Oil resistant silicone sealants

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to room temperature vulcanizing (RTV) silicone compositions, curable in the presence of moisture, comprising polydiorganosiloxanes, acyloxy-functional crosslinkers and additives such as metal acetylacetonates and metal oxides which provide oil resistance to the cured composition.
2. Background of the Information
The use of room temperature vulcanizing (RTV) silicone sealants for creating formed-in-place gaskets is well known in both original equipment manufacture and in repair and maintenance. A problem with certain conventional silicone sealants is their tendency in the presence of hot oil to lose structural integrity leading to seal failure. Therefore, it is desirable to have silicone sealants providing increased oil resistance as demonstrated by increased tensile strength in the presence of hot oil.
Getson, et al., U.S. Pat. No. 4,123,472, describe oil resistant organopolysiloxane compositions prepared by polymerizing an acrylic ester and an acrylic nitrile in the presence of an organopolysiloxane and a free radical initiator at an elevated temperature. This modified polysiloxane when mixed with a crosslinking agent, such as an acyloxy-functional silane, and exposed to moisture and heat aging, cures to an oil resistant composition.
Beers, U.S. Pat. No. 4,680,363, describes a process for forming a one component RTV silicone rubber composition with good bonding properties at high humidity conditions, and Beers, U.S. Pat. No. 4,758,611, describes the RTV silicone composition, such composition comprising a silanol-endblocked diorganopolysiloxane, an acyloxy-functional crosslinking agent, a curing promoter which is a salt of a carboxylic acid, and a magnesium or zinc salt of a carboxylic acid as an acid scavenger.
Beers, U.S. Pat. No. 4,833,037, describes a laminated article comprising a plurality of metal substrates, wherein between the metal substrates there is a layer of a one component RTV silicone rubber composition with good bonding properties at high humidity conditions, the composition comprising a silanol-endblocked diorganopolysiloxane, an acyloxy-functional crosslinking agent, a curing promoter which is a salt of a carboxylic acid, and an acid scavenger selected from magnesium or zinc oxide, magnesium, aluminum or zinc metal, magnesium or zinc salt of a carboxylic acid, or mixtures thereof.
Beers, U.S. Pat. No. 4,257,932 describes a self-bonding silicone RTV comprising a silanol endstopped polydiorganosiloxane; a fluid polysiloxane having a high degree of tri or tetrafunctionality; a silica filler; a crosslinking silane evolving relatively low volatility carboxylic acid fragments on hydrolysis; and a tin catalyst. Beers, also discloses the improvement of high temperature performance with the addition of an iron oxide thermal stabilizer.
Letoffe, et al., U.S. Pat. No. 4,797,462, describe organopolysiloxanes curable into elastomeric state and well adapted as sealing materials for a variety of substrates, comprising a polyhydroxylated polysiloxane, a polyacyloxysilane crosslinking agent and an effective amount of at least one of calcium oxide, strontium oxide and/or barium oxide cure accelerator therefor.
The present inventors have unexpectedly determined that the addition of a metal acetylacetonate, preferably along with a metal oxide, to a RTV silicone composition comprising a polydiorganosiloxane, acyloxy-functional crosslinker, filler, and tin catalyst results in a cured composition having increased hot oil resistance. In addition, these compositions may find use when cured as sealants, adhesives, gaskets, coatings, molding and potting compounds, and gels.
The objective of this invention is to provide a RTV silicone composition having increased hot oil resistance upon curing.
SUMMARY OF THE INVENTION
The present invention is a RTV silicone composition having increased hot oil resistance when cured. The RTV silicone composition which is curable in the presence of moisture comprises a polydiorganosiloxane, an acyloxy-functional crosslinker, a metal salt of a carboxylic acid catalyst, a filler, and a metal acetylacetonate.
DETAILED DESCRIPTION OF THE INVENTION
This invention is a RTV silicone composition which is curable in the presence of moisture and has increased hot oil resistance upon curing comprising:
(A) 100 parts by weight of a polydiorganosiloxane in which the terminal groups are selected from the group consisting of silanol and triorganosilyl groups, provided at least 60 mole percent of the terminal groups are silanol groups;
(B) 1 to 15 parts by weight of an acyloxy-functional crosslinking agent described by the formula
R.sub.m Si(OCOR').sub.4-m
where R is a monovalent hydrocarbon radical comprising from 1 to about 12 carbon atoms, each R' is an independently selected monovalent hydrocarbon radical comprising from 1 to about 12 carbon atoms, and m is 0 or 1;
(C) 0.001 to 1 part by weight of a metal salt of a carboxylic acid catalyst;
(D) 5 to 150 parts by weight of a filler; and
(E) an effective amount of a metal acetylacetonate.
Component (A) is a polydiorganosiloxane having terminal groups selected from the group consisting of silanol and triorganosilyl groups, provided at least 60 mole percent of the terminal groups are silanol groups. The polydiorganosiloxane may be one type of polymer or a mixture of different polymers. The polydiorganosiloxanes may have a linear structure and may be homopolymers or copolymers. In addition, the organic groups linked to any particular silicon atom may be the same or different. The organic groups of the polydiorganosiloxane can include any monovalent hydrocarbon group or any monovalent halohydrocarbon group comprising 1 to about 18 carbon atoms. Preferred organic groups are methyl, ethyl, propyl, phenyl, vinyl, and 3,3,3-trifluoropropyl, with methyl being most preferred.
The terminal groups of the polydiorganosiloxane are selected from the group consisting of silanol and triorganosilyl groups. The organic substituent of the triorganosilyl groups can include any monovalent hydrocarbon group or any monovalent halohydrocarbon group comprising 1 to about 18 carbon atoms. The preferred organic substituent of the triorganosilyl groups are methyl, ethyl, propyl, phenyl, vinyl, and 3,3,3-trifluoropropyl, with methyl being most preferred.
Although the terminal groups are selected from silanol and triorganosilyl groups, it is required that at least 60 mole percent of the terminal groups be silanol groups in order to obtain the desired properties of the composition when cured. Preferably, 80 to 100 mole percent of the terminal groups of the polydiorganosiloxane are silanol groups.
The viscosity of the polydiorganosiloxane may be from about 1 to 150 Pa.multidot.s at 250.degree. C. The preferred viscosity of the polydiorganosiloxane is from about 5 to 100 Pa.multidot.s at 25.degree. C.
The methods of manufacture of the silanol terminated polydiorganosiloxanes are well known in the art. One common method is based upon the hydrolysis of diorganodichlorosilane, the separation of a diorganotetrasiloxane cyclic material from the hydrolysis mixture, and the subsequent polymerization of the cyclic material to the polydiorganosiloxane through the use of an alkaline catalyst. The triorganosilyl terminated polydiorganosiloxanes are also prepared by known methods, such as described in Dupree, U.S. Pat. No. 3,274,145, which is hereby incorporated by reference.
Component (B) is an acyloxy-functional crosslinking agent described by the formula
R.sub.m Si(OCOR').sub.4-m
where R is a monovalent hydrocarbon radical comprising from 1 to about 12 carbon atoms, each R' is an independently selected monovalent hydrocarbon radical comprising from 1 to about 12 carbon atoms, and m is 0 or 1.
R is a monovalent hydrocarbon radical comprising from 1 to about 12 carbon atoms. The monovalent hydrocarbon radicals represented by R may be linear or branched and can include alkyl radicals such as methyl, ethyl, isopropyl, or hexyl; alkenyl radicals such as vinyl, allyl or hexenyl; alkynal radicals such as propargyl; cycloaliphatic radicals such as cyclopentyl, cyclohexyl or cyclohexenyl; aromatic radicals such as phenyl or tolyl; and aralkyl radicals such as benzyl or beta-phenylethyl. R is preferably methyl or ethyl.
Each R' is an independently selected monovalent hydrocarbon radical comprising from 1 to about 12 carbon atoms. Examples of R' include those provided for R. R' is preferably methyl or ethyl, with methyl being most preferred.
The acyloxy-functional crosslinker may have trifunctionality, as occurs when m is 1 or tetrafunctionality, as occurs when m is 0. It is preferred that m be 1.
Examples of preferred acyloxy-functional crosslinkers include methyltriacetoxysilane, ethyltriacetoxysilane, methyl-trisbenzoxysilane, vinyltriacetoxysilane and methyl-tris-2-ethylhexanoxy silane.
The acyloxy-functional crosslinker can be present in the present composition in amounts from 1 to 15 parts by weight based on 100 parts by weight of the polydiorganosiloxane, and preferably from 2 to 10 parts by weight on the same basis. The acyloxy-functional crosslinker may be added as a single species or as a mixture of two or more species.
Component (C) is a metal salt of a carboxylic acid catalyst. The metal component of the catalyst is preferably tin, but may be , for example, lead, chromium, antimony, iron, cadmium, barium, titanium, bismuth, or magnesium. Examples of suitable metal salts of carboxylic acids include tin naphthenate, lead octoate, tin octoate, iron stearate, tin oleate, dibutyltindilaurate, dibutyltindiacetate, dibutyl tin oxide, and dimethyl tin bis-neodecanoate. Preferred catalysts are dibutyltindilaurate, dibutyltindiacetate, and dimethyl tin bis-neodecanoate. The most preferred catalysts are dibutyltindilaurate and dibutyltindiacetate.
The catalyst can be present in the present composition in amounts from 0.001 to 1 part by weight based on 100 parts by weight of the polydiorganosiloxane, and preferably from 0.01 to 0.3 part by weight on the same basis. It is most preferred to have 0.01 to 0.2 part by weight catalyst present in the composition on the same basis. The catalyst may be added as a single species or as a mixture of two or more species.
In order to obtain the desired physical properties of the present composition when cured, a filler (Component (D)) is added to the composition. This filler may include reinforcing fillers, semi-reinforcing fillers, or non-reinforcing fillers also called extending fillers, or any combination thereof. One or more of each type of filler is also acceptable.
Reinforcing fillers include any finely divided form of silica which can be prepared by precipitation or a pyrogenic process and may be treated or untreated. Generally, methods of treating the silica can include mixing the silica with polycyclosiloxane such as disclosed in Lucas U.S. Pat. No. 2,938,009, and Lichtenwalner U.S. Pat. No. 3,004,859, or silazanes as disclosed in Smith U.S. Pat. No. 3,635,743, which are incorporated herein by reference. The treating agents may also include liquid hydroxyl-terminated polydiorganosiloxanes which can contain an average of about 2 to 20 repeating units and can contain at least one alkenyl unit. The treating agent may also be an alkylhalosilane, such as dimethyldichlorosilane or an alkoxysilane. Carbon black is also useful as a reinforcing filler in this invention. Semi-reinforcing fillers include barium sulfate and crystalline silica. Non-reinforcing or extending fillers include glass spheres, wollastonite, diatomaceous earths, clay, and talc. The preferred fillers are untreated fumed silica and treated fumed silica.
The filler can be present in the present composition in amounts from 5 to 150 parts by weight based on 100 parts by weight of the polydiorganosiloxane, and preferably from 5 to 30 parts by weight on the same basis. The filler may be added as a single species or as a mixture of two or more species.
Component (E) is a metal acetylacetonate. The inventors have unexpectedly determined that the addition of a metal acetylacetonate to an RTV silicone composition provides the composition upon curing with increased hot oil resistance.
The metal portion of the metal acetylacetonate is preferably copper, iron or zirconium, with copper being most preferable, but may be selected from the group consisting of copper, chromium, iron, aluminum, zinc, titanium, and zirconium. Examples of Component (E) include copper II acetylacetonate, ferric acetylacetonate, chromium III acetylacetonate, and zinc acetylacetonate.
An effective amount of the metal acetylacetonate is an amount which provides increased hot oil resistance to the RTV silicone composition upon curing. Typically, about 0.01 to 5 parts by weight metal acetylacetonate based on 100 parts by weight of the polydiorganosiloxane is effective. It is preferable to add about 0.05 to 1.5 parts by weight metal acetylacetonate on the same basis, with about 0.1 to 0.6 part by weight metal acetylacetonate on the same basis being most preferred. The metal acetylacetonate may be added as a single species or as a mixture of two or more species.
In a preferred embodiment Component (F), a metal oxide, is also added to the RTV silicone composition. The metal portion of the metal oxide is most preferably calcium, but may also be selected from the group consisting of calcium, zinc, magnesium, aluminum, zirconium, barium, titanium, strontium and copper. Examples of Component (F) include calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, zirconium oxide, barium oxide, titanium IV dioxide, and copper II oxide.
The metal oxide can be present in the present composition in amounts from about 0.01 to 10 parts by weight based on 100 parts by weight of the polydiorganosiloxane, It is preferable to add from about 0.01 to 1.5 parts by weight on the same basis and most preferably from about 0.01 to 1 part by weight on the same basis. The metal oxide may be added as a single species or as a mixture of two or more species.
In preferred embodiments, the present compositions can also optionally include up to about 2 parts by weight of an adhesion promoter based on 100 parts by weight of the polydiorganosiloxane. Examples of useful adhesion promoters include ethylpolysilicate and glycidoxypropyltrimethoxysilane.
In addition to the above ingredients, the present composition may include additives which impart or enhance certain properties of the cured composition or facilitate processing of the curable composition. Typical additives include, but are not limited to: plasticizers, functional and non-functional diluents, pigments, dyes, heat and/or ultraviolet light stabilizers, flame-retardant agents, thickeners, rheology modifiers, and preservatives. The effect of any such additives should be evaluated as to their result and impact on other properties of the composition.
The RTV silicone composition of this invention may be prepared by mixing all the ingredients together in amounts as specified to provide a composition which is stable in the absence of moisture and which cures to an elastomeric material when exposed to moisture.
These compositions are preferably prepared by mixing the ingredients under anhydrous conditions. This means that the amounts of moisture or water in the ingredients used should be minimized and the conditions of mixing should minimize the amounts of moisture or water allowed into the system. Excess moisture or water may have deleterious effects on the composition, such as causing curing in the storage package or reduced cured properties.
The present compositions may be prepared as either a one package system or a two (or multi) package system. With a one package system, all the ingredients are mixed together and stored in an anhydrous state. with a two or multi package system the ingredients may be stored separately and then mixed prior to use. For example, it is often convenient to form a "base" blend comprising a polydiorganosiloxane, a filler and, if needed, a plasticizer (I). Another blend comprising curing agents such as the crosslinker and catalyst may also be mixed together (II) and still another blend comprising additional ingredients including Components (E) and (F) may also be mixed together (III). As described above, the components comprising (I), (II) and (III) may be mixed together or separately. If mixed and stored together a one part sealant results. obviously a two or multi package system is possible if (I), (II), and (III) are mixed and packaged separately. It is also possible to mix and store two of the components together, ie (I) and (III) and later mix in (II). In a preferred embodiment of the present invention it is preferred to mix and store (I) and (II) together and then later mix in (III) as required.
The present RTV silicone compositions may be used, for example, as gasket materials for sealing gaps or seams in a given substrate or for sealing between substrates. Due to the oil resistance of the present RTV silicone compositions when cured these compositions are preferably used for sealing gaps or substrates having surfaces exposed to oil or hot oil. However, these RTV silicone compositions may also be used to seal gaps or substrates which may not have surfaces exposed to oil or hot oil.
A method for sealing using the present composition comprises for example, (i) providing at least two substrates having a plurality of surfaces; (ii) applying a layer of a RTV silicone composition which is curable in the presence of moisture, to at least a portion of at least one of the surfaces of at least one of the substrates, the RTV silicone composition comprising Components (A)-(E) and preferably also Component (F), as described above; (iii) bringing at least two of the substrates, where at least one of the substrates has the RTV silicone composition applied thereto, into proximity so as to form a gasket of the RTV silicone composition therebetween; and (iv) exposing the gasket of step (iii) to moisture to effect curing of the RTV silicone composition.
The substrates useful for this preferred embodiment can be metal materials, composites or certain plastic materials. Preferably the substrates are metal materials.

EXAMPLES
The following examples are presented for illustrative purposes and should not be construed as limiting the invention which is delineated in the claims.
In the following examples, unless otherwise noted, the compositions were mixed at 23.degree. C..+-.2.degree. C. and 50%.+-.5% relative humidity; cast, and then cured for 7 days at 23.degree. C..+-.2.degree. C. and 50%.+-.5% relative humidity before oil immersion testing. The cured samples were then immersed in oil for 14 days at 150.degree. C. per ASTM D471 except the samples were cooled to 23.degree. C..+-.2.degree. C. in the test fluid rather than in a cooling fluid. The oil used for immersion testing was Goodwrench 5W30 SAE SH/SG. The durometer (Shore A) results provided in each table were obtained using the method described in ASTM D2240 with the following exceptions: 2.54 cm.times.1.91 cm tabs having a thickness of 0.64 cm were tested and an average of 5 readings was reported. The tensile, 100% modulus, and elongation results provided in each table were obtained using the method described in ASTM D412 with each tensile, 100% modulus, and elongation value reported as the average of 3 samples. Adhesion testing was conducted according to ASTM D903 with the following exceptions: 1) the speed of testing was 5.08 cm/min., 2) substrates were cleaned with MIBK (methylisobutylketone) followed by an acetone rinse, 3) the flexible substrate was 1.27 cm wide. Volume swell % results were obtained using the method described in ASTM 471. Also, as used herein "part" or "parts" are by weight and "AcAc" refers to acetylacetonate.
Prior to use, the metal oxide powder was dried at 105.degree. C. for a minimum of 2 hrs. All metal oxides used in the examples with the exception of copper II oxide were obtained from Fisher Scientific (Pittsburgh, Pa.). Copper II oxide was obtained from Aldrich Chemical (Milwaukee, Wis.). Copper II AcAc was obtained from Acros Organics (Pittsburgh, Pa.) and Aldrich Chemical. Chromium III AcAc, Iron III AcAc and Aluminum AcAc were obtained from Acros Organics. Zinc AcAc Hydrate, Titanium IV Oxide AcAc and Zirconium AcAc were obtained from Aldrich Chemical. The fumed silica was obtained from Cabot Corp (Tuscola, Ill.). The dibutyl tin diacetate was obtained from Atochem Corporation (Philadelphia, Pa.). The silane and siloxane compounds were obtained from Dow Corning Corporation (Midland, Mich.). Ethylpolysilicate was obtained from Huls of America, Inc. (Piscataway, N.J.).
Example 1
Formulations were prepared as shown in Table 1.1. Ingredients numbered as 1, 2, 3 and 8 were combined with a compounder at approximately 70.degree. C., packaged into cartridges and then deaired. Ingredients numbered 4, 5, 6, 7 and 9 were mixed together and then injected into and mixed with the mixture of ingredients 1, 2, 3 and 8 using a Semco mixer (Model 388, Products Research and Chemical Corp, Glendale, Calif.). Samples were cast, cured and then tested in hot oil. Formulations 1A and 1C are controls while Formulations 1B and 1D have added copper acetylacetonate and calcium oxide. The post oil immersion tensile strength improved from less than 0.09 N/mm.sup.2 without the additives to greater than 0.75 N/mm.sup.2 with the additives. The results are provided in Tables 1.2(a) and 1.2(b).
TABLE 1.1______________________________________Formulations Form. Form. Form. Form.Component (parts) 1A* 1B 1C* 1D______________________________________1. 17.5 Pa .multidot. s, 85% silanol 100.00 100.00 100.00 100.00 terminated and 15% trimethyl terminated polydimethylsiloxane2. Untreated fumed silica 13.86 13.79 12.38 11.69 having a surface area of approximately 200 m.sup.2 /g3. Mixture of methyl (.about.45%) 6.19 6.19 5.55 5.23 and ethyl (.about.55%) triacetoxysilane4. 0.1 Pa .multidot. s Trimethyl 4.80 4.80 4.72 4.68 Endblocked Polydimethylsiloxane5. Approximately 0.075 Pa .multidot. s 2.40 2.4 2.36 2.34 hydroxy-terminated polydimethylsiloxane6. Copper acetylacetonate 0.00 0.24 0.00 0.247. Calcium Oxide 0.00 0.36 0.00 0.358. Dibutyl tin diacetate 0.03 0.03 0.03 0.039. Blue Silicone Paste** 0.64 0.64 0.63 0.63______________________________________ *Formulations 1A and 1C are the controls, with no additives included. **Ferro SV1232, Ferro Corp. (Edison, NJ)
TABLE 1.2(a)______________________________________Initial Results Prior to Oil Immersion Form. Form. Form. Form. 1A* 1B 1C* 1D______________________________________Durometer, Shore A 23 28 28 23Tensile Strength, N/mm.sup.2 1.48 1.69 2.16 1.48Elongation, % 349 366 460 349Modulus @ 100%, N/mm.sup.2 0.50 0.54 0.56 0.50______________________________________ *Formulations 1A and 1C are the controls, with no additives included.
TABLE 1.2(b)______________________________________5W30 Oil Immersion Results Form. Form. Form. Form. 1A* 1B 1C* 1D______________________________________Durometer, Shore A 0 6 0 4Tensile Strength, N/mm.sup.2 0.09 0.75 0.04 0.71Elongation, % 233 442 26 502Modulus @ 100%, N/mm.sup.2 0.08 0.28 N/A 0.21Volume Swell % 55 51 35 52______________________________________ *Formulations 1A and 1C are the controls, with no additives included.
Example 2
The ingredients listed in Table 2.1 were mixed and tested as described in Example 1. Ingredients numbered as 1, 2, 3 and 7 were combined with a compounder at approximately 70.degree. C. The mixture was then pigmented by mixing in ingredient 8, packaged into cartridges and then deaired. Ingredients numbered 4, 5, and 6 were mixed together and then injected into and mixed with the mixture of ingredients 1, 2, 3, 7 and 8 using a Semco mixer. The post oil immersion tensile strength was improved with the addition of the copper AcAc or calcium oxide added individually, however the combined effect is greater than either with copper AcAc or calcium oxide added individually. The results are provided in Tables 2.2(a) and 2.2(b).
TABLE 2.1______________________________________Formulations Form. Form. Form. Form.Component (parts) 2A* 2B 2C 2D______________________________________1. 17.5 Pa .multidot. s, 85% silanol 100.00 100.00 100.00 100.00 terminated and 15% trimethyl terminated polydimethylsiloxane2. Untreated fumed silica 13.36 13.36 13.36 13.86 having a surface area of approximately 200 m.sup.2 /g3. Mixture of methyl (.about.45%) 5.97 5.97 5.97 6.19 and ethyl (.about.55%) triacetoxysilane4. 12 Pa .multidot. s Trimethyl 1.98 1.98 1.98 2.05 Endblocked Polydimethylsiloxane5. Copper acetylacetonate 0.00 0.31 0.00 0.646. Calcium Oxide 0.00 0.00 0.62 0.647. Dibutyl tin diacetate 0.02 0.02 0.02 0.038. Black Pigment** 2.48 2.48 2.48 2.57______________________________________ *Formulation 2A is the control, with no additives included. **Paste of LV1011 Lampblack Powder, Harcross Pigments (Fairview Heights, IL)
TABLE 2.2(a)______________________________________Initial Results Prior to Oil Immersion Form. Form. Form. Form. 2A* 2B 2C 2D______________________________________Durometer, Shore A 25 26 26 27Tensile strength, N/mm.sup.2 2.02 1.73 2.01 1.70Elongation, % 473 426 469 405Modulus @ 100%, N/mm.sup.2 0.47 0.49 0.48 0.50______________________________________ *Formulation 2A is the control, with no additives included.
TABLE 2.2(b)______________________________________5W30 Oil Immersion Results Form. Form. Form. Form. 2A* 2B 2C 2D______________________________________Durometer, Shore A 0 0 0 6Tensile Strength, N/mm.sup.2 0.00 0.28 0.42 1.05Elongation, % 0 849 589 574Modulus @ 100%, N/mm.sup.2 0.00 0.08 0.16 0.26Volume Swell % N/A 57 58 54______________________________________ *Formulation 2A is the control, with no additives included.
Example 3
The ingredients listed in Table 3.1 were mixed and tested as described in Example 1. Ingredients numbered as 1, 2, 3 and 7 were combined with a compounder at approximately 70.degree. C., packaged into cartridges and then deaired. Ingredients numbered 4, 5, and 6 were mixed together and then injected into and mixed with the mixture of ingredients 1, 2, 3, and 7 using a Semco mixer. In this example different amounts of the copper AcAc and calcium oxide were used individually (Tables 3.1(a) and 3.1(b) respectively) and in combination (Table 3.1(c)). The results are provided in Tables 3.2(a) and 3.2(b).
TABLE 3.1(a)______________________________________Addition of Copper Acetylacetonate OnlyComponent (parts) 3A 3B 3C 3D 3E______________________________________1. 17.5 Pa .multidot. s, 85% 100.00 100.00 100.00 100.00 100.00 silanol terminated and 15% trimethyl terminated polydi- methylsiloxane2. Untreated fumed 22.21 22.21 22.21 22.21 22.21 silica having a surface area of approximately 200 m.sup.2 /g3. Mixture of methyl 9.15 9.15 9.15 9.15 9.15 (.about.45%) and ethyl (.about.55%) triacetoxy- silane4. 12 Pa .multidot. s Trimethyl 1.97 1.97 1.97 1.97 1.97 Endblocked Poly- dimethylsiloxane5. Copper acetyl- acetonate 0.32 0.52 0.99 1.31 1.976. Calcium Oxide 0.00 0.00 0.00 0.00 0.007. Dibutyl tin diacetate 0.05 0.05 0.05 0.05 0.05______________________________________
TABLE 3.1(b)______________________________________Addition of Calcium Oxide OnlyComponent (parts) 3F 3G 3H 3I______________________________________1. 17.5 Pa .multidot. s, 85% silanol 100.00 100.00 100.00 100.00 terminated and 15% trimethyl terminated polydimethyl- siloxane2. Untreated fumed silica having 22.21 22.21 22.21 22.21 a surface area of approxi- mately 200 m.sup.2 /g3. Mixture of methyl (.about.45%) 9.15 9.15 9.15 9.15 and ethyl (.about.55%) triacetoxy- silane4. 12 Pa .multidot. s Trimethyl End- 2.10 2.10 2.10 2.10 blocked Polydimethylsiloxane5. Copper acetylacetonate 0.00 0.00 0.00 0.006. Calcium Oxide 0.33 0.65 0.98 1.327. Dibutyl tin diacetate 0.05 0.05 0.05 0.05______________________________________
TABLE 3.1(c)______________________________________Addition of Copper Acetylacetonate and Calcium OxideComponent (parts) 3J 3K______________________________________1. 17.5 Pa .multidot. s, 85% silanol terminated 100.00 100.00 and 15% trimethyl terminated polydimethylsiloxane2. Untreated fumed silica having a 22.21 22.21 surface area of approximately 200 m.sup.2 /g3. Mixture of methyl (.about.45%) and 9.15 9.15 ethyl (.about.55%) triacetoxysilane4. 12 Pa .multidot. s Trimethyl Endblocked 2.10 2.63 Polydimethylsiloxane5. Copper acetylacetonate 0.33 0.666. Calcium Oxide 0.98 0.667. Dibutyl tin diacetate 0.05 0.05______________________________________
TABLE 3.2(a)______________________________________Initial Results Prior to Oil Immersion 100% Durometer Tensile Elongation ModulusFormulation Shore A N/mm.sup.2 % N/mm.sup.2______________________________________3A 46 2.47 240 1.303B 46 2.70 269 1.273C 48 2.79 280 1.273D 49 2.42 239 1.283E 49 2.43 244 1.283F 45 2.73 306 1.143G 46 2.68 299 1.143H 44 2.83 318 1.133I 43 2.97 328 1.123J 44 2.73 283 1.213K 47 2.47 251 1.27______________________________________
TABLE 3.2(b)______________________________________5W30 Oil Immersion Results Durometer Tensile Elongation 100% Modulus VolumeFormulation Shore A N/mm.sup.2 % N/mm.sup.2 Swell %______________________________________3A 13 0.88 354 0.42 363B 15 0.92 294 0.49 353C 17 1.14 329 0.53 353D 15 1.05 311 0.52 353E 14 0.96 305 0.5 353F 14 0.72 260 0.45 373G 17 1.07 271 0.61 373H 18 1.32 317 0.59 373I 19 1.27 266 0.59 343J 22 1.45 290 0.68 323K 23 1.50 282 0.74 29______________________________________
Example 4
The ingredients listed in Table 4.1 were mixed and tested as described in Example 1. Ingredients numbered as 1, 2, 3 and 8 were combined with a compounder at approximately 70.degree. C., packaged into cartridges and then deaired. Ingredients numbered 4, 5, 6, 7, 9, and 10 were mixed together and then injected into and mixed with the mixture of ingredients 1, 2, 3 and 8 using a Semco mixer. In this example an adhesion promoter (10) was also added. The adhesion promoter did not result in degraded oil resistance. The results are provided in Tables 4.2(a) and 4.2(b).
TABLE 4.1______________________________________Formulations Form. Form. Form. Form.Component (parts) 4A 4B 4C 4D______________________________________1. 17.5 Pa .multidot. s, 85% silanol 100.00 100.00 100.00 100.00 terminated and 15% trimethyl terminated polydimethylsiloxane2. Untreated fumed silica 13.89 13.93 15.05 15.15 having a surface area of approximately 200 m.sup.2 /g3. Mixture of methyl (.about.45%) 6.20 6.22 6.78 6.82 and ethyl (.about.55%) triacetoxysilane4. 0.1 Pa .multidot. s Trimethyl 4.81 4.83 2.09 2.11 Endblocked Polydimethylsiloxane5. Approximately 0.075 Pa .multidot. s 2.41 2.41 2.45 2.46 hydroxy-terminated polydimethylsiloxane.6. Copper acetylacetonate 0.24 0.25 0.25 0.257. Calcium Oxide 0.36 0.36 0.37 0.378. Dibutyl tin diacetate 0.03 0.03 0.03 0.039. Blue Silicone Paste* 0.48 0.48 0.48 0.4910. Ethylpolysilicate 0.64 1.29 0.65 1.32______________________________________ *Ferro SV1232, Ferro Corp. (Edison, NJ)
TABLE 4.2(a)______________________________________Initial Results Prior to Oil Immersion Form. Form. Form. Form. 4A 4B 4C 4D______________________________________Durometer, 25 25 28 28Shore ATensile 1.70 1.95 2.01 2.13Strength,N/mm.sup.2Elongation, % 425 452 429 469Modulus @ 0.48 0.44 0.52 0.52100%, N/mm.sup.2Adhesion to 6/28 14/32 6/34 22/381010 steel/ (1.05/4.9) (2.45/5.6) (1.05/5.95) (3.85/6.65)aluminum, pli(N/mm)______________________________________
TABLE 4.2(b)______________________________________5W30 Oil Immersion Results Form. Form. Form. Form. 4A 4B 4C 4D______________________________________Durometer, Shore A 3 4 5 6Tensile Strength, N/mm.sup.2 0.70 0.74 0.91 0.97Elongation, % 572 557 560 583Modulus @ 100%, N/mm.sup.2 0.19 0.21 0.23 0.23Volume Swell % 55 52 49 48______________________________________
Example 5
The ingredients listed in Table 5.1 were mixed and tested as described in Example 1. Ingredients numbered as 1, 2, 3 and 8 were combined with a compounder at approximately 70.degree. C., packaged into cartridges and then deaired. Ingredients numbered 4, 5, 6, 7, 9, and were mixed together and then injected into and mixed with the mixture of ingredients 1, 2, 3 and 8 using a Semco mixer. In this example, each Form. 5A incorporates copper acetylacetonate with a metal oxide as described in the results Tables 5.2(a)(1) and (b)(1). Each Form. 5B incorporates calcium oxide with a metal AcAc as described in the results Tables 5.2(a)(2) and (b) (2).
TABLE 5.1______________________________________FormulationsComponents (parts) Form. 5A Form 5B______________________________________1 17.5 Pa .multidot. s viscosity 85% silanol 100 100 terminated and 15% trimethyl terminated polydimethylsiloxane2 Untreated fumed silica having a 13.09 13.09 surface area of approximately 200 m.sup.2 /g3 Mixture of methyl (.about.45%) and 5.86 5.86 ethyl (.about.55%) triacetoxysilane4 0.1 Pa s Trimethyl Endblocked 4.76 4.76 Polydimethylsiloxane5 Approximately 0.075 Pa .multidot. s viscosity 2.38 2.38 hydroxy-terminated polydimethylsiloxane. 6a copper acetylacetonate 0.24 0.0 6b metal acetylacetonate (see Tables 0.0 0.24 5.2(a) (1) and (b) (1)) 7a calcium oxide 0.0 0.36 7b metal oxide (see Tables 5.2(a) (2) 0.36 0.0 and (b) (2))8 Dibutyl tin diacetate 0.03 0.039 Blue Silicone Paste* 0.44 0.4410 ethylpolysilicate 0.59 0.59______________________________________ *Ferro SV1232, Ferro Corp. (Edison, NJ)
TABLE 5.2(a)______________________________________Initial Results Prior to Oil Immersion 100% Durometer Tensile Elongation ModulusAdditive (Shore A) N/mm.sup.2 % N/mm.sup.2______________________________________(1) Samples containing a Metal AcAc and CaO (Form. (B))Chromium III AcAc 24.0 1.89 392 0.48Iron III AcAc 28.0 1.64 348 0.56Aluminum AcAc 29.0 1.44 333 0.55Zirconium AcAc 30.0 1.59 289 0.63Zinc AcAc Hydrate 26.0 1.53 347 0.52Titanium IV Oxide 33.0 1.59 270 0.68AcAc(2) Samples containing Copper AcAc and a Metal Oxide (Form. (A))Zinc Oxide 26.0 1.65 393 0.50Magnesium Oxide 26.0 1.56 400 0.48Titanium Dioxide 26.0 2.04 484 0.48Barium Oxide 24.0 1.64 435 0.45Aluminum Oxide 24.0 1.48 398 0.46Zirconium Oxide 25.0 1.65 409 0.48Copper II Oxide 30.0 1.88 392 0.54______________________________________
TABLE 5.2(b)______________________________________5W30 Oil Immersion Results Elonga- 100% Durometer Tensile tion Modulus VolumeAdditive (Shore A) N/mm.sup.2 % N/mm.sup.2 Swell %______________________________________(1) Samples containing a Metal AcAc and CaO (Form. (B))Chromium III AcAc 0 0.60 829 0.12 56Iron III AcAc 3 0.92 539 0.23 50Aluminum AcAc 0 0.40 705 0.11 50Zirconium AcAc 5 0.81 382 0.24 45Zinc AcAc Hydrate 4 0.72 583 0.19 54Titanium IV Oxide 4 0.76 446 0.23 50AcAc(2) Samples containing Copper AcAc and a Metal Oxide (Form. (A))Zinc Oxide 0 0.46 789 0.12 56Magnesium Oxide 4 0.78 632 0.18 52Titanium Dioxide 1 0.59 807 0.12 50Barium Oxide 0 0.54 715 0.12 53Aluminum Oxide 0 0.43 610 0.12 51Zirconium Oxide 1 0.51 706 0.12 51Copper II Oxide 1 0.53 632 0.13 52______________________________________

Number	Name	Date
3542901	Cooper et al.	Nov 1970
4123472	Getson et al.	Oct 1978
4257932	Beers	Mar 1981
4680363	Beers	Jul 1987
4689363	Inoue et al.	Aug 1987
4758611	Beers	Jul 1988
4797462	Letoffe et al.	Jan 1989
4833037	Beers	May 1989
5268441	Barthel et al.	Dec 1993
5489479	Lucas et al.	Feb 1996
5665805	Hatanaka et al.	Sep 1997
5708113	Beuschel et al.	Jan 1998

Oil resistant silicone sealants

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Entry
Chemical Abstracts, vol. 115, No. 12, Sep. 23, 1991, Columbus, OH, US.
Dow Corning Docket No. DC4538, Oil Resistant Silicone Sealants Containing Metal Acetates, Philip D. Beljanski, Peter J. Houck, Loren D. Lower filed concurrently with DC4539.