text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 16, 1980
|Filing date
|Aug 2, 1979
|Priority date
|Aug 2, 1979
|Also published as
|Publication number
|Gary R. Homan, Chi-Long Lee
|Original Assignee
|Dow Corning Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (6), Non-Patent Citations (3), Referenced by (7), Classifications (16)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
This invention relates to compositions including organosiloxane polymers containing sulfur and to a method of forming higher molecular weight products from such compositions. This invention also relates to organosiloxane gels, elastomers and resins containing sulfur.
2. Description of the Prior Art
Compositions containing mercaptoorganosiloxanes free of any vinyl functionality which are polymerized by means of the mercapto groups to resins and sealants are known in the art. For example, in U.S. Pat. No. 4,133,939, Bokerman and Gordon teach a method of coating a substrate with a silicone release coating involving the radiation cure of mercapto-functional polydiorganosiloxane fluids mixed with a sensitizer such as benzophenone. While a radiation curing mechanism is rapid and provides one-package systems stable in the absence of light and heat, it is useful only for relatively thin coatings and requires a high intensity radiation source such as ultraviolet light or electron beams.
Peroxide cure of mercaptoorganosiloxanes free of vinyl unsaturation is also known, as demonstrated by Homan and Lee in U.S. Pat. No. 4,070,329. In that patent, the patentees teach mixtures of mercaptoorganopolysiloxanes, organic peroxide and, optionally, a filler to provide a composition which cures at room temperature or by heating to form elastomers which are useful as sealants and rubber articles. Likewise, Homan and Lee in U.S. Pat. No. 4,070,328 claim mixtures of mercaptoorganopolysiloxanes, organic hydroperoxides, a nitrogen compound and, optionally, a filler which produce compositions which cure at room temperature to elastomers which are useful as sealants and rubber articles. However, the above compositions are not one-package systems since the polymerization or cure begins immediately upon mixing the ingredients.
Vanderlinde, in U.S. Pat. No. 3,445,419, teaches the production of a type of mercapto-functional copolymer consisting of organosiloxanes with mercapto-functional organic compound segments which are prepared by grafting a mercapto-functional carboxylic acid ester such as pentaerythritol tetrakis (3-mercapto-propionate) onto a vinyl-terminated organosiloxane. When an alkaline catalyst such as an amine is added to the resulting graft-copolymer, there is obtained a composition which is stable in the absence of air, but cures to an elastomer at room temperature upon exposure to air. However, to prepare the Vanderlinde compositions, the use of both an aliphatically unsaturated organopolysiloxane and a grafting operation which introduces an additional amount of organic compound into the cured product is required. Furthermore, Vanderlinde does not suggest that a cobaltocene can be used either to prepare or to polymerize or cure the compositions hereinafter described.
The novel distinguishing features of the present invention are that the use of a cobaltocene compound catalyst produces compositions which are one-package, storage-stable in the absence of oxygen, and easily cured by simply exposing the composition to an oxygen atmosphere, such as air, or pure oxygen gas. The compositions of the present invention have an advantage over acetoxy-functional, moisture-cured, one-component compositions, such as those found in U.S. Pat. Nos. 3,035,016 and 3,077,465, in that no corrosive by-products are evolved during cure. The compositions of the present invention are substantially free of any volatile by-products during polymerization or cure. Compositions which do not evolve volatile by-products such as those which utilize platinum-catalyzed addition of SiH to vinyl are preferably cured by heating when formulated into one-package systems. These one-package, platinum-catalyzed systems cure very slowly at room temperature. Fast, room temperature cures require the use of a two-package system while compositions of the present invention are one-package systems which cure much faster at room temperature than one-package platinum catalyzed systems.
This invention relates to a composition, stable in the absence of oxygen, which comprises a product obtained by mixing the following substantially in the absence of oxygen
(A) 100 parts by weight of at least one mercapto-functional organosiloxane, said mercapto-functional organosiloxane having an average of at least two mercapto-functional siloxane units per molecule selected from the group consisting of mercapto-functional siloxane units of the average unit formula ##EQU1## any other siloxane units present having the average unit formula ##EQU2## wherein each R2 is a hydroxyl radical or an organic radical selected from the group consisting of R6 and 3,3,3-trifluoropropyl radicals,
each R6 is R5 or OR1,
each R5 is an alkyl radial of 1 to 4 inclusive carbon atoms or phenyl radical,
each R1 is an alkyl radical of 1 to 4 inclusive carbon atoms,
n has a value of from 2 to 4 inclusive,
w has a value of from 0 to 1 inclusive,
x has a value of from 1 to 2 inclusive,
y has a value of from 0 to 2 inclusive,
z has a value of from 0 to 3 inclusive and the sum of x+y has a value of from 1 to 3 inclusive,
and the ratio of the total R5, HSCn H2n --, ##STR1## and 3,3,3-trifluoropropyl radicals to silicon atoms in the mercapto-functional organosiloxane is in the range of 0.98/1 to 3.00/1;
(B) 0-200 parts by weight of at least one filler; and
(C) a catalytic amount of a cobaltocene of a formula (R3 C5 H4)Co(C5 H4 R4) wherein each R3 and R4 is a hydrogen atom or methyl.
The invention also relates to a method of forming a higher molecular weight product which comprises the steps of (I) mixing 100 parts by weight of at least one mercapto-functional organosiloxane defined in (A) above and a catalytic amount of a cobaltocene defined in (C) above to form a mixture and (II) exposing such mixture to oxygen. This invention further relates to the product obtained by exposing the above composition or mixture to oxygen.
For the purposes of this application, the term "oxygen" is intended to mean gaseous oxygen which can be in the form of pure oxygen gas or atmospheric oxygen. Mercapto-functional organosiloxanes will also be referred to as mercaptoorganosiloxanes and includes disiloxanes, trisiloxanes, and polysiloxanes consisting of siloxane units, some of which are mercapto-functional. Techniques for mixing compositions which are oxygen or moisture sensitive are well-known in the art. Bread dough mixers can be used for viscous mercaptoorganosiloxanes and low-shear mixers can be used for lower viscosity compositions.
This invention has two aspects. One is a novel method of polymerizing or curing mercapto-functional organosiloxanes to form higher molecular weight products. The other is directed toward the formation of storage-stable compositions. In order to accomplish the first aspect, one merely exposes a mixture of the mercapto-functional organosiloxane and a cobaltocene to oxygen. Thus, if storage stability is not required, the mercapto-functional organosiloxane and cobaltocene can be mixed together in the presence of oxygen and immediately allowed to polymerize or cure.
When storage-stable compositions are desired, the ingredients are mixed in the substantial absence of oxygen by any well-known means. The preferred procedure is to mix the mercaptoorganosiloxanes and filler, if any, under a dry nitrogen atmosphere. The mixture may then be subjected to a vacuum, such as 30 mm of mercury, for a short time to remove any trapped oxygen and water. The cobaltocene catalyst can then be added, preferably as a solution in an organic solvent such as toluene. Since cobaltocenes are somewhat sensitive to water and oxidation by oxygen (such compounds can also absorb carbon dioxide), it is preferable that the compositions be substantially free of both water and oxygen to maximize storage life. Small amounts of water merely reduce the cure rate slightly while the presence of oxygen will cause premature gelation. Therefore, the containers used to store the catalyzed compositions should be carefully selected to avoid materials which are sufficiently oxygen permeable to appreciably affect storage stability.
The substituents attached to silicon atoms can be R2 which can be hydroxyl, R6 or 3,3,3-trifluoropropyl radicals. R6 can be R5 which can be alkyl radicals of 1 to 4 inclusive carbon atoms such as methyl, ethyl, propyl, isopropyl and butyl, phenyl radicals, or alkoxy radicals of the formula OR1, where R1 is an alkyl radical of 1 to 4 inclusive carbon atoms, such as methoxy, ethoxy, isopropoxy and butoxy. The mercapto-functional substituents present in the form of HSCn H2n --where n is 2 to 4 can be, for example, beta-mercaptoethyl, gamma-mercaptopropyl, 3-mercaptobutyl, and 3-mercapto,2-methylpropyl. Another mercapto-functional substituent can be 2-mercaptotetramethylene where both ends of the 2-mercaptotetramethylene molecule are attached to the same silicon atom.
The siloxane units containing no mercapto groups which have the average unit formula ##STR2## can be SiO2 units, monosubstituted units such as monomethylsiloxane units, monoethylsiloxane units, monopropylsiloxane units, monobutylsiloxane units or monophenylsiloxane units; disubstituted units such as dimethylsiloxane units, diethylsiloxane units, diphenylsiloxane units, phenylmethylsiloxane units, methylbutylsiloxane units, phenylethylsiloxane units, 3,3,3-trifluoropropylmethylsiloxane units, and methylisopropylsiloxane units; and trisubstituted units such as trimethylsiloxane units, phenyldimethylsiloxane units, triethylsiloxane units, diphenylmethylsiloxane units, diphenylisopropylsiloxane units, 3,3,3-trifluoropropyldimethylsiloxane units, diphenylbutylsiloxane units, and triphenylsiloxane units.
The mercapto-functional siloxane units which have the average unit formula ##STR3## include the following: wherein the values of R1, R5, and n are defined above, and preferably n is 3. Mercaptoorganosiloxanes useful in the present invention contain an average of at least two mercapto-functional siloxane units per molecule.
The cured products of this invention can range in properties from soft gels to tough elastomers to hard resins. Physical properties such as durometer value and hardness are related to cross-link density. Cross-link density can be varied by several mechanisms. One mechanism is by adjusting the ratio of organic substituents (total alkyl, mercapto-functional, 3,3,3-trifluoropropyl and phenyl substituents) bonded through Si-C bonds to silicon. Generally, the lower the ratio, the harder the cured product will be when all other variables, such as types of substituents and structure, are kept equal. Another means for varying the cross-link density is to increase the number of mercapto-functional siloxane units per molecule in the mercaptoorganosiloxane.
Compositions consisting only of mercapto-organosiloxanes which contain an average of only two mercapto groups per molecule are generally only capable of chain-extension upon exposure to oxygen and thus produce higher molecular weight gums which could find utility as encapsulants. Compositions containing an average of more than two mercapto groups per molecule are capable of polymerizing in the presence of oxygen to form three-dimensional networks which can range from soft gels where the average number of mercapto groups per molecule is close to two to hard resins where the mole percent of mercapto-functional siloxane units based on the total number of siloxane units in the mercaptoorganosiloxane approaches 100 percent.
The compositions of the present invention are especially useful in forming elastomeric products with tack-free surfaces which are produced by simply exposing the composition to air. Compositions curable to elastomers with a wide variety of physical properties can easily be formulated by selecting the proper mercapto-functional polydiorganosiloxanes.
Pendant-functional mercaptopolydiorganosiloxanes useful in compositions of the present invention are mercaptopolydiorganosiloxanes containing R3 5 SiO0.5 or R2 5 (HO)SiO0.5 endblocking siloxane units, and mercapto-functional siloxane units selected from the group consisting of ##STR4## any remaining siloxane units being R2 5 SiO, wherein R5 and n are defined above, the average number of mercapto-functional siloxane units per molecule is greater than 2 and the number average molecular weight of the pendant-functional mercaptopolydiorganosiloxane is less than 400,000. Compositions consisting solely of pendant-functional mercaptopolydiorganosiloxanes can result in products which range in properties from soft gels to elastomers to hard resins when exposed to oxygen.
When the pendant-functional mercapto-polydiorganosiloxanes are used as the sole type of mercaptoorganosiloxane in formulations curable to elastomers, it is preferred that R5 is methyl, n is 3, and the pendant-functional mercaptopolydiorganosiloxane has a number average molecular weight of less than 100,000 and contains a sufficient number of mercapto-functional siloxane units to result in a weight percentage of mercapto groups in the range of 0.1 to 2.5 percent based on the total weight of pendant-functional mercaptopolydiorganosiloxane.
Terminal-functional mercaptopolydiorganosiloxanes useful in elastomeric sealant, gel and gum formulations as chain-extending polymers are mercaptopolydiorganosiloxanes containing mercapto-functional siloxane units selected from the group consisting of ##STR5## any remaining units being R2 5 SiO, wherein R5, R1 and n are defined above and the number average molecular weight of the terminal-functional mercaptopolydiorganosiloxane is less than 400,000. Preferably, the mercapto-functional siloxane units are selected from the group consisting of ##STR6## each R5 and R1 is methyl, n is 3, the number average molecular weight of the mercaptopolydiorganosiloxane is less than 100,000 and the weight percentage of mercapto groups present is in the range of 0.07 to 0.5 percent of the total weight of terminal-functional mercaptopolydiorganosiloxane. Polymerization of terminal-functional structures alone generally produces gums because only linear chain-extension is possible.
Another type of mercaptopolydiorganosiloxane useful in compositions of the present invention is a terminal-functional mercaptopolydiorganosiloxane which also contains pendant mercapto-functional siloxane units (hereinafter referred to as hybrid-functional mercaptopolydiorganosiloxanes). Such mercaptopolydiorganosiloxanes contain two terminal mercapto-functional siloxane units selected from the group consisting of ##STR7## and at least one mercapto-functional siloxane unit selected from the group consisting of siloxane units of the formula ##STR8## any remaining siloxane units being R2 5 SiO, wherein R1, R5 and n are defined above and the number average molecular weight of the mercaptopolydiorganosiloxane is less than 400,000. Compositions consisting solely of hybrid-functional mercaptopolydiorganosiloxanes can result in products which range in properties from soft gels to elastomers to hard resins when exposed to oxygen.
Hybrid-functional mercaptopolydiorganosiloxanes are quite versatile and can be used as the sole type of mercaptopolydiorganosiloxane in formulations which cure to elastomers. In such formulations, it is preferred that the terminal mercapto-functional siloxane units are selected from the group consisting of ##STR9## each R1 and R5 is methyl and the hybrid-functional mercaptopolydiorganosiloxane has a number average molecular weight of less than 100,000 and contains a sufficient number of mercapto-functional siloxane units to result in a weight percentage of mercapto groups in the range of 0.1 to 3 percent based on the total weight of hybrid-functional mercaptopolydiorganosiloxane. Hybrid-functional mercaptopolydiorganosiloxanes can be produced which cure to elastomeric products which range in properties from soft products with high elongation values to hard products which are not easily elongated by adjusting the molecular weight and/or the weight percent of mercapto groups in the mercaptopolydiorganosiloxane.
Blends of pendant- and terminal-functional mercaptopolydiorganosiloxanes can be used to obtain products which range in properties from soft gels to hard resins or from gums to hard rubbers. Likewise, the properties of hybrid-functional mercaptopolydiorganosiloxanes can also be altered by blending them with terminal-functional mercaptopolydiorganosiloxanes. To obtain blends which cure to elastomers it is preferred that mercaptopolydiorganosiloxanes which are within the aforementioned preferred ranges for the mercaptopolydiorganosiloxanes be used. Thus, a blend of pendant- and terminal-functional mercaptopolydiorganosiloxanes would contain at least 0.1, but less than 2.5, weight percent of mercapto groups based upon the total weight of the mercaptopolydiorganosiloxanes in the blend while a blend of hybrid- and terminal-functional mercaptopolydiorganosiloxanes would contain at least 0.1, but less than 3, weight percent mercapto groups based upon the total weight of the mercaptopolydiorganosiloxanes in the blend.
The methods for preparing the above mercaptopolydiorganosiloxanes are well-known in the art. One method for making a type of pendant-functional mercaptopolydiorganosiloxane containing (HSCn H2n)R5 SiO and R3 5 SiO0.5 siloxane units is taught by Viventi in U.S. Pat. No. 3,346,405. Another method is taught in the Bokerman, et al, patent described previously. Pendant-functional mercaptopolydiorganosiloxanes containing (HSCn H2n)R5 SiO and (HO)R2 5 SiO0.5 siloxane units can be produced by modifying the Viventi or Bokerman, et al, methods above. For example, such hydroxyl-endblocked mercaptopolydiorganosiloxanes can be produced by omitting the addition of triorganochlorosilane from the reaction mixture in the method taught by Viventi. Le Grow, in U.S. Pat. No. 3,655,713, teaches a procedure for making both pendant-functional and terminal-functional types of mercaptopolydiorganosiloxanes containing siloxane units possessing 2-mercaptotetramethylene substituents.
Several methods for producing terminal-functional mercaptopolydiorganosiloxanes containing (HSCn H2n)R2 5 SiO0.5 siloxane units are known. One method involves the use of a disiloxane bearing a silicon-bonded mercaptoalkyl radial, such as sym-tetramethyl bis(3-mercaptopropyl)disiloxane, and a cyclic polydiorganosiloxane such as octamethylcyclotetrasiloxane. Appropriate amounts of the mercapto-functional disiloxane and cyclic polydiorganosiloxane are heated together with an acidic catalyst such as trifluoromethanesulfonic acid for 3 to 8 hours. The mixture is then neutralized and the mercapto-terminated polydiorganosiloxane is recovered. Hybrid-functional polymers can be prepared using the same type of compounds and techniques outlined above for producing terminal-functional mercaptopolydiorganosiloxanes by adding a cyclic mercaptopolydiorganosiloxane such as {HSCH2 CH2 CH2 (CH3)SiO}4 to the reaction mixture to introduce pendant-functional groups into the mercaptopolydiorganosiloxane. Likewise, the compounds and techniques used in preparing pendant-functional mercaptopolydiorganosiloxanes can be used to produce hybrid-functional types by substituting mercapto-functional endblocking units, which can be introduced in the form of a disiloxane such as sym-tetramethyl bis(3-mercaptopropyl)disiloxane, in place of non-functional endblocking units, such as those introduced in the form of hexamethyldisiloxane, in the reaction mixture.
Cyclic mercaptopolydiorganosiloxanes can be prepared by various methods, one of which involves preparing the corresponding chloroalkylsilane, such as 3-chloropropylmethyldichlorosilane, and hydrolyzing the silanes to form a mixture of linear and cyclic polydiorganosiloxanes. If desired, the ratio of cyclic to linear polydiorganosiloxanes can be altered by heating in the presence of an acidic catalyst for a period of time, during which time a portion of the cyclic polydiorganosiloxanes formed is being removed by distillation to shift the equilibrium of the reaction in the direction which favors the formation of cyclic polydiorganosiloxanes. Then, for example, Viventi teaches that the chloroalkyldiorganosiloxanes can be reacted with sodium sulfohydride to produce mercaptopolydiorganosiloxanes. Mercapto-functional silanes containing alkoxy groups such as 3-mercaptopropylmethyldimethoxysilane can also be hydrolyzed at about 40�-50� C. in the presence of an acidic catalyst and vacuum-stripped at 120� C. to remove the alcohol and other undesirable volatiles generated. Such mixtures can also be referred to as, for example, the 3-mercaptopropylmethyl hydrolyzate of 3-mercaptopropyldimethoxysilane. Other means for preparing cyclic mercaptopolydiorganosiloxanes will be apparent to persons skilled in the art.
The production of a type of mercapto-functional organosiloxane resins by the partial hydrolysis of silanes such as HSCn H2n Si(OR1)3 and R2 5 Si(OR1)2 is also demonstrated by the Viventi patent. Likewise, mercapto-functional organosiloxane resins result when a sufficient number of siloxane units such as R5 SiO1.5 are present in the mercaptoorganolsiloxanes taught in the Le Grow patent. The Viventi, Le Grow and Bokerman, et al, patents are hereby incorporated by reference to teach the production of mercaptoorganosiloxanes useful in the compositions of the present invention.
Mercaptopolydiorganosiloxanes which contain endblocking units of the formula ##STR10## can be prepared by reacting a hydroxyl endblocked polydiorganosiloxane and a (mercaptoalkyl)trialkoxysilane of the formula HSCn H2n Si(OR1)3 in the presence of solid potassium hydroxide or potassium silanolate catalysts. The potassium silanolate catalyst is preferred for higher viscosity polydiorganosiloxanes. The (mercaptoalkyl)trialkoxysilane is preferably used in excess of about 10 mole percent of stoichiometric amounts. The resulting product is essentially a polydiorganosiloxane endblocked with units of the formula ##STR11## There may be some small amounts of units wherein two SiOH groups have reacted with one (mercaptoalkyl)trialkoxysilane molecule, but these amounts are small enough that the character of the endblocked polydiorganosiloxane is not noticeably altered.
Compositions with various properties may be formulated using the above mercaptopolydiorganosiloxanes. Generally, use of only the pendant-functional mercaptopolydiorganosiloxanes results in elastomers with higher modulus values than formulations which additionally include terminal-functional mercaptopolydiorganosiloxanes. The latter give elastomers with lower modulus values which are thus capable of much greater elongation before the cured composition tears. As a result, the sole use of pendant-functional mercaptopolydiorganosiloxanes results in cured sealants which are less readily elongated and are therefore primarily useful where there is only a small amount of movement in the joint to be sealed. Combinations of the pendant- or hybrid-functional and terminal-functional mercaptopolydiorganosiloxanes are preferred where elastomeric building sealant formulations are desired for use in applications where a relatively large degree of joint movement occurs due to varying temperatures although such combinations can also be used in many other sealant applications. Formulations which cure to elastomers having elongation values of greater than 1000 percent at break and a modulus value at 100 percent elongation in the range of 210 to 415 kilopascals (kPa) are sometimes called low modulus elastomeric sealants. The use of hybrid-functional mercaptopolydiorganosiloxanes alone, blends of pendant- and terminal-functional mercaptopolydiorganosiloxanes, or blends of hybrid- and terminal-functional mercaptopolydiorganosiloxanes can result in a low modulus elastomeric sealant product with excellent unprimed adhesion to a large number of building substrates. To prepare such low modulus elastomeric sealant compositions, it is preferred that the mercaptopolydiorganosiloxanes utilized are those described above wherein R1 and R5 are methyl, n is 3, the average molecular weight of the mercaptopolydiorganosiloxanes utilized is less than 100,000 and the weight percent mercapto groups present in the hybrid-functional mercaptopolydiorganosiloxane or present in the total blend is in the range of 0.1 to 0.45 weight percent. It should be noted that cured elastomers with higher modulus values, especially those formulated with pendant-functional mercaptopolydiorganosiloxanes alone, do not have exceptionally good adhesion to substrates and can require the use of primers in certain applications.
Fillers may be used with the compositions of this invention, but are not required. Extending fillers can preferably be used in amounts of 10 to 200 parts by weight per 100 parts by weight of mercaptoorganosiloxane, especially in the elastomeric sealant formulations. Suitable extending fillers can be titanium dioxide, calcium carbonate, talc, clay, ground or crushed quartz, diatomaceous earth, fibrous filler such as glass or asbestos, and the like. Reinforcing fillers such as fume silica, surface-treated fume silica, carbon black and the like may also be used. As is well-known in the art, reinforcing fillers cannot be used in as large an amount as extending fillers can be used, thus any formulation including such fillers would not contain more than 70 parts by weight of reinforcing filler per 100 parts by weight of the mercaptoorganosiloxanes and preferably, from 5 to 30 parts. Extending fillers can also be included in formulations containing reinforcing fillers in amounts of up to 200 parts by weight per 100 parts by weight of the mercaptoorganosiloxanes less the amount of reinforcing filler present, provided that the capacity of the mercaptopolydiorganosiloxanes to accept such amounts of filler is not exceeded. Other additives such as coloring pigments, fire-retardant compounds and the like are also contemplated as being useful in the present invention. Since the catalytic action of cobaltocene is affected by water, it is preferred that any fillers or additives be substantially free of water to provide maximum shelf life. Routine testing can determine the effect of fillers and additives on shelf life.
Cobaltocenes contemplated as being useful as catalysts in the practice of the present invention are cobaltocene or dicyclopentadienyl cobalt, (C5 H5)Co(C5 H5), and substituted cyclopentadienyl derivatives such as (CH3 C5 H4)Co(C5 H5) and (CH3 C5 H4)Co(C5 H4 CH3). The amount of catalyst necessary is not critical. Any catalytic amount can be employed which will adequately polymerize or cure the compositions in the presence of oxygen to result in a product which is satisfactory for the desired end use. Changing the level of catalyst can alter the rate of polymerization or cure and can alter the properties of the product, especially in the elastomers. We have found that a range of 0.01 to 6 parts by weight of compound per 100 parts by weight of the mercaptoorganosiloxanes present is preferred. The preferred catalyst is cobaltocene. For elastomeric sealant compositions, 0.08 to 0.30 parts by weight of cobaltocene per 100 parts by weight of mercaptoorganosiloxanes present is preferred.
As noted above, cobaltocenes are oxidized by air and can absorb carbon dioxide. Water also appears to reduce the catalytic activity of the compounds somewhat and results in a longer cure time. Thus it is preferable to dissolve the cobaltocenes in a non-polar organic solvent such as toluene. We have utilized an 8 percent by weight solution of cobaltocene in toluene with good results. Cobaltocenes are known in the art and methods for the preparation of the cobaltocenes may be found in the literature such as in Green, Pratt and Wilkinson, "A New Type of Transition Metal-Cyclopentadiene Compound," Journal of the Chemical Society, pp. 3753-3767 (1959) which is hereby incorporated by reference to teach the production of cobaltocenes useful in the present invention.
It is believed that the compositions of the present invention polymerize or cure to form higher molecular weight products by the formation of disulfide (--SS--) bonds upon exposure to oxygen due to the action of the cobaltocene catalyst.
The compositions polymerize or cure rapidly at room temperature and appear to cure from the surface in contact with oxygen inward. Elastomeric sealant compositions have been shown to cure to a 0.3 centimeter thick section in 5 hours and to a 2.5 centimeter thick section in fourteen days. Heating will accelerate the rate of cure in the manner that most chemical reactions are accelerated by a rise in temperature. Compositions containing low amounts of mercapto groups, such as those containing less than 2 weight percent mercapto groups, are essentially free of offensive odor. When compared to moisture-cure sealants which evolve acetic acid during cure, such as those found in U.S. Pat. Nos. 3,035,016 and 3,077,465, the compositions of this invention are non-corrosive to the substrate and evolve practically no volatile by-products of cure. The polymerization reaction only requires the presence of oxygen which is readily available from the atmosphere. In practicing the present invention, a formulator may select polymers and fillers which together with the proper level of catalyst will yield a variety of products such as encapsulating gels, hard resins, coatings and especially useful elastomeric sealants.
The following examples are intended as being merely illustrative and are not to be construed as limiting the scope of the present invention, which is properly defined by the appended claims.
To demonstrate the utility of the present invention in forming elastomeric sealants, the following composition was prepared. A pedant-functional, mercaptopolydiorganosiloxane which was a trimethylsiloxy-endblocked copolymer of dimethylsiloxane and 3-mercaptopropylmethylsiloxane units was prepared using the following procedure. The following ingredients were added to a 22 liter three-necked flask equipped with a thermometer, stirrer and reflux condenser: 51.5 grams of hexamethyldisiloxane and 256 grams of the 3-mercaptopropylmethyl hydrolyzate of 3-mercaptopropylmethyldimethoxysilane. The contents were heated with stirring and dry nitrogen gas purge to 65� C. At 65� C., two milliliters of trifluoromethanesulfonic acid was added. Then 2 liters (1900 grams) of a cyclic polydimethylsiloxane mixture having an average formula (Me2 SiO)˜4 was added to the flask over a two-hour period. The cloudy mixture was heated to 80� C., 9.2 milliliters of trifluoromethanesulfonic acid was added, and the mixture was held at that temperature until the mixture became clear (approximately 30 minutes). At that point, 16,793 grams of the above cyclic polydimethylsiloxane mixture was rapidly added to the reaction mixture in the flask over a period of 15 minutes. When the addition was complete, the reaction mixture was allowed to equilibrate by allowing the mixture to stir at 80� C. for an additional 16 hours. Then 1.14 grams of distilled water was added and the mixture was allowed to equilibrate for another 8 hours at 80� C. The reaction mixture was then cooled and 112 grams of sodium bicarbonate was added to neutralize the acid catalyst. The reaction mixture was then diluted with an equal volume of toluene to facilitate filtration and filtered through a charcoal filter. The volatile materials were then distilled from the filtrate by heating at a pressure of approximately 5 millimeters of mercury until the temperature of the material left in the flask reached 155� C. The mercaptopolydiorganosiloxane (hereinafter referred to as polymer A) obtained after removal of the volatile portion had a viscosity of 38.93 Pa�s (Pascal�seconds) at 25� C. and contained 0.41 weight percent mercapto groups. The weight percent of mercapto groups was determined analytically using the iodine titration test outlined in Critchfield, Organic Functional Group Analysis, MacMillan Co., NY, p. 166 (1963). Polymer A had a number average molecular weight of 80,500 as determined by fast gel permeation chromatographic analysis using polydimethylsiloxane reference standards.
A base was prepared by milling 100 parts by weight of the above polymer with 150 parts by weight of a calcium carbonate filler on a three-roll mill. This base was then placed in a SemKit� tube (commercially available from Semco, Inc., division of Products Research and Chemical Corp., Glendale, CA) which is a cylinder having the appearance of a tube commonly used for caulking compounds which contains a means for stirring the contents and is designed to be placed in a vacuum to remove volatile materials from compositions placed inside the tube. Since the base was milled in the presence of air, the base was de-aired by subjecting it to a vacuum of 30 millimeters of mercury for 30 minutes. A seal was then placed on the back of the tube. Various levels, as defined in Table I, of cobaltocene, (C5 H5)Co(C5 H5), catalyst were injected into the sealed SemKit� tubes as an 8 percent by weight solution in toluene and the stirrer was used to evenly incorporate the catalyst into the base.
Upon exposure to air at room temperature (22� C.), the compositions rapidly formed a surface skin (skin-over time) and became tack-free to touch with a polyethylene sheet in less than an hour. The levels of catalyst and the properties of the composition cured for 7 days at room temperature are tabulated in Table I. The durometer was determined by ASTM-D-2240 with the results reported in Shore A while the tensile strength, elongation and modulus at 100 percent elongation were determined by ASTM-D-412.
TABLE I__________________________________________________________________________Elastomeric Sealant Compositions Skin-Over Tack-Free Modulus Parts1 of Time Time Durometer Tensile Elongation @ 100% ElongationFormulation (C5 H5)2 Co (Minutes) (Minutes) (Shore A) (kPa) (percent) (kPa)__________________________________________________________________________A 0.040 (0.10) 4 10 33 793 250 724B 0.024 (0.06) 8 30 30 814 300 724C 0.008 (0.02) ˜20 ˜40 16 745 650 345__________________________________________________________________________ 1 Parts of catalyst per 100 parts of base, added as an 8 percent by weight solution in toluene. The figures in parentheses are parts of catalyst added per 100 parts of mercaptopolydiorganosiloxane.
The use of both pendant- and terminal-functional mercaptopolydiorganosiloxanes to produce a low modulus sealant composition suitable for use as a building sealant was demonstrated. Cured compositions possessed excellent unprimed adhesion to glass, concrete and metals such as aluminum.
A terminal-functional mercaptopolydiorganosiloxane which was a 3-mercaptopropyldimethylsiloxy-endblocked polydimethylsiloxane (hereinafter referred to as Polymer B) was prepared according to the following procedure. The following ingredients were added to a 5 liter, 3-necked flask containing a stirrer, reflux condenser and a nitrogen sparge tube: 2988.9 grams (˜3136 ml) of the same type of cyclic polydimethylsiloxane mixture used in Example 1 and 11.06 grams of sym-tetramethyl bis(3-mercaptopropyl)disiloxane. The contents were stirred and purged with dry nitrogen gas while heating to 65� C. At a constant 65� C., 1.77 ml. of trifluoromethanesulfonic acid was added. After 4.6 hours of reaction in the presence of the acid catalyst, 6 microdrops (˜0.06 grams) of distilled water was added to the contents. After another 1.9 hours at 65� C., the mixture was neutralized with 17.7 grams of sodium bicarbonate and allowed to stir overnight at room temperature. The mixture was diluted with an equal volume of toluene, pressure filtered and vacuum distilled to remove volatile matter at less than 1 millimeter of mercury pressure to a pot temperature of 150� C. Polymer B contained 0.14 weight percent of mercapto groups, had a viscosity of 41.01 Pa�s at 25� C. and had a number average molecular weight of 49,600.
The pendant-functional mercaptopolydiorganosiloxane used in this example was from a different batch of Polymer A which contained 0.41 weight percent of mercapto groups, had a viscosity of 40.10 Pa�s at 25� C. and had a number average molecular weight of 104,000.
The samples used in this example were prepared according to the procedure outlined in Example 1. A base was prepared using 87 parts of Polymer B, 13 parts of the above pendant-functional mercaptopolydiorganosiloxane and 150 parts of a calcium carbonate filler. The levels of catalyst added to this base are shown in Table II. The catalyzed compositions were then extruded and cured for 7 days at room temperature in the presence of air before determining the physical properties of the cured sealant compositions.
TABLE II__________________________________________________________________________Low Modulus Elastomeric Sealant Compositions Skin-Over Tack-Free Tensile Modulus Parts1 of Time Time Durometer Strength Elongation @ 100% ElongationFormulation (C5 H5)2 Co (Minutes) (Minutes) (Shore A) (kPa) (percent) (kPa)__________________________________________________________________________A 0.12 6 18 15 621 1360 241B 0.08 25 55 14 482 1250 241__________________________________________________________________________ 1 Parts of catalyst per 100 parts of mercaptopolydiorganosiloxane, added as an 8 percent by weight solution in toluene.
Various levels of cobaltocene catalyst were used to discover the optimum level of catalyst necessary for low modulus building sealant compositions of the formulation used in Example 2. A base was prepared using 87 parts by weight of a terminal-functional mercaptopolydimethylsiloxane of the same general structure as polymer B, but from a different batch, which contained 0.1 weight percent mercapto groups and a viscosity of 37.80 Pa�s at 25� C. The same type and amount of pendant-functional mercaptopolydiorganosiloxane (from a different batch with almost identical viscosity and weight percent mercapto groups) and filler was used as in Example 2. Four different levels of catalyst were added to this base and the properties obtained are summarized in Table III.
TABLE III__________________________________________________________________________Optimized Catalyst Concentration, Low Modulus Sealant Composition Skin-Over Tack-Free Tensile Modulus Parts1 of Time Time Durometer Strength Elongation @ 100% ElongationFormulation (C5 H5)2 Co (Minutes) (Minutes) (Shore A) (kPa) (percent) (kPa)__________________________________________________________________________A 0.16 9 14 15 745 1510 276B 0.12 9 15 15 724 1560 262C 0.08 12 32 14 676 1515 262D 0.04 65 2 days 8 379 1170 138__________________________________________________________________________ 1 Parts per 100 parts by weight of mercaptopolydiorganosiloxane, added as an 8 percent by weight solution in toluene.
To demonstrate the formation of a resin by curing compositions of the present invention, 3-mercaptopropylmethyl hydrolyzate of 3-mercaptopropylmethyldimethoxysiloxane was prepared wherein the weight percent of mercapto groups was 24.6 and the viscosity at 25� C. was 0.08 Pa�s. Twenty grams of this hydrolyzate was mixed with 2.5 grams of an 8 percent by weight solution of cobaltocene in toluene and exposed to air at room temperature. After 10 hours exposure to air, a layer which was approximately 0.25 millimeters (mm) thick of highly cross-linked material had formed on the surface. After three days at room temperature, a brittle layer approximately 1.4 mm thick had formed while the viscosity of the unexposed liquid was relatively unchanged. After 6 days, the cured layer was approximately 1.8 mm thick. Heating would be expected to greatly accelerate the cure time. Generally, protective coating films range in thickness from 0.1 to 0.50 mm depending upon the application. Thus, thin layers of this composition could be used to form a resinous coating on a substrate.
The cure rate of sealants of the present invention was investigated by measuring the thickness of cured sealant compositions as a function of time. Clear, cylindrical glass jars with a volume of approximately 15 milliliters and an outside diameter of 1.9 centimeters were used. A low modulus sealant composition, the same as Formulation A of Example 3, was extruded into these jars so that the surface was left exposed to air and the thickness of the cured layer could be observed from the side. The compositions were left exposed to air at room temperature (22� C.) and the thickness of the cured compositions at various intervals is summarized below.
______________________________________ THICKNESSTIME (Millimeters)______________________________________0 02 hours 1.65 hours 3.220 hours 6.42 days 9.55 days 15.912 days 23.814 days 25.420 days 30.223 days 33.3______________________________________
The above experiment demonstrates that the composition cures from the surface exposed to air inward.
The above data also demonstrates a significant advantage possessed by these sealants over room temperature vulcanizable (RTV) one-package sealants currently available. Moisture-cured RTV sealants generally take at least one day to cure to a depth of 3.2 to 6.4 mm and may take several weeks to cure to a depth of 12.7 mm. The above data shows that a thickness of 1.6 mm can be attained in 2 hours, a 6.4 mm thickness in 20 hours and 25.4 mm in two weeks. Thus, substantially faster room temperature cure rates can be obtained using compositions of the present invention.
An investigation of the shelf-life of catalyzed compositions was made. The composition used in the study was the same composition used in Formulation B of Example 3. The composition used was sealed into a number of identical aluminum toothpaste type tubes and samples were stored at room temperature (22� C.) and in an oven at 70� C. A slight amount of catalyst was lost in mixing and adding the samples to the tubes. However, the cured properties were not significantly affected, so the testing was continued. After aging for a period of time, the contents of the sealed tube was extruded at room temperature in the presence of air and both the tack-free time and the skin-over time were recorded. After 7 days at room temperature, the properties of the cured compositions were determined and are summarized in Table IV.
TABLE IV______________________________________Shelf-Life Stability Testing______________________________________A. Room Temperature Storage (22� C.) Skin- Tack- Modulus Over Free Duro- Elon- @ 100%Stor- Time Time meter Tensile gation Elon-age (Min- (Min- (Shore Strength (per- gationtime utes) utes) A) (kPa) cent) (kPa)______________________________________Initial 10 22 15 772 1310 2761 day 12 25 -- -- -- --3 days 13 30 16 779 1360 2767 days 13 36 15 793 1270 29015 days 12 34 16 689 1280 27622 days 16 48 16 724 1230 29628 days 15 33 16 758 1275 290______________________________________B. Oven Stability (70� C.) Skin- Tack- Modulus Over Free Duro- Elon- @ 100%Stor- Time Time meter Tensile gation Elon-age (Min- (Min- (Shore Strength (per- gationTime utes utes A) (kPa) cent (kPa)______________________________________Initial 10 22 15 772 1310 2762 days 12 36 -- -- -- --3 days 11 57 15 758 1280 2767 days 14 56 15 793 1310 27615 days 16 76 14 711 1340 27622 days 14 78 13 655 1230 27628 days 19 76 13 642 1240 26937 days 22 80 -- -- -- --13 weeks 18 63 12 621 1370 207______________________________________
From the above data, it appears that storage affects the tack-free time more than the skin-over time. The other properties change little with time. Based on prior experience, the oven stability data indicates that the compositions should have a shelf life in excess of a year in aluminum tubes.
A hybrid-functional mercaptopolydiorganosiloxane polymer was prepared by the following procedure. 3.8 grams of sym-tetramethyl bis(3-mercaptopropyl)disiloxane and 1.35 grams of the 3-mercaptopropylmethyl hydrolyzate of 3-mercaptopropylmethyldimethoxysilane were added to a 2 liter, 3-necked flask equipped with a stirrer, reflux condenser and a thermometer. Then 100 milliliters (˜95 grams) of a cyclic polydimethylsiloxane mixture having an average formula {(CH3)2SiO}˜4 was added and the cloudy mixture was stirred while heating to 65� C. At 65� C., 0.59 ml (˜1 gram) of trifluoromethanesulfonic acid was added and the temperature was raised to 85� C. and held there for 15 minutes. At that point, the mixture became clear. Then, 944 ml (˜899 grams) of the above cyclic polydimethylsiloxane mixture was slowly added over a one hour period while the stirring reaction mixture was maintained at 85� C. When the addition was complete, the mixture was allowed to equilibrate by stirring the mixture for an additional 6 hours at 85� C. The reaction mixture was then cooled and 5.9 grams of sodium bicarbonate was added to neutralize the acid catalyst. The reaction mixture was then removed and reduced in viscosity with an equal volume of toluene to facilitate filtration and filtered through a charcoal filter. The volatile materials were distilled from the reaction mixture by heating at a pressure of less than 2 millimeters of mercury and collecting the distillate until the temperature of the distillation pot reached 150� C. The hybrid-functional mercaptopolydiorganosiloxane product obtained had a viscosity of 38.4 Pa�s at 25� C., contained 0.13 weight percent mercapto groups and was a 3-mercaptopropyldimethylsiloxy-endblocked copolymer of dimethylsiloxane and 3-mercaptopropylmethylsiloxane units. The number average molecular weight of the product determined by fast gel permeation chromatographic analysis using polydimethylsiloxane reference standards was 65,600.
A low modulus sealant composition was then prepared using the SemKit� procedure outlined in Example 1. The formulation consisted of the following: 100 parts by weight of the hybrid-functional polymer prepared above; 150 parts of a calcium carbonate filler; and 2 parts of an 8 percent by weight solution of cobaltocene in toluene. When a sample of this composition was extruded in the presence of air at room temperature (22� C.), a skin-over time of 5 minutes and a tack-free time of 11 minutes was observed. After seven days exposure to air at room temperature, the cured composition exhibited the following physical properties: durometer (Shore A)-18; tensile strength-827 kPa; elongation at break-1280 percent; and modulus at 100 percent elongation-345 kPa. Samples tested for adhesion exhibited good unprimed adhesion to substrates such as cold-rolled steel.
|Cited Patent
|Filing date
|Publication date
|Jun 16, 1945
|Apr 12, 1949
|Thiokol Corp
|Polysulfide polymer
|Jan 21, 1966
|May 20, 1969
|Dow Corning
|Room temperature vulcanizable silicones
|Mar 3, 1976
|Jan 3, 1978
|Dow Corning Corporation
|Sulfur containing silicone elastomer and method of preparation
|Jan 3, 1977
|Jan 24, 1978
|Dow Corning Corporation
|Mercaptoorganopolysiloxanes cured to elastomers with peroxides and nitrogen compounds
|Jan 3, 1977
|Jan 24, 1978
|Dow Corning Corporation
|Siloxane elastomer prepared from mercaptoorg anopolysiloxanes
|Dec 16, 1977
|Jan 9, 1979
|Dow Corning Corporation
|Method for applying a silicone release coating and coated article therefrom
|Condensed Chemical Dictionary, 8th Edition, Van Nostrand Reinhold Co. p. 223 (1971).
|Cranker et al., "Use of Polysulfide Liquid Polymers for Impregnation of Leather," American Leather Chem. Assn. Journal, 47 pp. 171-191 (1952).
|High Polymers, Ch XIII, Polyether Part III, Gaylord, ed., Interscience Publishers, pp. 175, 191-192, 215, 219, 223 (1962).
|Citing Patent
|Filing date
|Publication date
|Dec 28, 1983
|Jul 2, 1985
|Union Carbide Corporation
|Organosiloxane polymers and compositions containing same curable upon exposure to gaseous oxygen
|Aug 19, 1985
|Feb 25, 1986
|Dow Corning Corporation
|Foamable polyorganosiloxane compositions
|Nov 19, 1987
|May 16, 1989
|Minnesota Mining And Manufacturing Company
|Moisture resistant splice assembly
|Aug 14, 1989
|Jul 16, 1991
|Minnesota Mining And Manufacturing Company
|Method of making vinyl-silicone copolymers using mercapto functional silicone chain-transfer agents and release coatings made therewith
|Dec 29, 1992
|Feb 21, 1995
|Shin-Etsu Chemical Co., Ltd.
|Silicone rubber curing and anaerobic silicone rubber composition therefor
|Apr 9, 1998
|Nov 30, 1999
|Dow Corning Corporation
|Compositions comprising mercapto-functional organosilicon compounds
|Sep 23, 2009
|Mar 4, 2014
|3M Innovative Properties Company
|Method for treating wheel rims and composition for use therein
|U.S. Classification
|524/588, 528/30, 528/15
|International Classification
|Cooperative Classification
|European Classification


text:
Cervical Cancer Health Center
Cervical Cancer Prevention (PDQ®): Prevention - Patient Information [NCI] - About This PDQ Summary
About PDQ
Physician Data Query (PDQ) is the National Cancer Institute's (NCI's) comprehensive cancer information database. The PDQ database contains summaries of the latest published information on cancer prevention, detection, genetics, treatment, supportive care, and complementary and alternative medicine. Most summaries come in two versions. The health professional versions have detailed information written in technical language. The patient versions are written in easy-to-understand, nontechnical language. Both versions have cancer information that is accurate and up to date and most versions are also available in Spanish.
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Read the Understanding Cervical Cancer -- Symptoms article > >
PDQ is a service of the NCI. The NCI is part of the National Institutes of Health (NIH). NIH is the federal government's center of biomedical research. The PDQ summaries are based on an independent review of the medical literature. They are not policy statements of the NCI or the NIH.
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This PDQ cancer information summary has current information about cervical cancer prevention. It is meant to inform and help patients, families, and caregivers. It does not give formal guidelines or recommendations for making decisions about health care.
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Editorial Boards write the PDQ cancer information summaries and keep them up to date. These Boards are made up of experts in cancer treatment and other specialties related to cancer. The summaries are reviewed regularly and changes are made when there is new information. The date on each summary ("Date Last Modified") is the date of the most recent change.
The information in this patient summary was taken from the health professional version, which is reviewed regularly and updated as needed, by the PDQ Screening and Prevention Editorial Board.
Clinical Trial Information
A clinical trial is a study to answer a scientific question, such as whether one treatment is better than another. Trials are based on past studies and what has been learned in the laboratory. Each trial answers certain scientific questions in order to find new and better ways to help cancer patients. During treatment clinical trials, information is collected about the effects of a new treatment and how well it works. If a clinical trial shows that a new treatment is better than one currently being used, the new treatment may become "standard." Patients may want to think about taking part in a clinical trial. Some clinical trials are open only to patients who have not started treatment.

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We discuss the simplification of non-deterministic multi-valued (MV) networks and their internal nodes using internal flexibilities. Given the network structure and its external specification, the flexibility at a node is derived as a non-deterministic MV relation. This flexibility is used to simplify the node representation and enhance the effect of Boolean resubstitution. We show that the flexibility derived is maximum. The proposed approach has been implemented and tested in MVSIS. Experimental results show that it performs well on a variety of MV and binary benchmarks.
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Posted by ESPN.com's Tim Graham
DANA POINT, Calif. -- The Buffalo Bills already have paid Terrell Owens a $4 million signing bonus.
But the controversial receiver obviously didn't feel like he owed it to the Bills to join them at the start of their voluntary offseason conditioning program Monday in Orchard Park, N.Y.
Then again, Bills head coach Dick Jauron wasn't there either. Jauron, 2,000 miles away at the annual NFL owners' meeting in Southern California, wasn't concerned about Owens' absence.
"It's voluntary," Jauron said Monday at the St. Regis Hotel. "We'd love to have everybody there. It's a voluntary session. We know, as you know, that he's a guy that you don't have to worry about him being in shape. He'll be in shape."
Jauron noted the conditioning program is not a critical time for installing the offense or for a new player to get on the same page from an X's and O's standpoint.
"This is more conditioning and strength training," Jauron said.
But the Bills probably wouldn't mind seeing Owens a little more eager to get to know his new teammates, particularly quarterback Trent Edwards and receiver Lee Evans.


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Pidilizumab (CT-011) is a humanized monoclonal antibody (mAb) that modulates the immune response and inhibits tumor growth and the spread of metastases. Mechanistically, pidilizumab activity leads to extended survival of lymphocytes, primarily effector/memory T cells. Pidilizumab also augments anti-tumor activities of NK cells. The enhanced activities of T and NK cells are translated into the intensification of anti-tumor immune response and the generation of tumor-specific memory cells. Pidilizumab is being developed as a treatment for hematological malignancies and solid tumors.
A Phase I, dose escalation, clinical study in 17 hematological malignancy patients has been completed. The study showed that a single administration of CT-011 (0.2 to 6.0mg/kg) was overall safe and well tolerated with no observed serious/unexpected treatment-related adverse events and no observed infusion-related responses or autoimmune reactions. No single dose MTD could be established in this study. Interestingly, apparent clinical responses were observed in six of the patients exhibited as extended survival as follows: one Complete Remission (NHL - follicular lymphoma), four Stable Disease (HD, 2 CLL, and MM), and one minimal response (AML). Amongst immune modulating molecules, CT-011 presents a safe alternative exhibiting no signs of autoimmunity which commonly occurs in the presence of other immune-modulating antibodies.
An international Phase II program has been initiated to explore the safety and efficacy of pidilizumab in hematological malignancies and solid tumors. A Phase II in patients with diffuse large B-cell lymphoma following autologous stem cell transplantation has been successfully completed. In this open‑label, non‑randomised, international Phase II study in 72 patients with DLBCL following autologous stem cell transplantation, pidilizumab treatment was shown to result in a progression-free survival of 72% and overall survival of 84% 18 months after transplant. Among the 27 high-risk patients who remained PET positive after salvage chemotherapy, the 18 month progression-free survival was 69%. Among the 40 patients with measurable disease after transplant, the overall response rate after pidilizumab treatment was 45%. Treatment was associated with early and persistent increases in specific subsets of circulating lymphocytes. Efficacy data compare favourably with previously reported cohorts and suggest that PD-1 blockade after autologous transplant using pidilizumab may represent a promising therapeutic strategy in this disease.Enrolment of patients to 2 additional Phase II studies in patients with metastatic colorectal cancer and metastatic melanoma has been completed. Several other studies in different hematological and solid malignacies are ongoing.


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Been trying to understand shared pointer for a few days now and it feels like I cant seem to get it. Not sure if it's just to obvious or if it's too complicated. First of all, could anyone please give me an example where you would ACTUALLY use shared pointers. The examples on Wikipedia makes no sense to me. And how would you pass a shared pointer to another function or create an object with a shared pointer. So, how do you pass it around and where would you use it? ANY information or examples would be great.
Also, I have this issue where I don't know what to use. I have this function where I allocate a
QFile and passes it to a function in another class. That function takes the file as a
QIODevice* and then creates an object containing the file. I was wondering what the best solution would be here and how (if I should) use a shared pointer here? How can I make a shared pointer with
<QFile> and pass it in where the function takes
<QIODevice>. Feels like I don't get shared pointers at all...
My other approach would be to put the allocation of the
QFile in a
QScopedPointer. I then pass it to the class and when creating the object where the file will be stored, I use
QPointer or
QScopedPointer. In the end of the first calling function I should call take() right?
function () {
QScopedPointer<QFile> item(new QFile("filename"));
SomeClass::doStuff(QIODevice *item) {
_currentObject = new MyObject(item); // should _currentObject be a smartpointer?
class MyObject {
QPointer<QIODevice> _item;
MyObject(QIODevice *item) { _item = item; }
So I want a way to store pointers and a way to handle them during creation if "new" throws an exception.


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LED LENSER® H7.2 250-lumen Headlamp. A hands-free lighting solution with 3 different beam programs!
Turn night into day! When you need your hands free and a bright beam, reach for this LED LENSER H7.2 Headlamp. It pumps out an incredibly bright 250-lumen beam that's sure to light up any area. Designed with Smart Lens TechnologyTM with 3 different lighting options (low / high, high / low, and high / strobe) to suit all of your needs. Plus, the tilt mechanism is adjustable so you can put the beam exactly where you want it. It's the perfect lighting solution for working under the sink, your car, or in any other tight spaces. And not only is it great for work, but for hunters, too. Light up the woods walking to your tree stand or use it for late-night tracking.Features:
- Produces 250 lumens
- Can be seen up to 524' away
- Smart Lens Technology with 3 light programs
- Advanced Focus SystemTM for a crisp, clear beam
- Battery life: 7 hours (high), 60 hours (low)
- Water resistant with an IPX4 rating
- Scroll wheel easily adjusts the brightness setting
- Tilt mechanism puts light where you need it
- Ergonomic design with adjustable head strap to maximize comfort
- Carabiner hook
- Easy on / off switch even with gloves on
- Runs on 4 AAA batteries (not included)
- Weighs 5 3/4 ozs.


text:
Occupants' window opening behaviour: A literature review of factors influencing occupant behaviour and models
Publication: Research - peer-review › Journal article – Annual report year: 2012
Energy consumption in buildings is influenced by several factors related to the building properties and the building controls, some of them highly connected to the behaviour of their occupants.In this paper, a definition of items referring to occupant behaviour related to the building control systems is proposed, based on studies presented in literature and a general process leading to the effects on energy consumptions is identified.Existing studies on the topic of window opening behaviour are highlighted and a theoretical framework to deal with occupants' interactions with building controls, aimed at improving or maintaining the preferred indoor environmental conditions, is elaborated. This approach is used to look into the drivers for the actions taken by the occupants (windows opening and closing) and to investigate the existing models in literature of these actions for both residential and office buildings. The analysis of the literature highlights how a shared approach on identifying the driving forces for occupants' window opening and closing behaviour has not yet been reached. However, the reporting of variables found not to be drivers may reveal contradictions in the obtained results and may be a significant tool to help direct future research.
|Original language
|Building and Environment
|Pages (from-to)
|Published - 2012
|Web of Science® Times Cited: No match on DOI
- Occupant behaviour, Energy consumption, Influencing factors, Window opening
Download as:


text:
Finding Your RootsTragedy + Time = Comedy | Sunday, 8 p.m.
Uncover a history of tragedies and triumphs in the families of three of America's funniest men -- Jimmy Kimmel, Norman Lear and Bill Hader -- as they learn how comedy truly has its place in all aspects of life.
The TunnelEpisode 5 | Monday, 9 p.m.
The "Truth Terrorist"'s third "truth" begins as Benji carries out his Samurai mission. Sophie's life is now at stake and police believe they can use her to stop the terrorist's rampage. Karl gets more than he bargained for while visiting Charlotte.
Jon Roemer - Dakota, IL
"I actually came to Eastern looking for a degree in broadcasting or journalism of some sort. When I came through (Hit-Mix 88.9) on a student tour, they said you can get experience on-air. That's pretty cool."
WEIU membership is important to Jon, and you can also be a proud member! Also, send us a message and let us know what WEIU means to you!
Judy - Mattoon, IL
"Being an avid dog lover, I've learned much from the veterinarian guests you've had on The Paw Report as well as about several animal rescue organizations I didn't previously know existed. I hope WEIU will continue airing this program. Another of my favorites is Heartland Highways! I'm always wanting to see more interesting facts and video about the communities you visit. Thank you WEIU-TV."
WEIU membership is important to Judy, and you can also be a proud member! Also, send us a message and let us know what WEIU means to you!
Kate Pleasant - Producer/Director
When Did You Start at WEIU? Summer 2007
What Does WEIU Mean to You? WEIU means a safe, family-friendly entertainment and learning source.
Favorite Show on WEIU: I have a 2-year-old, so we're really getting into Super Why and Word World. My personal favorite is a lot of our local programming because it really connects me to our community. On the national side, I'm starting to get into Downton Abbey!
What have you learned while working at WEIU?: What haven't I learned!? WEIU has taught me about valuing my community. WEIU has taken me places I never thought I would go (like an underground river for Heartland Highways). I have learned that not only is WEIU great, quality programming, but the people behind it really believe in the mission too.
Why should someone become a member of WEIU? Everyone should become a member of WEIU. I'm a member. If you value educational programming, information straight from your own backyard, and family-friendly TV, then WEIU is for you. You should know, too, that everyone behind the scenes here at the station really believes in what we do too. For us, it's personal. We're a family and we're always looking to expand, so come be a part of our story!
Is WEIU as important to you as it is to Kate? Become a member today! Also, send us a message and let us know what WEIU means to you!
We love to hear from you!
I support WEIU because I know that at any time, day or night we can tune in and we can count on good, quality entertainment and good wholesome programming made available to us. WEIU is what I consider to be a family friendly television station because I know that if my children or grandchildren are visiting and they enter the room where I'm watching TV, I don't have to worry about anything inappropriate being on my TV screen. I know that I can trust WEIU and I love that!
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Mary Ann Stepp - Our Story Bonus Feature
Mary Ann Stepp shares her experiences living in the Pearce Funeral Home in Marshall.
Mary Ann would love for you to tune in to Effingham: This is Our Story on Thursday, Oct. 2, at 7 p.m. We hope you'll join us!
Rick Medsker - Our Story Bonus Feature
Rick Medsker talks about the long-lasting impact of the Velsicol plant in Marshall.
Rick would love for you to tune in to Effingham: This is Our Story on Thursday, Oct. 2, at 7 p.m. We hope you'll join us!


text:
Compelling Mexico to Pay for the Wall
Introduction: The provision of the Patriot Act, Section 326 - the "know your customer" provision, compelling financial institutions to demand identity documents before opening accounts or conducti
By: nagger74 | Comments: 53 | Views: 1007 | Votes: 6 | Shared: 0
Leaked: Jun-27-2016 in Politics
Not All The Bad Guys Are Behind Bars
If the founders could see the leader we have, and how vulnerable to collapse we are at present, they would weep A while back I was invited to tour a newly opened maximum-security prison.
By: Detroit Iron | Comments: 22 | Views: 1803 | Votes: 9 | Shared: 0
Location: Liberal, Kansas, United States | Leaked: May-29-2016 in Politics
Top 10 Nations That Work The Hardest
We may feel at the end of a hard day's work that we work longer hours than anyone on the planet; however, there are plenty of societies across the globe where long hours are not only the norm, but a
By: WiFi | Comments: 9 | Views: 2051 | Votes: 0 | Shared: 0
Leaked: May-20-2016 in Other News
Notorius British Cuckold says Trump is leading the US into Tyranny.
I hope he's right! If a british pedophile cuckold hates Trump, then Trump must be doing something right! America Has Never Been So Ripe for Tyranny As this dystopian election campaign has unfolded
By: a salt and battery | Comments: 33 | Views: 3318 | Votes: 1 | Shared: 0
Leaked: May-2-2016 in Politics
How to survive doomsday: Humans must upload their minds to machines or try to move Earth's orbit, warn scientists
How to survive doomsday: Humans must upload their minds to machines or try to move Earth's orbit, warn scientists In roughly 500 million years, scientists believe humans will no longer live on the
By: Islamophobia246 | Comments: 32 | Views: 1423 | Votes: 2 | Shared: 0
Location: United States | Leaked: May-9-2016 in Other News
My Favorite George Carlin Moment - Save The Planet
We're all just a bad case of Fleas... RIP George.
By: stirgy | Comments: 10 | Views: 1256 | Votes: 10 | Shared: 18
Location: Earth, Texas, United States | Leaked: Jul-13-2012 in Other Entertainment
How to save the planet
The Wizard of New Zealand on the differences between men and women. The Wizard knows how to save the planet.
By: -suicidebomber- | Comments: 6 | Views: 4806 | Votes: 2 | Shared: 0
Leaked: Jan-10-2010 in Arts and Entertainment
Save the planet: eat a dog?
Liberal 'theology' turns on itself, eats mans best friend..ever heard of "Breath-arians"? They believe you that if you learn to breathe properly, you don't have to eat or drink. One of their proponent
By: HydrogenEconomy | Comments: 12 | Views: 9924 | Votes: 0 | Shared: 0
Leaked: Nov-1-2009 in News
Transsexuals want to save the planet
Save the whales but cut off Willy.
By: mojosebo008 | Comments: 16 | Views: 6301 | Votes: 0 | Shared: 1
Leaked: Nov-13-2007 in Other
Save The Planet
Or we all have to miss all these great things....
By: xchristox | Comments: 10 | Views: 7020 | Votes: 2 | Shared: 0
Leaked: Oct-25-2007 in Other
24 Days To Al Gore's '10 Years To Save The Planet' And 'Point Of No Return' Planetary Emergency Deadline…
Via WUWT: http://wattsupwiththat.com/2016/01/02/24-days-to-al-gores-10-years-to-save-the-planet-and-point-of-no-return-planetary-emergency-deadline/ On January 25th, 2006, while at the Sundan
By: copperdog3 | Comments: 127 | Views: 1617 | Votes: 6 | Shared: 0
Location: United States | Leaked: Jan-3-2016 in Politics
ExxonMobil's CEO Asks: 'What Good Is It to Save the Planet?'
Here's a not-very-surprising development: At the ExxonMobil annual shareholder meeting in Dallas on May 29, the corporation's CEO, Rex Tillerson, told those in attendance that an economy that
By: Detroit Iron | Comments: 23 | Views: 1779 | Votes: 0 | Shared: 0
Location: Dallas, Texas, United States | Leaked: Jun-1-2013 in Other News
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text:
Even though we ARE Nikon lovers,we are NOT affiliated with Nikon Corp. in any way.
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Tallahassee, Florida, US
2945 posts
"RE: Lens for Car Photography"
You may be able to get the look you want at the 18mm end of your 18-55, so give that a try. But three of the four photos you've posted do look like they used a wider lens. Here are three you might consider:Sigma 10-20mm f4-5.6 (excellent value, good image quality, definitely the value leader for DX wide angles.)Nikon 10-24 (wider zoom range might help at the long end, and it's a Nikon.)Sigma 8-16 (widest lens at the wide end, excellent image quality.)There are a few other options for wide angles, but from what you've said those are the three I'd look at.Randy


text:
PowerColor Radeon RX 480 RED DEVIL review
Guru3D Rig of the Month - July 2016
Radeon RX 480 vs GeForce GTX 1060 FCAT Frametime Analysis Review
Gigabyte GeForce GTX 1060 G1 GAMING Review
Anidees AI-Crystal Tempered Glass review
MSI GeForce GTX 1060 GAMING X Review
Palit GeForce GTX 1060 Super Jetstream Review
GeForce GTX 1060 Review
GeForce GTX 1060 FCAT Frametime Analysis Review
MSI GeForce GTX 1080 GAMING Z 8G review
Intel HD Graphics 188.8.131.529 Driver out
by Hilbert Hagedoorn on: 09/20/2011 03:50 AM | Source | 0 comment(s)
These are HD drivers for Intel integrated processor chipsets like in Core i3/i5/i7 Sandy bridge processors and Intel Core i3/i5 series 500/600 Dual-Core processors based on the Clarkdale core
Performance Improvements
- This driver release was designed to increase 3D gaming performance on mobile platforms across a variety of titles.
Fixed Issues
- Resolved intermittent crashing when an HDMI monitor is connected
- WebGL rendering anomaly in Google Chrome* and Mozilla Firefox* browsers resolved.
- Eliminated minor rendering artifacts that were present in a few particular scenes in the following games:
- Assassin's Creed
- Darkspore
- The Elder Scrolls IV: Oblivion
- Empire: Total War
- King of Kings 3
- Mass Effect 2
- Medal of Honor
- StarCraft II: Wings of Liberty
- Sudden Attack
- Tom Clancy's H.A.W.X
- Warhammer 40,000: Dawn of War II - Retribution*
- Fixed corruption issue in the Battlefield: Bad Company 2* game (DirectX* 9 version)
- Fixed corruption in James Cameron
« Compro IP70 security camera review · Intel HD Graphics 220.127.116.119 Driver out · Blacklight: Retribution - Dev Diary #1 »


text:
Journal of Applied Probability
For over four decades, the Journal of Applied Probability has provided a forum for original research and reviews in applied probability. Its wide audience includes leading researchers in the many fields where stochastic models are used, including operations research, telecommunications, computer engineering, epidemiology, financial mathematics, information systems and traffic management.
Top downloads over the last seven days
Card counting in continuous timeVolume 49, Number 1 (2012)
A threshold limit theorem for the stochastic logistic epidemicVolume 35, Number 3 (1998)
- ISSN: 0021-9002 (print), 1475-6072 (electronic)
- Publisher: Applied Probability Trust
- Discipline(s): Statistics and Probability
- Full text available in Euclid: 1998--
- Access: By subscription only
- Euclid URL: http://projecteuclid.org/jap


text:
what is the coil gauge?
The mattress exceeded expectations. My mother is disabled and needed a new bed. She LOVES this pillowtop mattress and says it is much more comfortable. it took several weeks to ship and shipping was delayed a week. When it arrived, the shippers were pros and removed the old mattress for free. The mattress says full and her old bed frame didn't work because it was a bit too small, so I would suggest getting a small metal frame as well. All said, an excellent mattress for a very good price plus free shipping! Even on sale at brick and mortar stores we couldn't find anything close. I will purchase from Overstock.com in the future....
Serta Perfect Sleeper Liberation Pillowtop Full-size Mattress and Box Spring Setby Serta
ITEM#: 13692117This is the first official mattress of the National Sleep Foundation. This mattress set is designed to help address five common sleep issues: tossing and turning, lack of back support, temperature concerns, partner disturbance and sagging.
- Set includes: Mattress, foundation
- Construction: Pillowtop
- Support: Plush
- Materials: Memory foam, cotton, foam, fiber, wood, steel
- Awarded a Consumers Digest 'Best Buy'
- Convoluted foam designed to provide additional pressure relief at the shoulders, arms and hips
- Rows of continuous give the innerspring more stability
- Total Edge Foam Encasement prevents sagging at the mattress edges
- Meets all federally mandated flammability standards with Serta's patented FireBlocker system
- Mattress set: 22 inches high x 53 inches wide x 74.5 inches long
- Mattress: 13 inches high x 53 inches wide x 74.5 inches long
- Foundation: 9 inches high x 53 inches wide x 74.5 inches long
White glove home deliveries require a 4-hour window to complete delivery; this includes delivery of the mattress, set-up in the room of your choice, removal of all packaging and debris and removal of your old mattress upon request. Please note that there is no surcharge for additional flights of stairs. You will be contacted by the home delivery agent when the product is ready for delivery (typically 1 to 3 weeks), we recommend requesting product removal at the same time you schedule your home delivery appointment.
30-Day Comfort Guarantee - If you are not satisfied with your purchase within 30 days, you may return your order for a refund less a re-stocking fee. After 30 days, the mattress cannot be returned.
|Mattress Type
|Innerspring, Memory Foam
|13 Inch
|Mattress Top
|Pillow Top
|See product description
|10 year Limited Manufacturer
|Model Number
|Country of Origin
|United States
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Customer Reviews
Most Recent
Great mattress and box springs for the money
The mattress exceeded expectations. My mother is disabled and needed a new bed. She LOVES this pillowtop mattress and says it is much more comfortable. it took several weeks to ship and shipping was delayed a week. When it arrived, the shippers were pros and removed the old mattress for free. The mattress says full and her old bed frame didn't work because it was a bit too small, so I would suggest getting a small metal frame as well. All said, an excellent mattress for a very good price plus free shipping! Even on sale at brick and mortar stores we couldn't find anything close. I will purchase from Overstock.com in the future.Read More
Most Helpful
Serta-nly a sound sleep
I really don't know how to compare mattresses, this was an upgrade for me after sleeping on futons for years and years. So I love it. It's super thick and cushy, and I think it'll last a long time. I travel for work and sleep in a lot of hotels and this to me feels on par with what you get in a nice hotel.Read More
Aches and Pains are Gone
I reached my limit with waking up feeling like I hadn't slept, went online to research and purchase a good mattress and box spring and came across this one. It's a model no longer made but comparable to others currently on the market, at twice the price. The first night I spent on this new mattress, I slept nine hours (unheard of) and woke up feeling like I had actually rested. And my back and hips were not hurting! I highly recommend this product. A great nights sleep is worth any amount of money but it sure doesn't hurt to not have to break the bank! I also can't say enough good things about the quality of delivery. I was kept informed by both Overstock and the delivery company they subcontract with, sent very detailed information, the delivery was made ahead of schedule and the delivery team was fast, efficient, courteous and even took my old mattress away for me - a bonus I had not expected!Read More
Excellent firm mattress I have been looking for
I was looking for two sets of mattress for my children (2 and 4 years old), but didn't want to pay a lot of $$$. Then, I found this product in this website at very low price. So I purchased this one for my first child and another product for my second child. I was very satisfied when this product was delivered (was faster than expected) and with the other, too. The other product had very good reviews, but this one had no review. However, I knew the name of this brand and I had a trust in it, and I was right. This is a great product especially if you are looking for a firm mattress. I can tell the quality at a first sight. My husband even ejoys lying on it. I think it will last long for my daugher. Very good products!!!Read More
Best quality mattress for the money
I went to the big mattress/furniture store here in town and was disappointed by how expensive a mediocre full size mattress cost. For $400 I could get something that wasn't much better than what I was trying to replace in my home. I was not impressed, so I scoured Craigslist, but was a bit reluctant to buy a used quality mattress that way too. Then a friend recommend Overstock (they were also having a great sale). I was very excited about the top quality brands and the unbeatable prices, and the FREE white glove delivery service was the icing on the cake!! After all the sale promotions were tallied, I saved over $100 on a GREAT mattress (that already had a great low price) and the old one got taken away for free. I did have to wait 10 days to get it delivered, but it was so worth it! I will definitely buy here again when searching for another mattress, you just can beat the prices or the delivery for the quality you receive.Read More
Questions & Answers
The coil gauge is 13.
how many coils?
The coil density is 442.
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5 Tips to Help You Defeat Insomnia from Overstock.com. If you have trouble sleeping, you're not alone. Did you know that 1 in 10 people have insomnia? Here are five methods that have helped many people get a better night's sleep.
How to Select a Mattress Set
How to Select a Mattress Set from Overstock.com. People spend anywhere between six to nine hours each day in their beds, making it one of the most used pieces of furniture in any home.
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1-4 week delivery after the item ships:**
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text:
Breakaway congregation sued over building Church sues 12-member congregation
Published: Wednesday, January 11, 1995 at 3:15 a.m.
Last Modified: Wednesday, January 11, 1995 at 12:00 a.m.
An Atlanta-based evangelical church said it's fine for a 12-member Lyman congregation to break away. They just can't keep their building. Fire Baptized Holiness Church of the Americas filed suit Tuesday in Spartanburg County court to have the parishioners removed. In November, members of the Fire Baptized Holiness Church near Lyman seceded from their main organization to follow a pastor who had fallen out of favor with church officials. But the lawsuit says the former members refused to vacate the property. Richard H. Rhodes, a Spartanburg lawyer representing the denomination's general board of trustees in the lawsuit, said the parish and the pastor are free to leave. However, Rhodes said the property stays with the main church. Robina Gist, a 20-year member of the church, said the dispute is really between denomination officials and the pastor. "They didn't want our pastor with us, and we wanted to follow him," she said. "I don't know exactly who owns the building." The Rev. Eugene Bethel could not be reached at his Columbia home. But a woman answering the phone said, "there's no comment." J.O. Hargrove, a presiding elder of the church from Charlotte, said he doesn't know why the congregation decided to split off. He said, however, that Bethel was about to be replaced because he wasn't doing an effective job. Hargrove, who described the organization as a Christian Protestant movement, said the main church owns more than 300 churches nationwide. He said there are at least 18 in South Carolina, including ones in Spartanburg, Greer, Gaffney, Landrum, Pacolet, Campobello, Blacksburg and Jonesville. The main church is asking a judge to rule that it is the rightful owner of the property and that the congregation be required to leave the premises. Original Atex file name: HOLYWA.R1
Reader comments posted to this article may be published in our print edition. All rights reserved. This copyrighted material may not be re-published without permission. Links are encouraged.
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text: Does anybody know of a way to prevent the timestamp of an executable from changing? I'm trying to generate a consistent hash code for the .exe but I think the timestamp may be preventing that from happening. Each time I recompile the code (VS C++) the FastSum generates a different checksum.


text:
All States K-9 Detection & Dog Training
Cesar Millan with K9 Viper - see the whole story under our 'In the News' section. Daddy was the initial link to Viper (fear of people) becoming a well-balanced dog.
This is the first of three NATGEO segments with Cesar - see also an unedited version of 'Cesar's Worst Bite' (where Lamb gets bitten by Holly, too) and the 2nd half of "Unadoptable Maury", who Cesar brought to us to learn a new job.
Check out our History Channel segment with Stan Lee's Superhumans, filmed at the All States K-9 training facility- story inside under 'In the News' section.
All States K-9 Principal
"Lamb" Lambert & K9 Sugar
The way to a pup's heart could be through his owner, finds new research in the journal Animal Behavior. When dogs were offered treats from two strangers, one who was a mean owner and another who was helpful, they much more often went to the kind one - because, like humans, dogs sense and act on emotional cues, explains study author Kazuo Fujita.
Next time you want to pet a pooch, befriend the owner first. You'll stay on Fido's good side - and out of the doghouse.
We are not accepting new contract clients, but we remain passionate about the welfare and lifestyle of pet families.
Here's what we're up to:
Today's Feature - how to


text:
Naked & Famous
Weird Guy
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Raw cotton slim leg five-pocket jeans in sashiko knit with button fly. Tonal stitching. 11" rise. 36" inseam. 14" leg opening. Made in Canada. Cotton. Dry clean.Style # 502249403
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