolet light lamp. The front of the box was a hinged door at the top, which allowed the sample to be inserted and removed. A small hole in one side of the box was attached to an oxygen source flowing into the box at a flow rate of approximately 1-5 standard liters / minute. Ozone was prepared in situ by the action of ultraviolet light on molecular oxygen.

The wafer pieces were then individually impregnated for 4 minutes in a 40 wt% solution of ammonium fluoride in water sparged with nitrogen for at least 30 minutes to remove dissolved oxygen. This procedure etched the native oxide (SiO ₂ ) on the wafer, resulting in an atomically flat Si (111) surface terminated with hydride.

Finally, the silicon wafer pieces were washed with water and isopropyl alcohol and blow dried with nitrogen.

General Method B: Grafting of Olefin on Silicon Substrates Having Surface Si-H Bonds

A piece of silicon wafer having a surface Si-H bond prepared according to the general method A was applied to a test tube previously sprayed with nitrogen for 30 minutes containing 5% by volume of the desired olefin in hexadecane or FSOLV to remove residual oxygen. Put in.

After introducing the olefin, the test tube was sealed with a silicone rubber diaphragm and the solution was sparged with nitrogen for another 15 minutes. The test tubes were placed in a heating bath to allow internal test tube temperatures to reach 200 ° C. The heating bath is specifically a 1200 mL stainless steel beaker (Shibugan, WI) polar wear in a heating mantle (Glas-Col, Terre Hout, Indian, catalog number TM630) for metal beakers. (Obtained from Polar Ware). The stainless steel beaker was filled to within 3 cm of the top with a chrome steel ball (approximately 3.2 mm in diameter from Hartford Ball Co., Hartford, CT). The bath temperature is ace glass in Vineland, NJ, catalog number 12113-50, equipped with a type K thermocouple (4.8 mm diameter, 10 cm length) enclosed in stainless steel located within the bath. Obtained from). After 3 hours, the test tube was removed from the heating bath and cooled to room temperature. Silicon wafer pieces were removed from the test tubes. When hexadecane was used as the solvent, the silicon wafer pieces were washed sequentially with heptane, acetone and isopropyl alcohol. When FSOLV was used as the solvent, the silicon wafer pieces were washed with SHFE. Silicon wafer pieces were further washed sequentially with heptane, acetone and isopropyl alcohol. The cleaned silicon wafer pieces were then dried using a dry nitrogen stream.

General Method C: Grafting of Olefin on Silicon Substrates with Surface Si-H Bonds

5 weight percent olefin, 2-hydroxy-2-methyl-1-phenyl-1-propane (available from Ciba Specialty Chemicals under the trade name "Darocur 1173") of 5 weight percent free radical photoinitiator and 90 weight percent solvent The solution was placed in a quartz tube and sparged with nitrogen for 15 minutes. Thereafter, a piece of silicon wafer having a surface Si—H bond prepared according to the general method A was added, and the quartz tube was sealed under dry nitrogen. Ultraviolet fluorescence (obtained under the trade name “BLACKLIGHT BLUE BLB 15W” from Osram Sylvania, Danbus, Mass.) Was spun into the solution under dry nitrogen for 30 minutes. The solution was placed about 2 cm away from the light source. The wafer functionalized with non-fluorinated olefins was then washed sequentially with heptane, acetone and isopropyl alcohol and then blow dried with dry nitrogen. Silicon wafers functionalized with fluorinated olefins were washed sequentially with SHFE, heptane, acetone and isopropyl alcohol and then blow dried with dry nitrogen.

General Method D: Grafting of Olefin on Silicon Substrates Having Surface Si-H Bonds

A test tube from which a silicon wafer piece having a surface Si-H bond prepared according to the general method A was sparged with nitrogen for 30 minutes, containing a 5% by volume solution of olefins shown in Table 3 below in FSOLV, to remove residual oxygen in advance. Put in.

After introducing the silicon wafer pieces, the test tube was sealed with a silicon rubber septum and the solution was sparged with nitrogen for at least 15 minutes. Still under nitrogen the test tubes were placed in a silicone oil heating bath set at 180 ° C. The heating bath was obtained from Ace Glass under the trade name "INSTATHERM OIL BATH, HIGH FORM" (Part No. 9603-O2), filled with high temperature silicone oil (Ace Glass, part number 14115-12). . Temperature is a temperature controller (trade name "THERM-O-WATCH L7-1100SA / 28T"), Instruments for Research and Industry, Inc., in Cheltenham, Pennsylvania. Obtained from). After 15 minutes in the oil bath, the test tubes were removed and the test tubes were allowed to cool to room temperature by placing them in water at room temperature. Wafer pieces were removed from the test tubes. Wafer pieces were cleaned with SHFE. The wafer pieces were further washed sequentially with heptane, acetone and isopropyl alcohol. Thereafter, the wafer pieces were blow-dried with dry nitrogen.

Examples 1 to 11 and Comparative Examples 1 to 3

A series of olefins corresponding to Examples 1 to 11 and Comparative Examples 2 to 3 was grafted onto a piece of silicon (111) wafer with Si—H bonds prepared according to General Method B, as described in Table 1 below. For Examples 1 to 10 and Comparative Examples 2 to 3, the advancing and receding contact angles of water and hexadecane with respect to the olefin treated surface of the silicon wafer pieces are reported in Table 1. Comparative Example 1 was a silicon chip prepared according to the general method A, but was not treated with any olefins. Contact angles for water and hexadecane reported in Table 1 were measured using the etched silicon wafer piece surface without subsequent olefin treatment.

Example 12

Unreleased (ie still having protective photoresist) a series of MEMS cantilever beams (R. Maboudian et al., Tribology Letters, vol. 3, pp. 215-221 (1997) 0.5 cm x 0.5 cm square silicon chips with the same as described in the following] were prepared using the Chronos MUMPS method with the following changes. The unopened beam was made of polycrystalline silicon and placed parallel to the polycrystalline silicon surface at a 2 μm distance. The beams were spaced regularly to form an array (20 μm pitch), which had a 3.5 μm thickness, 10 μm width, and a length varying 50 μm intervals from 200 μm to 1500 μm. The chip also had a reference post with a height of 5.5 μm thick.

To remove the protective photoresist generated from the MUMPS method, the chip was removed using an ultrasonic bath (available from Fisher Scientific, Pittsburgh, Penn. Under the trade name "Fischer SCIENTIFIC FS3 ULTRASONIC CLEANER"). Sonication in acetone for 20 minutes, followed by 5 minutes in isopropyl alcohol as described above.

Opening of the MEMS cantilever beam and cleaning of the MEMS chip are described in R. Maboudian et al., Sensors and Actuators A (2000), vol. 82, pages 219-223, was performed in a "fill / drain" apparatus similar to that described. The "fill / drain" device consisted of a block of polytetrafluoroethylene with large holes (3.8 cm deep and 3.8 cm diameter), forming a reservoir. A drainage hole drilled in the bottom center of the reservoir was fitted with a polytetrafluoroethylene plug assembly to allow the reservoir to be filled when the closure was closed and drained when opened. Six small slots (9.5 mm diameter, 1.6 mm deep) are mechanically created in the bottom of the reservoir along the circle around the drain hole (the drain hole and the top of the slot are in the same plane), even after draining the MEMS chip in the reservoir It was placed below the surface of the liquid.

The chip was placed in the slot of the "charge / drain" device. CMOS grade 49 wt% aqueous HF (J.T. Baker, Philipsburg, NJ) was added and left to stand for 3 minutes to open the cantilever beam MEMS device. Thereafter, the apparatus was drained. 25 mL volume of deionized water (18 megohms or more) was added to the apparatus from the purification system (available under the trade name "Milli-Q") to discharge the aqueous HF. Thereafter, the water was drained and the process was repeated nine more times, continuing to be washed with water for 10 minutes, using a total of 250 mL of water. The remaining water was drained, 5 mL of CMOS grade 49 wt% aqueous HF was added and the MEMS chip was etched again for 3 minutes. The aqueous HF was drained back. The etched chips were then washed sequentially with isopropyl alcohol for 10 minutes and with SHFE for 10 minutes, each such wash being performed in 10 charge / drain cycles over 10 minutes in the same manner as the water wash. Washing with FSOLV was performed by addition and draining 5 mL of FSOLV, which was repeated two more times to perform a total of three charge / drain cycles.

The chip was removed from the “fill / drain” device and placed in a test tube containing a 5 wt% solution of E1 in FSOLV. This solution was sparged with nitrogen for 15 minutes before use. The solution was heated and cooled at 200 ° C. for 1 hour. After cooling, the MEMS chip was removed from the El and FSOLV solutions, placed in a small glass cup containing SHFE (approximately 2 ml) and washed by adding an additional 30 mL of SHFE to the small cup over 10 minutes. Drying of the MEMS chips was carried out by placing a small glass containing SHFE and MEMS chips in an oven at 140 ° C. for 10 minutes.

To determine whether the MEMS cantilever beam was attached to the silicon chip surface, the MEMS chip was tested using an optical microscope (available from Nikon, Nelville, NY, under the trade name "OPTIPHOT 150"). . MEMS cantilever beams were tested under high magnification (1000 ×) and focused on the reference posts. The beam with the free tip on the same hyperfar side as the reference post was judged to be open and free of sticking. A beam having a focal plane near the silicon chip surface rather than the top surface of the reference post at the same time (with the reference post) at the free tip was determined to be stuck (ie, indicating sticking).

Treated MEMS cantilever beams produced in the above, 1500 m or more in length, were observed to have no sticking to the silicon chip surface by this technique.

Comparative Example 4

The MEMS chip containing the cantilever beam was sonicated for 20 minutes in acetone and then for 5 minutes in isopropyl alcohol as in Example 12 to remove the photoresist. The chip was then placed in the slot of the “fill / drain” device of Example 11, etched with 5 mL of 49 wt% aqueous HF for 3 minutes, then 10 times with 25 mL of deionized water (> 18 megohms) each time. After washing, each time washed 10 times with 25 mL of isopropyl alcohol. The etched chips were taken out, placed in a small glass cup containing isopropyl alcohol, and the cup, MEMS chip and isopropyl alcohol were dried in an oven at 140 ° C. for 10 minutes. By this method, using the analysis method of Example 12, the cantilever beam having a length of 400 µm or less was adequately opened, and no evidence of fixation was seen. However, beams longer than 400 μm did not adequately open the silicon chip surface (ie, the beam stuck to the chip surface).

Examples 13-21 and Comparative Examples 5-13

Examples 13-16, and Comparative Examples 5, 6, and 8 were prepared by General Method C.

Example 17 was carried out by changing the general method C as follows: The solution was odorless as inorganic spirits (trade name “TRIGONOX 21-C50”, Akzo, Chicago, Illinois, USA). 10 parts by weight of 50% by weight tert-butyl peroxy-2-ethylhexanoate, 10 parts by weight of E1, and 80 parts by weight of SHFE solvent. Instead of a black light blue BLB 15W bulb, a germicidal lamp (trade name "15 W G15T8", available from Osram Sylvania) which mainly emits 254 nm electromagnetic radiation was used.

Example 18 was carried out as in Example 17, except no light exposure was used. Instead, the sample was heated in an oil bath at 50 ° C. for 30 minutes.

Example 19 shows a polycrystalline silicon wafer as a substrate (10,000 Å undoped polysilicon on a 100 mm diameter Si (100) wafer obtained from WaferNet; 49 wt% HF in CMOS grade instead of etching the wafer pieces in ammonium fluoride solution). Prepared according to general method A, except etching in an aqueous solution for 3 minutes), and mixtures of E1 with 5% by weight 2-hydroxy-2-methyl-1-phenyl-1-propanone and 50% by weight heptane The procedure was carried out according to general method C, except that 45 wt% of the compound was used.

Example 20 was carried out as in Example 19, except that E1 was used as 5% by weight in a 5% by weight 2-hydroxy-2-methyl-1-phenyl-1-propanone and 90% by weight heptane mixture.

Example 21 was carried out using silicon 100 1 × 1 cm pieces (obtained from wafernet). The pieces were cleaned by washing in the order of heptane, acetone and isopropyl alcohol. The cleaned pieces were exposed to UV and ozone for 10 minutes using the ozone apparatus described in General Method A. Silicon pieces were placed in test tubes. Acetone was added and the mixture was sonicated for 20 minutes. Acetone was decanted. Isopropyl alcohol was added and the mixture was sonicated for 20 minutes. Isopropyl alcohol was decanted and the silicon pieces were dried in air. The silicon pieces were placed in a CMOS-grade 49 wt% HF aqueous solution and left for 3 minutes. Silicon pieces were removed from HF and placed in approximately 100 mL of water (≧ 18 megohm resistance) in a plastic container. The silicon pieces were again placed in a CMOS-grade 49 wt% HF aqueous solution and left for 3 minutes. After the silicon pieces were removed from the HF, they were placed in approximately 100 mL of isopropyl alcohol in a plastic container. It was then removed from isopropyl alcohol and placed in a small glass cup (approximately 2 mL volume) filled with isopropyl alcohol. Isopropyl alcohol was replaced with 30 mL of heptane over 10 minutes. The silicon pieces were placed in a quartz tube containing a solution of 45% by weight of E1 and 5% by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone in nitrogen sparged for 15 minutes. The silicon pieces were spun for 30 minutes as in general method B. Silicon pieces were removed from the tubes and placed in small glass cups (approximately 2 mL volumes) filled with heptane. After heptane (30 mL) was added to the cup over 10 minutes to wash the silicon pieces, 30 mL of isopropyl alcohol was added over 10 minutes and 30 mL of SHFE was added over 10 minutes. The wafer was removed from the cup and blow dried with nitrogen.

Comparative Examples 7 and 9 were carried out according to general method C, except that no solvent was used. The solution consisted of 5% by weight 2-hydroxy-2-methyl-1-phenyl-1-propanone in the indicated olefins.

Comparative Examples 10 and 11 are the same as Comparative Examples 7 and 6, except that 2,2-dimethoxy-2-phenylacetophenone was used instead of 2-hydroxy-2-methyl-1-phenyl-1-propanone. Was performed.

Comparative Examples 12 and 13 were performed as in Comparative Examples 10 and 11, except that five freeze-thaw cycles were used to deoxygenate the contents of the tube.

The olefins and solvents used in Examples 13 to 21 and Comparative Examples 5 to 13, and the contact angle measurement results are shown in Table 2 below.

Example 22

A silicon chip containing a MEMS cantilever beam prepared as in Example 12 and from which the photoresist was removed was placed in a "charge / drain" apparatus. A 49 mL% aqueous HF solution of 5 mL volume CMOS grade was added to the device and the chip was etched for 3 minutes to open the cantilever beam MEMS device. The chip was then washed with 10 × 25 mL portions of deionized water (≧ 18 megohm resistance) over a total of 10 minutes. After draining the last portion of water, 5 mL of a CMOS grade 49 wt% HF aqueous solution was added and the MEMS chip was etched again for 3 minutes. The aqueous HF solution was drained again. The etched chips were then washed in order with isopropyl alcohol for 10 minutes and with heptane for 10 minutes, with washing being performed at 10 charge and drain cycles over 10 minutes in the same manner as the water wash, respectively.

The chip was removed from heptane and contained 5 parts by weight of E1, 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone (trade name "Daroker 1173") free radical photoinitiator and 90 parts by weight of heptane. Into a quartz tube in a solution (sparging with dry nitrogen for 15 minutes). The tube was fitted to a rubber septum and spun for 30 minutes under the conditions of Example 11. After spinning, the MEMS chip was removed from the quartz tube and placed in a small glass cup (approximately 2 mL volume) containing heptane. 30 ml of heptane was added to the cup over 10 minutes to wash the MEMS chip (excess extra). Then 30 mL of isopropyl alcohol was added to the cup over 10 minutes, and then 30 mL SHFE was added to the cup over 10 minutes. The cup containing the MEMS chip (under SHFE) was placed in an oven at 140 ° C. for 10 minutes to dry the MEMS chip. According to this procedure, 1150 μl long cantilever beams were observed to be liberated from the surface (according to the method of Example 12) and longer beams showed evidence of fixation.

Example 23

As in Example 12, the cantilever beam MEMS device was opened by immersing the chip containing the MEMS cantilever beam and removing the photoresist in a 49% wt. HF aqueous solution of CMOS grade for 3 minutes. The chip was then washed with deionized water (≧ 18 megohm resistance) over 10 minutes. The etched chips were then washed for 2 minutes with isopropyl alcohol and for 3 minutes with another isopropyl alcohol. The chips were transferred to a third isopropyl alcohol bath in a small dish (˜2 mL volume) used for sample coating. Isopropyl alcohol in the dish containing chips was replaced with 10 × 2 mL portions of SHFE. The SHFE was then replaced with 6 × 2 mL portions of a 1.0 mM E10 solution (approximately 90 g) in SHFE containing two drops of a solution of 1 g of chloroplatinic acid in 10 mL of isopropyl alcohol and left for 1 minute. The coating solution was then replaced with 10 × 2 mL portions of SHFE. The sample dish containing the chips under SHFE was placed in a heated 10 mL high pressure stainless steel vessel equipped with a high pressure pump at the inlet and a vent line at the outlet to dry the MEMS chip. The vessel was charged with 60 ° C., 200 atmospheric pressure (20 MPa) CO ₂ . The contents of the vessel were replaced with 5 × 10 mL portions of CO ₂ to effectively remove the SHFE. The CO ₂ remaining in the vessel was evacuated to atmospheric pressure, and the dried chips were taken out and evaluated according to the method of Example 12. A 1450 μl long cantilever beam was observed to be liberated from the surface, and longer beams showed evidence of fixation.

Examples 24-25 and Comparative Example 14

Examples 24-25 and Comparative Example 14 were carried out according to general method D. The specific fluorinated olefin, solvent and contact angle measurement results used are shown in Table 3 below.

Examples 26-30

The effect of hydrosilylation process conditions on fluorinated olefin E9 is reported in Examples 26-30. The general method A was used to prepare the silicon substrates used in Examples 26-30.

Example 26 was performed according to General Method B, except that pure E9 was placed in a test tube with polished glass fittings and fitted to a condenser. Prior to introducing the silicon wafer pieces, E9 in vitro was sparged with nitrogen for 30 minutes. After introducing the sample, nitrogen sparging was continued for 15 minutes.

Example 27 was performed according to General Method D, modified as follows: using pure E9 (ie, solventless), sparging E9 in vitro with nitrogen for 1 hour before introducing silicon wafer pieces, After introducing the silicon wafer pieces, nitrogen sparging was continued for 2.5 hours, and the samples were then heated in an oil bath at 180 ° C. for 30 minutes.

Example 28 was performed as in Example 27 except that a 5 vol% E9 solution in FSOLV was used instead of pure E9.

Example 29 was carried out as in Example 26, except that no capacitor was used.

Example 30 was performed using a glass apparatus consisting of three pieces of tubes connected in an "H" form. The top of each portion of the "H" was opened for the introduction of samples and reagents. The "stand" of "H" was 2 cm above the bottom of "H". A piece of Si wafer was put in one leg of "H", and 1 mL of E9 was put in the other leg. After sparging the wet compound on the wet side for 30 minutes with nitrogen, the etched silicon wafer pieces with Si—H bonds were placed on the dry side of “H”. The top of the "H" was sealed with a rubber septum and the device was purged with nitrogen for another hour. The drain tube for nitrogen purging was removed, but the inlet tube was left in the apparatus under a positive pressure of nitrogen. The apparatus was then placed in a heating bath according to General Method B for 4.5 hours, removed and cooled with water at room temperature for 5 minutes. The wafer pieces were removed, washed in order of SHFE, heptane, acetone, isopropyl alcohol, and blow dried.

The contact angle measurement results reported in Table 4 below can be compared with the results reported in Comparative Examples 1 and 9, for example.

Examples 31 to 34

Examples 31-34 illustrate the effect of hydrosilylation process conditions on fluorinated olefins E12 and E13.

Example 31 was carried out according to general method D, except using pure E12 (solvent free) and heating the tube at 180 ° C. for 30 minutes.

Example 32 was carried out as in Example 30, except that 100 mg of E12 was used instead of E9 as the olefin.

Example 33 was carried out as in Example 31, except that E13 was used instead of E12.

Example 34 was carried out as in Example 30, except that E13 was used instead of E9.

The contact angle measurement results are shown in Table 5 below.

Claims (23)

Providing a silicon substrate having a plurality of Si—H bonds; Providing a composition comprising a fluorinated olefin of formula: And Contacting the composition with the silicon substrate under conditions such that the fluorinated olefin will covalently adhere to the surface of the silicon substrate Method of modifying a silicon substrate comprising: Where m is an integer of 1 or more, n is an integer of 0 or more, Z is a divalent linking group, R _f is a highly fluorinated organic group. Providing a silicon substrate; Etching the silicon substrate to form a plurality of Si—H bonds; Providing a composition comprising a fluorinated olefin of formula: And Contacting the composition with the silicon substrate under conditions such that the fluorinated olefin will covalently adhere to the silicon substrate An article comprising a chemically modified silicon substrate prepared according to a method comprising: Where m is an integer of 1 or more, n is an integer of 0 or more, Z is a divalent linking group, R _f is a highly fluorinated organic group. An article comprising a chemically modified silicon substrate, wherein the chemically modified substrate comprises one or more silicon atoms covalently bonded to an organic group of the formula: Where m is an integer of 1 or more, n is an integer of 0 or more, Z is a divalent linking group, R _f is a highly fluorinated organic group, Si _sub is a substrate silicon atom directly bonded to one or more additional substrate silicon atoms. The method of claim 1 or the article of claim 2 or 3, wherein m is in the range of 1-20. The method of claim 1 or the article of claims 2 or 3, wherein m is 1. The method of claim 1 or the article of claim 2 or 3, wherein n is in the range of 0 to 20. The method of claim 1 or the article of claim 2 or 3, wherein n is in the range of 0-3. Z is a covalent bond, -O- or The method of claim 1 or the article of claim 2 or 3, wherein R ¹ is alkyl or H. 4. Z is -O- or Phosphorus, the method of claim 1 or the article of claim 2 or 3. The method of claim 1 or the article of claims 2 or 3, wherein R _f contains fluorine in an amount of at least 50% by weight or more. The method of claim 1 or the article of claims 2 or 3, wherein R _f contains fluorine in an amount of at least 60% by weight or more. The method of claim 1 or the article of claims 2 or 3, wherein R _f comprises a perfluoroalkyl group having 4 to 12 carbon atoms. The method of claim 1 or the article of claim 2, wherein the fluorinated olefin comprises a poly (perfluoroalkyleneoxy) group. Fluorinated Olefin Formula The method of claim 1 or the article of claim 2 having the same. Fluorinated Olefin Formula The method of claim 1, wherein the fluorinated olefin comprises a poly (perfluoroalkyleneoxy) group. The method of claim 1 or the article of claim 2, wherein the fluorinated olefin comprises a plurality of allyloxy groups. The method of claim 1 or the article of claims 2 or 3, wherein the silicon substrate comprises a microelectromechanical system device. The method of claim 1 or the article of claims 2 or 3, wherein the silicon substrate comprises a microfluidic device. The method of claim 1 or the article of claim 2, wherein the composition further comprises a solvent having a boiling point of 180 ° C. or higher. The method of claim 1 or the article of claim 2, wherein the conditions comprise a temperature above 180 ° C. 3. The article of claim 1, wherein the contact of the composition with the silicon substrate comprises contacting the fluorinated olefin vapor with the silicon substrate. The article of claim 1 or 2, wherein the composition further comprises at least one of a free-radical photoinitiator or a photocatalyst, wherein the condition comprises electromagnetic radiation. The method of claim 22, wherein the free-radical photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl-1-propanone.