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Moisture-curable silicone corrosion resistant coatings - Patent # 5162460 - PatentGenius
Moisture-curable silicone corrosion resistant coatings
5162460 Moisture-curable silicone corrosion resistant coatings
Application: 07/778,049
Inventors: Be; Anh (Midland County, MI)
Popa; Paul J. (Bay County, MI)
Vincent; Harold L. (Midland County, MI)
U.S. Class: 525/478; 528/17; 528/18; 528/31; 528/33
Field Of Search: 528/31; 528/33; 528/17; 528/18; 525/478
U.S Patent Documents: 3069451; 3101277; 3127383; 3145175; 3397046; 3450736; 4332844; 4477641; 4701380; 4849564; 5051311; 5068301
Foreign Patent Documents: 0299641; 56-145111
Other References: Rudoi, V. M., V. A. Ogarev and A. A. Trapesnikov. Kolloidn Zr. (Colloid Journal), 32(2), pp. 401-403 (1975)..
Abstract: A method for imparting corrosion resistance to a metal substrate comprising coating said substrate with a moisture-curable silicone composition is disclosed. The composition consists essentially of a tetrafunctional or hexafunctional silicone polymer (I) which is modified with a liquid organohydrogenpolysiloxane (II) such that, when the functional groups of (I) are alkoxy radicals, the organohydrogenpolysiloxane contains at least 4 silicon hydride groups per molecule and when the functional groups of (I) are oxime groups, the organohydrogenpolysiloxane contains at least 5 silicon hydride groups per molecule.
1. A method for imparting corrosion resistance to a metal substrate comprising coating said substrate with a moisture-curable silicone composition and subsequently curing said siliconecomposition on said substrate, said silicone composition consisting essentially of a homogeneous blend of (I) a silicone polymer selected from the group consisting of those having the average structure
wherein R and R' each represent a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, a halogenated alkyl radical having 1 to 3 carbon atoms, an aryl radical, an arylalkyl radical, and acycloaliphatic radical, at least 95 mole percent of groups R' being methyl, X is a hydrolyzable group selected from the group consisting of an alkoxy radical having 1 to 3 carbon atoms and an oxime group having the formula --ON.dbd.C(R'').sub.2 in whichR'' is independently selected from the group consisting of an alkyl radical having 1 to 20 carbon atoms and vinyl and n has a value such that said silicone polymer has a viscosity of about 1 to 500 Poise at 25.degree. C.; and (II) from about 10 toabout 50 parts by weight, per 100 parts by weight of said silicone polymer (I), of a liquid organohydrogenpolysiloxane, the organic groups of which are independently selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms and aphenyl radical, no more than 20 mole percent of said organic groups of said organohydrogenpolysiloxane (II) being phenyl with the proviso that when X of said silicone polymer (I) is said alkoxy radical, said silicone composition further comprises aneffective amount of a cure catalyst for said silicone polymer (I) and said organohydrogenpolysiloxane (II) contains at least 4 silicon hydride groups per molecule and when X of said silicon polymer (I) is said oxime group, said organohydrogenpolysiloxane(II) contains at least 5 silicon hydride groups per molecule.
2. The method according to claim 1, wherein X of said silicone polymer (I) is said alkoxy group and R' is methyl.
4. The method according to claim 3, wherein said organohydrogenpolysiloxane (II) is represented by the formula
in which Me represents a methyl radical. Q is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, a phenyl radical and hydrogen and the values of x and y are adjusted so as to provide at least 4 silicon hydridegroups per molecule of said organohydrogenpolysiloxane while maintaining the viscosity thereof below 100 Poise at 25.degree. C.
5. The method according to claim 4, wherein said organohydrogenpolysiloxane (II) is represented by the formula
in which Me denotes a methyl radical and b has an average value of 30 to 100.
6. The method according to claim 3, wherein 20 to 40 parts by weight of said organohydrogenpolysiloxane (II) are used for each 100 parts by weight of said silicone polymer (I).
9. The method according to claim 8, wherein said organohydrogenpolysiloxane (II) is represented by the formula
in which Me represents a methyl radical. Q is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, a phenyl radical and hydrogen and the values of x and y are adjusted so as to provide at least 5 silicon hydridegroups per molecule of said organohydrogenpolysiloxane while maintaining the viscosity thereof below 100 Poise at 25.degree. C.
10. The method according to claim 9 wherein said organohydrogenpolysiloxane (II) is represented by the formula
11. The method according to claim 8, wherein 20 to 40 parts by weight of said organohydrogenpolysiloxane (II) are used for each 100 parts by weight of said silicone polymer (I).
12. A moisture-curable silicone composition consisting essentially of a homogeneous blend of (I) a silicone polymer selected from the group consisting of those having the average structure
wherein R and R' each represent a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, a halogenated alkyl radical having 1 to 3 carbon atoms, an aryl radical, an arylalkyl radical, and acycloaliphatic radical, at least 95 mole percent of groups R' being methyl, X is a hydrolyzable group selected from the group consisting of an alkoxy radical having 1 to 3 carbon atoms and an oxime group having the formula --ON.dbd.C(R'').sub.2 in whichR'' is independently selected from the group consisting of an alkyl radical having 1 to 20 carbon atoms and vinyl and n has a value such that said silicone polymer has viscosity of about 1 to 500 Poise at 25.degree. C.; and (II) from about 10 to about50 parts by weight, per 100 parts by weight of said silicone polymer (I), of a liquid organohydrogenpolysiloxane, the organic groups of which are independently selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms and a phenylradical, no more than 20 mole percent of said organic groups of said organohydrogenpolysiloxane (II) being phenyl with the proviso that when X of said silicone polymer (I) is said alkoxy radical, said silicone composition further comprises an effectiveamount of a cure catalyst for said silicone polymer (I) and said organohydrogenpolysiloxane (II) contains at least 4 silicon hydride groups per molecule and when X of said silicone polymer (I) is said oxime group, said organohydrogenpolysiloxane (II)contains at least 5 silicon hydride groups per molecule.
13. The composition according to claim 12, wherein X of said silicone polymer (I) is said alkoxy group and R' is methyl.
15. The composition according to claim 14, wherein said organohydrogenpolysiloxane (II) is represented by the formula
in which Me represents a methyl radical, Q is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, a phenyl radical and hydrogen and the values of x and y are adjusted so as to provide at least 4 silicon hydride groupsper molecule of said organohydrogenpolysiloxane while maintaining the viscosity thereof below 100 Poise at 25.degree. C.
16. The composition according to claim 15, wherein said organohydrogenpolysiloxane (II) is represented by the formula
17. The composition according to claim 14, wherein 20 to 40 parts by weight of said organohydrogenpolysiloxane (II) are used for each 100 parts by weight of said silicone polymer (I).
20. The composition according to claim 19, wherein said organohydrogenpolysiloxane (II) is represented by the formula
in which Me represents a methyl radical, Q is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, a phenyl radical and hydrogen and the values of x and y are adjusted so as to provide at least 5 silicon hydride groupsper molecule of said organohydrogenpolysiloxane while maintaining the viscosity thereof below 100 Poise at 25.degree. C.
21. The composition according to claim 20, wherein said organohydrogenpolysiloxane (II) is represented by the formula
22. The composition according to claim 19, wherein 20 to 40 parts by weight of said organohydrogenpolysiloxane (II) are used for each 100 parts by weight of said silicone polymer (I).
The present invention relates to a method for imparting corrosion resistance to a metal substrate. More particularly, the invention relates to coating said substrate with a moisture-curable composition containing an alkoxy or oxime-functionalsilicone polymer and an organohydrogenpolysiloxane.
Various workers have noted that certain compounds and compositions containing hydrogen groups on silicon atoms (SiH groups) can impart a measure of corrosion resistance to metals under particular circumstances. This observation has beendocumented in such patents as U.S. Pat. No. 3,397,046 to Greyson, in which an organohydrogenpolysiloxane is heat cured on a silver coated copper conductor and then overcoated with a polymeric insulating layer. Likewise. U.S. Pat. No. 3,069,451 toFritz mentions that certain SiH-containing silanes prepared according to his method can form laquer-like coatings which can be utilized for anti-rust purposes. De Monterey, in U.S. Pat. No. 3,450,736. reacted SiH-functional polysiloxanes with anethylenically unsaturated compound to obtain a modified polymer having good lubricating and corrosion inhibition properties. Wright, in U.S. Pat. No. 3,145,175, discloses a grease composition which provides improved corrosion resistance to metals,which composition is a thickened copolymer containing SiH groups or a thickened mixture of a diorganopolysiloxane and an organohydrogenpolysiloxane. Japanese Kokai (Laid Open) 56-145111 to Asahi Chemical Industry Company teaches rust-preventing pigmentscomprising microparticulated hydrogenated silicon which can be added to paint formulations.
U.S. Pat. No. 4,701,380 to Narula et al. discloses curable compositions which provide corrosion protection to metals. These compositions are based on a hydroxy-terminated diorganopolysiloxane polymer and contain either a reaction product orblend of a resinous copolymeric siloxane and a liquid organohydrogenpolysiloxane in addition to an organosilane which promotes adhesion to substrates. Similar compositions, which are specifically designed to be applied by spraying, are also taught inU.S. Pat. No. 5.051.311 to Popa et al. European Patent Application 0299641 (published on Jan. 18, 1989) to Dow Corning Corporation discloses curable compositions which provide corrosion protection to metals. These compositions are similar to those ofthe above cited patent to Narula et al. and are also based on a combination of a hydroxy-terminated diorganopolysiloxane polymer and either a reaction product or blend of a resinous copolymeric siloxane and a liquid organohydrogenpolysiloxane butattribute improved corrosion performance to the addition of alumina or hydrates of alumina.
The use of SiH-containing compounds is also known in compositions which promote adhesion between silicone materials and various other substrates. For example, Hamada et al., in U.S. Pat. No. 4,332,844, teach primer compositions for siliconerubbers containing an alkoxy-functional silicon compound, an organotitanate and an organohydrogensilicon compound. In Kolloidn. Zr. (Colloid Journal), 32(2), p. 401-403 (1975), Rudoi et al. studied the kinetics of bond formation between a glasssurface and a hydroxy-terminated filled polydimethylsiloxane containing a crosslinker/adhesion promoter which was a product of hydrolytic condensation of tetraethoxysilane with oligomeric polydiethylethylhydrogensiloxane.
Although the above references may invite further experimentation with various SiH-containing compounds or compositions for the purpose of improving adhesion or corrosion resistance in other systems, there is no suggestion provided by this art asto the possible benefit to expect in any particular system. In other words, there is no practical guidance provided in the above literature that would lead the skilled artisan to reliably predict additional compositions which could be advantageouslymodified to obtain the desired properties.
Applicants have now discovered that two different types of moisture-curable silicone compositions can be used as corrosion resistant coatings when each is modified with particular organohydrogenpolysiloxanes according to the present invention. It has been found that silicone room temperature vulcanizing (RTV) compositions of the invention which cure through alkoxy or oxime functionality can be modified to provide significantly improved corrosion resistance when cured on a metal substrate bythe inclusion of specific amounts of certain organohydrogenpolysiloxanes. Thus, in order to be considered within the scope of the present invention, the corrosion resistance of a metal substrate coated with the cured silicone composition ischaracterized by at least 1000 hours of failure-free salt fog exposure, the test methods and definitions of "failure" being detailed infra. Furthermore, to be within the scope of the invention, the failure-free time in the above test must be at leasttwice that obtained for the corresponding control silicone composition which does not contain said organohydrogenpolysiloxane. To the contrary, at least one other moisture-curable silicone system of the type described in U.S. Pat. No. 3,817,909 toToporcer et al. and based on hydroxy-ended polydimethylsiloxane which was chain extended with an acetamidosilane and capped with aminoxysilicon functionality, could not be so modified and actually resulted in decreased corrosion protection relative tothe unmodified control RTV composition.
The present invention therefore relates to a method for imparting corrosion resistance to a metal substrate comprising coating said substrate with a moisture-curable silicone composition and subsequently curing said silicone composition on saidsubstrate, said silicone composition consisting essentially of a homogeneous blend of
wherein R and R' are monovalent hydrocarbon radicals, at least 95 mole percent of groups R' being methyl. X is a hydrolyzable group selected from the group consisting of an alkoxy radical having 1 to 3 carbon atoms and an oxime group having theformula --ON.dbd.C(R'').sub.2 in which R'' is independently selected from the group consisting of an alkyl radical having 1 to 20 carbon atoms and vinyl and n has a value such that said silicone polymer has viscosity of about 1 to 500 Poise at 25.degree. C.; and
(II) from about 10 to about 50 parts by weight, per 100 parts by weight of said silicone polymer (I), of a liquid organohydrogenpolysiloxane, the organic groups of which are independently selected from the group consisting of alkyl radicalshaving 1 to 4 carbon atoms and a phenyl radical, no more than 20 mole percent of said organic groups of said organohydrogenpolysiloxane (II) being phenyl with the proviso that
when X of said silicone polymer (I) is said alkoxy radical, said silicone composition further comprises an effective amount of a cure catalyst for said silicone polymer (I) and said organohydrogenpolysiloxane (II) contains at least 4 SiH groupsper molecule and
wherein R and R' each represent a monovalent hydrocarbon radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms; such as methyl, ethyl, isopropyl and butyl; a halogenated alkyl radical having 1 to 3 carbon atoms,such as trifluoropropyl and chloropropyl; an alkenyl radical having 1 to 3 carbon atoms; such as vinyl and allyl; an aryl radical, such as phenyl, tolyl, and xylyl; an arylalkyl radical, such as betaphenylethyl and beta-phenylpropyl; and a cycloaliphaticradical, such as cyclopentyl and cyclohexyl. For the purposes of this invention, at least 95% of R' radicals are methyl. Preferably, all R and R' groups are methyl. The value for n in the above formulas is selected so as to provide a viscosity ofabout 1 to 500 Poise for silicone polymer (I) at 25.degree. C. Preferably, this viscosity is about 40 to 150 Poise at 25.degree. C. The hydrolyzable group X in the above formulas is selected from the group consisting of an alkoxy radical having 1 to 3carbon atoms and an oxime group having the formula --ON.dbd.C(R'').sub.2, in which R'' is independently selected from the group consisting of an alkyl radical having 1 to 20 carbon atoms and vinyl.
The scientific and patent literature is replete with examples of conventional moisture-curable systems based on the above described silicone polymers and since these compositions are well known in the art and are available commercially, detaileddescription thereof is considered unnecessary. By way of illustration, the interested reader is referred to the extensive bibliographies provided in U.S. Pat. No. 3,635,887. hereby incorporated by reference, and chapter 8 of W. Noll's text Chemistryand Technology of Silicones. Academic Press. N.Y. (1968) for further descriptions of the above cure chemistries.
wherein R' and n are defined above, with a stoichiometric excess of a silane having hydrolyzable groups selected from the alkoxy or oxime moieties previously represented by the group X in formula (i) or (ii). For example, silanes such asmethyltrimethoxysilane. tetramethoxysilane, vinyltrioximosilane tetraoximosilane or methyltrioximosilane may be used. The hydrolyzable groups of the silane react with the terminal hydroxyls of the diorganopolysiloxane to form a capped silicone polymerwhich is then capable of curing by exposure to moisture. Typically, such room temperature vulcanizing (RTV) compositions also contain a filler such as silica calcium carbonate, titanium dioxide, and silicone resin, inter alia. It is herein preferredthat the moisture-curable composition used in the method of the present invention contain a silica filler having a surface area of about 50 to about 400 m.sup.2 /g. Such fillers are typically employed at about 1 to about 15 parts by weight for each 100parts by weight of said silicone polymer (I). The RTV compositions may further contain appropriate catalysts to promote the intended moisture cure under ambient conditions.
Organohydrogenpolysiloxane (II) is a linear, cyclic, or branched liquid siloxane which is miscible with said silicone polymer (I). For the purposes of the present invention, this component has a viscosity of less than about 100 Poise at25.degree. C. contains at least four silicon-bonded hydrogen radicals (i.e. SiH) per molecule when X of silicone polymer (I) is said alkoxy group and contains at least five SiH groups per molecule when X is said oxime group. The organic groups oforganohydrogenpolysiloxane (II) can be independently selected from alkyl radicals having 1 to 4 carbon atoms or a phenyl radical with the proviso that no more than about 20 mole percent of said organic groups are phenyl. When the organic groups of theorganohydrogenpolysiloxane (II) are selected from higher alkyl groups, or phenyl radicals are present at a level greater than about 20 percent, it has been observed that components (I) and (II) are not compatible and the objects of the invention are notachieved.
It is preferred that component (II) is a linear polymer or copolymer which comprises R'''(H)SiO.sub.2/2 units and, optionally. R'''.sub.2 SiO.sub.2/2 units, wherein R''' is independently selected from alkyl radicals having 1 to 4 carbon atoms orphenyl, as described above, the polymer or copolymer being otherwise in compliance with the provisions previously recited. The end groups of such polymers or copolymers are not considered critical as long as they are inert with respect to the otheringredients employed. Examples of suitable terminal groups include such structures as Me.sub.3 SiO.sub.1/2 and HMe.sub.2 SiO.sub.1/2, in which Me hereinafter denotes a methyl radical. Preferred structures of this type are based on linear liquidswherein R''' is methyl, such as those represented by the formula
in which Q is the above defined group R''' or H and the values of x and y are adjusted so as to provide the requisite number of SiH groups per molecule while maintaining the viscosity within the above stated limit. It is highly preferred thatx=0 in the above formula such that organohydrogenpolysiloxane (II) has the structure
in which b has an average value of 30 to 100. most preferably about 70.
According to the method of the present invention, moisture-curable compositions are first prepared by thoroughly mixing, on a solids basis, from about 10 to about 50 parts by weight, preferably from 20 to 40 parts of organohydrogenpolysiloxane(II) with 100 parts by weight of silicone polymer (I). If desired or appropriate, the moisture-curable compositions of this invention can further comprise typical additives used in the formulation of conventional RTV compositions, such as catalysts,fillers, pigments, dyes, flow modifiers, thickeners and cure-control additives, inter alia. As far as is known, the order of mixing is not critical with respect to such additions.
As stated above, when the moisture-curable composition is based on a silicone polymer (I) having alkoxy functionality, the organohydrogenpolysiloxane (II) utilized should contain at least four silicon hydride (SiH) groups in its molecule in orderto impart the improved corrosion resistance according to the present invention. In addition as is well known in the art, the curable systems based on the alkoxy-functional silicones should also contain a cure catalyst known to promote the hydrolysis ofthe alkoxy groups and the condensation of alkoxy with silanol groups to form a three-dimensional siloxane network. Catalysts suitable for this purpose may be selected from the organotitanates, such as tetraisopropyl titanate and tetrabutyl titanate andorganometallic compounds, such as dibutyltin dilaurate, tin octoate, dibutyltin diacetate, zinc octoate, cobalt octoate, cobalt naphthanate and cerium naphthanate. Typically, from about 1 to 10 parts by weight of the catalyst are employed for each 100parts by weight of the silicone polymer (I). For the purposes of the present invention, the preferred alkoxy functionality is methoxy (i.e., X in formula (i) or (ii) is --OMe).
In a similar way, when the moisture-curable composition is based on a silicone polymer (I) having oxime functionality, the organohydrogenpolysiloxane (II) utilized should contain at least five SiH groups in its molecule in order to impart theimproved corrosion resistance according to the present invention. Unlike the alkoxy systems however, a catalyst is not absolutely necessary in this case if the silicone polymer (I) is prepared with relatively pure silanes. Otherwise, a catalyst can beadvantageously employed to promote the curing reaction. Effective catalysts in this regard are exemplified by structures such as Ti(OR'''').sub.4 or (AcAc)Ti(OR'''').sub.2, in which R'''' is independently selected from alkyl radicals having 3 to 8carbon atoms and AcAc denotes an acetylacetonate group. A particularly preferred catalyst for this purposed is tetrabutyl titanate. For the purposes of the present invention, the preferred oxime functionality is given by the formula--ON.dbd.C(R'').sub.2 in which R'' is independently selected from methyl or ethyl radicals, a highly preferred oxime group of the invention being --ON.dbd.C(Me)(Et), in which Et hereinafter denotes an ethyl radical.
In practice, the above moisture-curable compositions are typically diluted with an organic solvent in order to provide a desired coating composition viscosity. Such solvents as hexane, heptane toluene, xylene, mineral spirits, ketones, andacetates are suitable for this purpose. Alternatively, a 100% solids system is also contemplated if the viscosity is not too great.
According to the instant method, the resulting coating composition is subsequently applied to a metal surfaces by any of the methods commonly practised in the coatings arts. For example. substrates may be dipped, brushed, sprayed, or flowcoated. Optimal amounts of solvents and catalyst to be included in such coating compositions may readily be determined by routine experimentation. After coating of the metal substrates with the coating compositions of this invention, the coatings,which typically should be at least 1 mil in thickness, preferably 3-5 mils, are cured by exposure to ambient humidity. This cure process can, of course, be hastened by increasing humidity and/or temperature.
The compositions of the present invention find particular utility as coating compositions for metal articles, such as sheet, wire and particles. When applied as 100% solids, or from solution, and cured on such substrates as iron, steel,aluminum, brass, cobalt-nickel alloys, magnesium, silver or copper, coatings comprising these compositions provide excellent corrosion protection to the metal surfaces. This is particularly true for the case of ferrous metals exposed to moisture andsalt, whereby the corrosion resistance of the substrate is characterized by at least 1000 hours of failure-free salt fog exposure, defined infra, and such failure-free exposure is at least twice that obtained with the corresponding composition which doesnot contain said organohydrogenpolysiloxane (II).
The following examples are presented to further illustrate the compositions of this invention, but are not to be constructed as limiting the invention, which is delineated in the appended claims. All parts and percentages in the examples are ona weight basis and viscosities are measured at 25.degree. C unless indicated to the contrary.
A conventional moisture-curable composition (RTV A) based on a tetramethoxy-functional polydimethylsiloxane polymer was prepared. RTV A consisted of a reaction product of: (A) 93.5% of a polymer base consisting of 83.3% hydroxyl-terminatedpolydimethylsiloxane (degree of polymerization of about 378 and a viscosity of about 40 Poise) and 16.7% of a trimethylated silica having a surface area of about 250 m.sup.2 /g, (B) 0.5% tetrabutyl titanate and (C) 6% of an endcapping compositionconsisting of 99.95% methyltrimethoxysilane and 0.05% of a fluorescent dye (UVITEX.TM. OB, Ciba-Geigy Corp., Greensboro, N.C.).
wherein Me hereinafter denotes a methyl radical, and a paraffinic solvent (ISOPAR.TM. G, Exxon Chemical Co., Houston, TX) as shown in Table 1.
TABLE 1 ______________________________________ Formulation 1 Form. 2 Form. 3 Form. 4 ______________________________________ RTV A 20 parts 15 15 15 Polysiloxane (a) 0 1.5 3 6 ISOPAR .TM. G 10 5 5 5 ______________________________________
Duplicate 3".times.6" SAE 1010 cold rolled steel smooth finish panels were cleaned with hot water and a Scotch-Brite.TM. pad, rinsed with deionized water and blown dry with filtered air. The panels were brush-coated to a final dry filmthickness (DFT) of 3-5 mils in two application (each coat 1.5-2.5 mils DFT), allowing each coat to cure overnight at ambient temperature and humidity. After the second coat was cured, the backs of the panels were coated with a commercially availablecorrosion resistant silicone coating. The edges of the panels were then taped with Kaptor.TM. tape and the panel was single-scribed according to American Society for Testing Materials (ASTM) D1654 using a tungsten carbide tool. The panels were placedin a salt fog chamber (ASTM B117; sodium chloride concentration of 5% and a temperature of 37.degree. C.) after curing at ambient conditions a total of seven days. The panels were removed from the salt fog cabinet every one to two weeks and evaluatedin accordance to ASTM D1654 and ASTM D610 for extent of corrosion. Time to failure was recorded in Table 2. failure being defined herein as a rating of less than 5 by ASTM D1654 (i.e. average corrosion creepage from scribe line greater than 5 mm=3/16inch) and less than 10 by ASTM D610 (i.e., essentially no surface rusting outside of the scribed area). The above mentioned ASTM standard tests are well known in the art and further description thereof is not considered necessary.
TABLE 2 ______________________________________ Example 1 Parts (per hundred RTV A) Formulation of polysiloxane (a) Hours to Failure ______________________________________ 1 (control) 0 750 2 10 3300 3 20 3300 4 40 3300 ______________________________________
TABLE 3 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 20 parts 20 15 PDMS fluid 0 4 6 ISOPAR .TM. G 10 10 7.5 ______________________________________
TABLE 4 ______________________________________ Example 2 Parts (per hundred RTV A) Formulation of PDMS Hours to Failure ______________________________________ 1 (Control) 0 750 2 20 550 3 40 1275 ______________________________________
A liquid alpha,omega-dihydroxydimethylpolysiloxane fluid having a degree of polymerization (DP) of about 539 and a viscosity of about 140 Poise was endcapped with methyltrimethoxysilane using tetrabutyl titanate to facilitate the reaction betweenthe silanols and the methoxy groups, this composition being shown in table 5.
TABLE 5 ______________________________________ Hydroxy-ended PDMS (DP = 539) 172.5 parts MeSi(OCH.sub.3).sub.3 13.8 Tetrabutyl titanate 1.4 ______________________________________
After being placed in a 100.degree. C. over for 11/2 hours, mixed and allowed to sit overnight at room temperature, the resulting composition, RTV B, comprised a silicone polymer having the calculated average formula ##STR1## RTV B was mixedwith different amounts of liquid organohydrogenpolysiloxanes (b) and (c) having the average formulas
______________________________________ Me.sub.3 SiO(MeHSiO).sub.4 SiMe.sub.3 (b) Me.sub.3 SiO(MeHSiO).sub.8 SiMe.sub.3 (c) ______________________________________
TABLE 6 ______________________________________ Formulation Form. Form. Form. Form. 1 2 3 4 5 ______________________________________ Base Polymer 20 parts 20 15 20 15 siloxane (b) 0 4 6 0 0 siloxane (c) 0 0 0 4 6 ISOPAR .TM. G 7.8 7.87.8 7.8 7.8 ______________________________________
TABLE 7 ______________________________________ Example 3 Parts (per hundred RTV B) Formulation of siloxane (b) or (c) Hours to Failure ______________________________________ 1 (Control) 0 325 2 20 parts (b) 2950 3 40 parts (b) 3475 420 parts (c) 4000 5 40 parts (c) 4000 ______________________________________
______________________________________ Me.sub.3 SiO(MeHSiO)SiMe.sub.3 (d) Me.sub.3 SiO(MeHSiO).sub.2 SiMe.sub.3 (e) ______________________________________
TABLE 8 ______________________________________ Formulation Form. Form. Form. Form. 1 2 3 4 5 ______________________________________ RTV B 20 parts 20 15 20 15 siloxane (d) 0 4 6 0 0 siloxane (e) 0 0 0 4 6 ISOPAR .TM. G 7.8 7.8 7.8 7.87.8 ______________________________________
TABLE 9 ______________________________________ Example 4 Parts (per hundred RTV B) Formulation of siloxane (d) or (e) Hours to Failure ______________________________________ 1 (Control) 0 325 2 20 parts (d) 650 3 40 parts (d) 575 4 20parts (e) 575 5 40 parts (e) 800 ______________________________________
______________________________________ Me.sub.3 SiO(MeHSiO).sub.10 (Me.sub.2 SiO).sub.103 SiMe.sub.3 (f) Me.sub.3 SiO(MeHSiO).sub.4 (Me.sub.2 SiO).sub.9 SiMe.sub.3 (g) ______________________________________
TABLE 10 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 15 parts 15 15 siloxane (f) 0 6 0 siloxane (g) 0 0 3 ISOPAR .TM. G 7.5 7.5 7.5 ______________________________________
TABLE 11 ______________________________________ Example 5 Parts (per hundred RTV A) Formulation of siloxane (f) or (g) Hours to Failure ______________________________________ 1 (Control) 0 600 2 40 parts (f) 2200 3 20 parts (g) 2800 ______________________________________
TABLE 12 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 15 parts 15 15 siloxane (h) 0 3 6 ISOPAR .TM. G 7.5 7.5 7.5 ______________________________________
TABLE 13 ______________________________________ Example 6 Parts (per hundred RTV A) Formulation of siloxane (h) Hours to Failure ______________________________________ 1 (Control) 0 600 2 20 1850 3 40 2800 ______________________________________
TABLE 14 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 15 parts 15 15 siloxane (i) 0 3 6 ISOPAR .TM. G 7.5 7.5 7.5 ______________________________________
TABLE 15 ______________________________________ Example 7 Parts (per hundred RTV A) Formulation of siloxane (i) Hours to Failure ______________________________________ 1 (Control) 0 600 2 20 675 3 40 675 ______________________________________
(where R=--(CH.sub.2).sub.17 CH.sub.3)
TABLE 16 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 15 parts 15 15 siloxane (j) 0 3 6 ISOPAR .TM. G 7.5 7.5 7.5 ______________________________________
TABLE 17 ______________________________________ Example 8 Parts (per hundred RTV A) Formulation of siloxane (j) Hours to Failure ______________________________________ 1 (Control) 0 600 2 20 675 3 40 275 ______________________________________
A moisture-curable composition (RTV C) was prepared according to the method described in Example 3 except that the liquid alpha,omega-dihydroxydimethylpolysiloxane fluid had a DP of about 378 and a viscosity of about 40 Poise, as shown in Table18. The silicone polymer of this composition had the calculated average formula ##STR2##
TABLE 18 ______________________________________ hydroxy-ended PDMS (DP = 378) 144 parts MeSi(OMe).sub.3 11.5 Tetrabutyl titanate 1.2 ______________________________________
TABLE 19 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV C 12 parts 12 11 siloxane (a) 0 2.4 4.4 ISOPAR .TM. G 1.5 1.5 1.5 Tetrabutyl titanate 0.1 0.1 0.1 ______________________________________
TABLE 20 ______________________________________ Example 9 Parts (per hundred RTV C) Formulation of siloxane (a) Hours to Failure ______________________________________ 1 (Control) 0 350 2 20 2625 3 40 2625 ______________________________________
TABLE 21 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV C 12 parts 12 11 siloxane (k) 0 2.4 4.4 ISOPAR .TM. G 1.5 1.5 1.5 Tetrabutyl titanate 0.1 0.1 0.1 ______________________________________
TABLE 22 ______________________________________ Example 10 Parts (per hundred RTV C) Formulation of siloxane (k) Hours to Failure ______________________________________ 1 (Control) 0 350 2 20 2625 3 40 2625 ______________________________________
TABLE 23 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV C 12 parts 12 11 siloxane (h) 0 2.4 4.4 ISOPAR .TM. G 1.5 1.5 1.5 Tetrabutyl titanate 0.1 0.1 0.1 ______________________________________
TABLE 24 ______________________________________ Example 11 Parts (per hundred RTV C) Formulation of siloxane (h) Hours to Failure ______________________________________ 1 (Control) 0 350 2 20 2625 3 40 2625 ______________________________________
TABLE 25 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV C 12 parts 12 11 siloxane (l) 0 2.4 4.4 ISOPAR .TM. G 1.5 1.5 1.5 Tetrabutyl titanate 0.1 0.1 0.1 ______________________________________
TABLE 26 ______________________________________ Example 12 Parts (per hundred RTV C) Formulation of siloxane (l) Hours to Failure ______________________________________ 1 (Control) 0 350 2 20 525 3 40 525 ______________________________________
A liquid alpha,omega-dihydroxydimethylpolysiloxane fluid having a DP of about 378 and a viscosity of about 40 Poise was endcapped with methyltris(methylethylketoxime)silane using tetrabutyl titanate to facilitate the reaction between the silanolsand the oxime groups. The constituents of this composition (RTV D) are shown in Table 27, wherein Et hereinafter denotes an ethyl radical.
TABLE 27 ______________________________________ Hydroxy-ended PDMS (DP = 378) 120 parts MeSi(ON.dbd.CMeEt).sub.3 8.4 Tetrabutyl titanate 6 ISOPAR .TM. G 20 ______________________________________
TABLE 28 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV D 11 parts 11 10 siloxane (a) 0 1.9 3.5 ______________________________________
TABLE 29 ______________________________________ Example 13 Parts (per hundred RTV D) Formulation of siloxane (a) Hours to Failure ______________________________________ 1 (Control) 0 240 2 20 3000 3 40 3000 ______________________________________
TABLE 30 ______________________________________ Formulation 1 Form. 2 ______________________________________ RTV D 11 parts 11 siloxane (k) 0 1.9 ______________________________________
TABLE 31 ______________________________________ Example 14 Parts (per hundred RTV D) Formulation of siloxane (k) Hours to Failure ______________________________________ 1 (Control) 0 240 2 20 3000 ______________________________________
TABLE 32 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV D 11 parts 11 10 siloxane (h) 0 1.9 3.5 ______________________________________
TABLE 33 ______________________________________ Example 15 Parts (per hundred RTV D) Formulation of siloxane (h) Hours to Failure ______________________________________ 1 (Control) 0 240 2 20 3000 3 40 3000 ______________________________________
TABLE 34 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV D 11 parts 11 10 siloxane (l) 0 1.9 3.5 ______________________________________
TABLE 35 ______________________________________ Example 16 Parts (per hundred RTV D) Formulation of siloxane (l) Hours to Failure ______________________________________ 1 (Control) 0 240 2 20 725 3 40 900 ______________________________________
TABLE 36 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 7 parts 7 7 silane (m) 0 1.4 2.8 ISOPAR .TM. G 5 5 5 ______________________________________
TABLE 37 ______________________________________ Example 17 Parts (per hundred RTV A) Formulation of silane (m) Hours to Failure ______________________________________ 1 (Control) 0 875 2 20 1200 3 40 240 ______________________________________
TABLE 38 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV A 15 parts 15 15 siloxane (n) 0 3 6 ISOPAR .TM. G 15 10 7.5 ______________________________________
TABLE 39 ______________________________________ Example 18 Parts (per hundred RTV A) Formulation of siloxane (n) Hours to Failure ______________________________________ 1 (Control) 0 825 2 20 1775 3 40 1825 ______________________________________
A liquid alpha,omega-dihydroxydimethylpolysiloxane fluid having a DP of about 539 and a viscosity of about 140 Poise was endcapped with a tetraoximosilane according to Table 40. The resulting moisture-curable composition, RTV E, comprised asilicone polymer having the calculated average formula
TABLE 49 ______________________________________ Hydroxyl-ended PDMS (DP = 539) 172.5 parts Si(ON.dbd.CMeEt).sub.4 36.2 ISOPAR .TM. G 8.0 ______________________________________
TABLE 41 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV E 20 parts 20 15 siloxane (c) 0 3.5 5.3 ISOPAR .TM. G 6.9 6.9 6.9 ______________________________________
TABLE 42 ______________________________________ Example 19 Parts (per hundred RTV E) Formulation of siloxane (c) Hours to Failure ______________________________________ 1 (Control) 0 150 2 20 2000 3 40 2000 ______________________________________
TABLE 43 __________________________________________________________________________ Formulation 1 Form 2 Form 3 Form 4 Form 5 Form 6 Form 7 __________________________________________________________________________ RTV E 20 20 15 20 1520 15 siloxane (b) 0 3.5 5.3 0 0 0 0 siloxane (d) 0 0 0 3.5 5.3 0 0 siloxane (e) 0 0 0 0 0 3.5 5.3 ISOPAR .TM. G 6.9 6.9 6.9 6.9 6.9 6.9 6.9 __________________________________________________________________________
TABLE 44 ______________________________________ Example 20 Parts (per hundred RTV E) Formulation of siloxane (b), (d) or (e) Hours to Failure ______________________________________ 1 (Control) 0 150 2 20 150 3 40 150 4 20 150 5 40 150 6 20 150 7 40 150 ______________________________________
A liquid alpha,omega-dihydroxydimethylpolysiloxane fluid having a DP of about 378 and a viscosity of about 40 Poise was endcapped with a tetraoximosilane according to the composition of Table 45. This composition, RTV F, contained siliconepolymer having the calculated average formula
TABLE 45 ______________________________________ Hydroxy-ended PDMS 115 parts Si(ON.dbd.CMeEt).sub.4 24.1 ISOPAR .TM. G 5.3 ______________________________________
TABLE 46 ______________________________________ Form. Form. Form. Form. Formulation 1 2 3 4 5 ______________________________________ RTV F 11 parts 11 10 11 10 siloxane (a) 0 1.9 3.5 0 0 siloxane (k) 0 0 0 1.9 3.5 ______________________________________
TABLE 47 ______________________________________ Example 21 Parts (per hundred RTV F) Formulation of siloxane (a) or (k) Hours to Failure ______________________________________ 1 (Control) 0 175 2 20 2350 3 40 1650 4 20 2465 5 40 1650 ______________________________________
TABLE 48 ______________________________________ Form. Form. Form. Form. Formulation 1 2 3 4 5 ______________________________________ RTV F 11 parts 11 10 11 10 siloxane (h) 0 1.9 3.5 0 0 siloxane (l) 0 0 0 1.9 3.5 ______________________________________
TABLE 49 ______________________________________ Example 22 Parts (per hundred RTV F) Formulation of siloxane (h) or (l) Hours to Failure ______________________________________ 1 (Control) 0 175 2 20 parts (h) 725 3 40 parts (h) 900 420 parts (l) 300 5 40 parts (l) 175 ______________________________________
TABLE 50 ______________________________________ Form. Form. Form. Form. Formulation 1 2 3 4 5 ______________________________________ RTV F 15 parts 15 15 15 15 siloxane (i) 0 2.6 5.3 0 0 siloxane (j) 0 0 0 2.6 5.3 ______________________________________
TABLE 51 ______________________________________ Example 23 Parts (per hundred RTV F) Formulation of siloxane (i) or (j) Hours to Failure ______________________________________ 1 (Control) 0 200 2 20 200 3 40 200 4 20 775 5 40 775 ______________________________________
A liquid alpha,omega-dihydroxydimethylpolysiloxane fluid having a DP of about 539 and a viscosity of about 140 Poise was endcapped with methylvinyl bis(n-methylacetamide)silane and an N,N-diethylaminoxypolysiloxane having the average formula##STR5## in dimethylformamide solvent according to the composition of Table 52 to form RTV G.
TABLE 52 ______________________________________ hydroxy-ended PDMS (DP = 539) 100 parts Methylvinyl bis(n-methylacetamide)silane 2.5 N,N-diethylaminoxypolysiloxane 1 Dimethylformamide 1 ______________________________________
RTV G, which is a moisture-curable composition of the type described in above-cited U.S. Pat. No. 3,817,909 to Toporcer et al., was mixed with different amounts of siloxane (a), described in Example 1, and a paraffinic solvent, as shown inTable 53.
TABLE 53 ______________________________________ Formulation 1 Form. 2 Form. 3 ______________________________________ RTV G 20 parts 20 20 siloxane (a) 0 4 8 ISOPAR .TM. G 7.5 7.5 7.5 ______________________________________
TABLE 54 ______________________________________ Example 24 Parts (per hundred RTV G) Formulation of siloxane (a) Hours to Failure ______________________________________ 1 (Control) 0 250 2 20 150 3 40 150 ______________________________________
The method of the present invention resulted in improved corrosion resistance to the extent that failure times in the above described salt fog test were at least two times greater for the instant compositions containing theorganohydrogenpolysiloxane (II) of the present invention than for control moisture-curable RTVs. Moreover, according to the requirements of the invention, the absolute failure times of the instant RTV systems was at least 1000 hours when measured bythese standard corrosion tests. The only inconsistency in these observations related to the cyclic organohydrogenpolysiloxane (h), shown in Example 6. This siloxane contained molecules having both 4 and 5 SiH groups and hence reflects the transitionfrom non-operative to operative embodiments for RTVs based on the silicone polymers having oxime functionality. Thus, RTV D of Example 15 met the criteria of the present method while RTV F of Example 22 did not, both systems employing theorganohydrogenpolysiloxane (h).
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