text:
|Publication number
|Publication type
|Publication date
|Jan 28, 1964
|Filing date
|Dec 23, 1957
|Priority date
|Dec 21, 1956
|Publication number
|Schultheis Heinz, Nordt Herbert, Kallert Wilhelm
|Original Assignee
|Bayer Ag, Mobay Chemical Corp
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (15), Referenced by (17), Classifications (17)
|External Links: USPTO, USPTO Assignment, Espacenet
United States Patent Ofilice 3,119,792 Patented Jan. 28, 1964 3,119,792 METAL AND METAL QGMPGUND CATALYTS FQR IQLYURETHANE PLASTICS Heinz Schultheis, Cologne-tammhcim, Herbert Nordt, Leverlrusen, and Wilhelm Kallert, Cologie-Stammheim, Germany, assignors, by direct and mesne assignments, of one-half to Farbeniabrihen Bayer Aktiengesellschait, Levcrhusen, Germany, a corporation of Germany, and onahali' to Mobay Chemical Company, Pittsburgh, Pa, a corporation of Delaware No Drawing. Dec. 23, 1957, Ser. No. 764,344 Claims priority, application Germany Dec. 21, 1956 7 Claims. (Cl. 260-775) This invention relates generally to the preparation of polyurethane plastics and, more particularly, to an improved process for making elastomeric or homogeneous plastics.
It has been proposed heretofore to prepare polyurethane plastics by a process wherein an organic compound having reactive hydrogens is reacted with an organic polyisocyanate and a crosslinking agent. The organic compound having reactive hydrogens may be a polyhydroxy compound, such as, for example, a polyester, polyesteramide, polyalkylene ether glycol, polythioether or polyacetal having terminal hydroxyl groups. The polyurethane may be prepared by reacting one of these compounds with an excess of the organic polyisocyanate to prepare an adduct or prepolyrner having terminal isocyanate groups and this adduct may then be reacted with a cross-linking agent while the liquid reaction mixture is cast into molds to form the final plastic. In an alternate procedure, the organic compound having reactive hydrogen atoms is reacted with less than the equivalent amount of organic polyisocyanate to produce an adduct having terminal hydroxyl groups and this adduct or storage-stable intermediate may then be mixed with a crosslinking agent to form a compound which is reacted with further organic polyisocyanate to form the finished product. The cross-linked rnillable gum is usually reacted with the organic polyisocyanate While it is being processed on a rubber mill or any other suitable apparatus customarily used in compounding rubber. It has been the practice heretofore to add various types of catalysts to the reaction mixture to accelerate the reaction. The heretofore available catalysts have the disadvantage, however, of sometimes adversely affecting the color, structural strength, elasticity or aging characteristics of the polyurethane and are not adaptable to wide commercial application.
It is therefore an object of this invention to provide an improved process for making elastomeric, homogeneous or substantially non-porous rubber-like polyurethane plastics. Another object of the invention is to provide a method for making substantially non-porous rubber-like polyurethane plastics having improved color, structural strength, elasticity, aging characteristics and other physical characteristics. Still another object of the invention is to provide an improved method for catalyzing the reactions which produce a substantially non-porous rubber-like polyurethane plastic. A further object of the invention is to provide improved catalysts for the reactions which produce polyurethane plastics.
Generally speaking, the foregoing objects and others are accomplished in accordance With this invention by providing a method for making polyurethane plastics wherein the reactions between an organic compound having reactive hydrogens and an organic polyisocyanate are brought about in the presence of gold, zinc, cadmium, titanium, antimony or bismuth. One or more of these metals may be present in the reaction mixture either as the metal per se or as a suitable compound of the metal. In accordance with this invention, the organic compound having reactive hydrogen atoms is reacted with the organic polyisocyanate in the presence of the catalyst and a crosslinking agent may be added, it necessary, to produce the polyurethane.
It is preferred that the catalyst provided by this invention be an inorganic or organic compound present in crystalloid or colloidal form in the reaction medium either as the metal per se or in the form of a compound of the metal. Any suitable compound of one of the metals mentioned hereinbefore or the metal itself may be used, it only being necessary that the metal be present in the reaction mixture. Examples of suitable catalysts of the class provided include colloidal gold, aurochlorohydric acid, titanium tetrabutylate, Zinc adipate, antimonylll-oxide, bismuth nitrate, cadmium chloride, or a complex of one of the metals, such as, for example, the titanium complexes of disalicylal ethylene diirnine of the type disclosed by P. Pfeilfer and H. Thielert, B. 71, 1938, p. 121, or the like.
The catalyst provided by this invention may be used to advantage to accelerate the reaction between any suitable organic compound having reactive hydrogen atoms, organic polyisocyanate and, it necessary, cross-linking agent which react together to form a substantially non-porous rubber-like polyurethane plastic. Examples of organic compounds having reactive hydrogens include polyesters having terminal hydroxyl groups and prepared by esterification of a polycarboxylic acid and a polyhydric alcohol. Adipic acid, succinic acid, terephthalic acid, sebacic acid or any other suitable polycarboxylic acid may be reacted with the polyhydric compound to prepare the polyester. The polyhydric alcohol may be a diol, such as, for example, ethylene glycol, diethylene glycol, or, in some instances, a trihydric alcohol, such as, for example, glycerol, or trimethyiol propane may be used in admixture with the diol. It is preferred that the pol ester have an acid number of from O to about 2. The polyalkylene ether glycol may be prepared by condensing a lower alkylene oxide, such as, for example, ethylene oxide, propylene oxide, butylene oxide, or the like, or by condensing one of the oxides with a glycol or other polyhydric alcohol. Polythioether glycol may be prepared by condensation of a suitable thioglycol, such as, for example, thiodiglycol or the like. The organic compound having reactive hydrogen atoms should preferably have a molecular weight of at least about 500 and an hydroxyl number of not more than about 224.
Any suitable organic polyisocyanate may be reacted with the organic compound having reactive hydrogen atoms, such as, for example, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, p-phenylene diisocy anate, napthylene-1,5-diisocyanate, 4,4'-diphenyl dimethyl methane diisocyanate, diisocyanates containing urea or uretdione linkages or the like.
Any suitable cross-linking agent heretofore disclosed may be used, such as, for example, any suitable glycol, including ethylene glycol or diethylene glycol, an amino alcohol, such as, for example, ethanolamine, a diamine, such as, for example, ethylene diamine, or a suitable hydrazine or the like, may be used. In fact, it is to be understood that the catalyst provided by this invention may be used in preparing any homogeneous or substantially nonporous rubber-like polyurethane and that the invention is not limited to the use of the catalyst with any particular reaction components. Examples of other components of a polyurethane plastic which may be used are disclosed in US. Patents 2,621,166, 2,620,516, 2,729,618, 2,764,565, 2,778,810 and any of the processes for making substantially non-porous rubber-like polyurethanes disclosed therein may be accelerated with the catalyst provided by this invention.
Any amount of the metal catalyst provided by this invention will efiect some acceleration of the reactions and any amount is therefore contemplated by the invention. However, in most instances, the quantity will be relatively small and it is preferred to use from about 0.01 percent to about 0.1 percent of the compound. It may be possible, however, to use even larger quantities in some cases, so the invention contemplates using any catalytic amount which does not interfere with the physical characteristics of the final product. Seldom will more than about 5 percent catalyst based on the weight of the reaction mixture be required.
It may be advantageous for these compounds to be previously admixed with one of the components required for the production of the plastic, this preferably taking place during the preparation of the component. In the preparation of a polyester from dicarboxylic acids and polyhydrie alcohols for use in this invention, it is, for example, advisable to add a small quantity of gold chloride to the esterification mixture. The polyester being formed then contains the gold in dissolved form. It is also possible for the metal compound concerned to be admixed with the polyhydroxy compound after the latter has been prepared, or even to admix it with the crosslinking agent. It is in each case important that the reaction producing the plastic is carried out in the presence of one of the said metals. It is, in certain circumstances, sufiicient for only the last stage of the reaction leading to the plastic to take place in the presence of the catalyst according to the invention.
In order better to describe and further clarify the invention, the following are specific embodiments thereof:
Example 1 About 1548 parts by weight of ethylene glycol and about 3285 parts of adipic acid are esterified to give a polyester with the OH number about 55 and an acid number of about 1.2. About 0.020 part by weight of gold trichloride is added at the commencement of the esterification. About 1000 parts by weight of the polyester prepared in this manner are stirred at about 126 C. with about 180 parts by weight of 1,5-naphthylene diisocyanate. After about 6 minutes, the reaction is practically completed, i.e., the temperature of the reaction mixture does not rise any further. About 20 parts by weight of 1,4- butylene glycol are incorporated by stirring into the thinly liquid melt and the mass is poured into waxed molds which are heated to about 110 C. The time available for the casting operation is about 3.5 minutes. A standard molded element can be removed from the mold after about 6 minutes.
An ester which was prepared in the same manner from adipic acid and ethylene glycol, but without any gold trichloride being added, produces under the same conditions by reaction with 1,5-naphthylene diisocyanate a reaction mixture which only reaches the maximum temperature after about 11 minutes. A standard molded element produced therefrom can only be taken from the mold after about 14-15 minutes, the time available for pouring being about 3.5 to about 4 minutes.
Example 2 About 1 part by weight of zinc adipate is dissolved at from about 60 C. to about 70 C. by stirring for several hours in about 2000 parts by weight of a polyester pre pared by thermal esterification of about 175.2 parts by weight of adipic acid, about 128.2 parts by weight of diethylene glycol and about 8.1 parts by weight of trimethylol propane. This polyester is then mixed at about 100 C. with about 140 parts by Weight of toluylene diisocyan-ate. The mixture is stirred for about minutes, the temperature rising to about 107 C. and is then poured into waxed molds, in which the mass remains liquid for about 8 minutes, gradually becomes more viscous and solidifies within about 1.5 hours to provide a soft mass which retains its shape. The product represents a very valuable plastic for the production of printing cylinders. The Shore hardness is about 22.
However, if the reaction described above is conducted without adding zinc adipate, the mixture of toluylene diisocyanate and polyester has only reached a temperature of about 103 C. after about minutes and, after the casting operation, it can only be removed from the mold after from about 2.5 to about 3 hours.
Example 3 About 500 parts by weight of a polyester prepared by thermal esterification of adipic acid and ethylene glycol, the initial components thereof having about 0.25 part by weight of cadmium chloride added thereto at the start of the esterification and the polyester having an OH number of about 52, are stirred at about 120 C. with about 67.5 parts by weight of 1,4-phenylene diisocyanate. The temperature of the mixture rises within about 4 minutes to about 129 C. After stirring for another 4 minutes, about 10 parts by weight of 1,4-butane diol are mixed therewith and the mixture is poured into waxed molds which are heated to about 110 C. A standard molded element can be removed from the mold after about 15 minutes. By heating for another 2 hours to about 105 C., a plastic is obtained which has very high tensile strength, notch toughness and resistance to oil and rubbing.
However, if the same polyester is processed in the same way but without adding cadmium chloride, the mixture with 1,4-phenylene diisocyanate only reaches a temperatureh of about 128 C. after about 7 minutes and the standard molded element prepared in the same way can only be removed from the mold after about to minutes.
Example 4 About 110 parts by weight of 1,5-naphthylcne diisocyanate are incorporated by stirring at about 122 C. into about 500 parts by weight of a. polythioether obtained from thiodiglycol and 1,4-butylene glycol in the mol ratio 1:1, the polythioether having an OH number of about 55. After about 6 minutes, the temperature of the reaction mixture does not rise any further and after about 18 parts by weight of 1,4-butylene glycol containing about milligrams of titanium tetrabutylate have been incorporated by stirring for about 20 seconds, the mixture is poured into waxed molds heated to about 105 C. The mass remains thinly liquid for about seconds and solidifies after about 8 minutes to provide a material with sufficiently high rigidity to allow it to be removed from the mold. After heating for another 24 hours at about C., a resilient plastic is formed which is characterized by high resistance to oil and saponification.
By carrying out the same process without addition of titanium tetrabutylate to the 1,4-butylene glycol, however, it is necessary to wait about 12 to 16 minutes before the cast element can be removed from the mold.
Example 5 About 2000 parts by weight of a polyester which has been prepared from ethylene glycol and adipic acid by thermal esterification and which has an OH number of about 52, are mixed at about C. with about 245 parts by weight of 1,4-phenylene diisocyanate. Previous ly, about 1.0 part by weight of disalicylal ethylene diimine-titanium hydroxy chloride have been admixed with the polyester. The temperature rises in about 6 minutes to about 132 C. After about 10 minutes, about 70 parts by weight of 1,4-butane diol are admixed therewith, the reaction mass is immediately discharged onto a heated sheet metal plate and after-treated for another 20 hours at about 110 C. A mass is formed which can be rolled and which is made suitable for vulcanization by admixing about parts by weight of dimcric 1,2,4- toluylene diisocyanate on the roller. By pressing at about 140 C., a highly elastic plastic which resists rubbing is obtained in about 30 minutes, and this can be removed at about 80 C. The tensile strength of this material is about 280 kilograms per square centimeter with about 650% elongation. However, if the same process is carried out without adding disalicylal ethylene diimine-titanium hydroxy chloride to the polyester, the vulcanization in the press takes about 70-80 minutes before the element can be removed at 80 C.
Example 6 About 60 milligrams of antimonic acid triethyl ester are mixed at about 50 C. with about 400 parts by weight of a polybutylene glycol with the OH number of about 48. About 48 parts by weight of p-phenylene diisocyanate are then incorporated therein at about 95 C. by stirring. After about 4 minutes, the temperature of the reaction mixture stops rising and after adding a mixture of about 6 parts by weight of thiodiglycol and about 2.5 parts by weight of trimethylol propane, the reaction mixture is poured into waxed molds heated to about 110 C. A standard molded element cast in this manner can be removed from the mold after about 50 minutes. A resilient plastic is obtained which is very resistant to saponification, has a tensile strength of about 105 kgjem. and a breaking elongation of about 440%.
A material prepared in the same manner, but without addition of the antimony compound, must be left in the mold about 110 to about 120 minutes before it can be removed. The physical characteristics of the molded body are then: Tensile strength, about 110 kg./cm. with about 380% breaking elongation.
Example 7 About 1548 parts by weight of ethylene glycol and about 3285 parts by weight of adipic acid are thermally esterified with simultaneous addition of about 3.8 parts by weight of bismuth trichloride to provide a polyester with the OH number about 55 and an acid number of about 1.0. About 850 parts by weight of the polyester prepared in this manner are mixed at about 1150 C. With about 2.5 parts by weight of 4,4'-diphenyl methane diisocyanate. The temperature of the mass rises within about 3 minutes to about 123 C. After another 7 minutes, a mixture of about 55 parts by weight of 1,5-naphthalene-fl-dihydroxyethyl ether with about 150 parts by weight of the aforementioned polyester, which mixture has been heated to about 145 C., is mixed with the said mass. The mixture is poured into waxed molds, which are heated to about 100 C. After about 12 minutes, a standard molded element can be removed. By heating for another 20 hours at about 110 C., there are obtained hi hly elastic molded bodies with a tensile strength of about 320 kg./cm. and a breaking elongation of about 620%.
If the same process is carried out with a polyester which does not contain any addition of bismuth trichloride, the first reaction stage between the polyester and the 4,4-diphenyl methane diisocyanate takes 5 minutes before the temperature maximum is reached. A standard molded element manufactured therefrom can be removed from the mold after about 25 minutes.
It is to be understood that any of the other metals or compounds of metals disclosed as a catalyst herein my be substituted in the foregoing examples for the catalyst specified and acceleration of the reaction will likewise be obtained.
The product of this invention may be used for making vehicle tires, machine parts, shoe soles or as a substitute for rubber in many other applications.
An essential advantage of the process according to the invention is that plastics are obtained which are light in color, these plastics also having an excellent structural strength, elasticity and resistance to aging. Furthermore, the setting time of the freshly manufactured plastic element is substantially shortened as compared with mixtures not containing metal, so that more articles can be manufactured in the same time as compared with previous processes.
It is already known to use metallic soap powders and metallic leafing powders as additive in the manufacture of porous polyurethanes to give an improved pore structure. These metal compounds are insoluble in the reaction medium. It, therefore, has been proposed to use instead liquid compounds of threeand higher valent metals in the manufacture of porous polyurethanes. These liquid metal compounds do not serve as reaction accelerators as can be seen from the fact that tertiary amine activators are always concurrently used with these liquid metal compounds. The reaction mechanism of the processes leading to porous polyurethanes and to homogeneous polyurethanes respectively are quite different which fact is illustrated by the following examples C and D. In the manufacture of homogeneous polyurethanes according to the present invention it is unnecessary to add an organic tertiary amine or the like for accelerating the process. Far more important, however, the addition of such an organic base will adversely affect the mechanical properties of the final product.
Example A 1548 parts of ethylene glycol and 3285 parts of adipic acid are esterified to give a polyester with the OH number 55, and the acid number 1.2. Esterification is performed in the presence of 0.05 part of titanium tetrab-utylate. 1000 parts of the polyester thus obtained are mixed with parts of 1.5-naphthylene diisocyanate at 126 C. 20 parts of 1.4-butylene glycol are introduced into the melt. The mass is poured into a waxed mold heated to 110 C. A test plate has the following physical properties:
Tensile strength "kg/om? 280 Elongation at break percent 750 Structural strength l g./om 60 Shore hardness at 20 C degrees 79 Shore hardness at 70 C do 79 Elasticity percent 5 1 Permanent elongation d0 19 Example B The procedure of Example A is repeated. 10 parts of the Iadipitc acid ester of N-diethyldiethanol amine are added to the polyester before reacting the polyester with 1,5-naphthylene diisooyanate. A blistery test plate is ob tained having the following mechanical properties:
Tensile strength kg./cm. Elongation at break percent 700 Structural strength kg./crn 58 Shore hardness at 20 C degrees 74 Shore hardness at 70 C do 73 Elasticity percent 54 Permanent elongation do 25 Whereas Examples A and B show that the presence of a tertiary amine catalyst in addition to the metal compounds of the invention is detrimental for the process the following Examples C and D show that the behavior of catalysts in the manufacture of polyurethane foams cannot be compared with the behavior in the manufacture of homogeneous polwrethane plastics.
Example C Following the procedure of US. Patent 2,764,565 100 parts of a polyester prepared from 175.2 parts of adipic acid, 128.2 parts of diethylene glycol and 8.1 parts of trimethylol propane are mixed with 43.2 parts of toluylene diisocyanate, 3 parts of o-benzyloxydiphenyl polyglycol ether (54% water content), 1.5 part of a sulfonated castor oil (54% Water content), 1 part of ricinoleic acid, 1 part of Water, 0.3 part of parafiin oil and 1.2 part of dimethylbenzyl amine. The foaming mass has expanded within 1.5 minutes and completely cured after 15 minutes. Bulk density 35 kg./m.
of 250 mm. of beryllium hydroxide. was well as the casting time are unchanged. That means ,in order to avoid undesired side reactions. found that such an acidic medium-metal compound-sys- 7 Example D Instead of 1.5 part of dimethylbenzyl amine 1.2 part of titanium tetrabutylate is added to the foam formulation. The foamable mass has expanded after 30 minutes. Curing time is 48 hours. A heavy, cracked foam is obtained of a bulk density of about 60 kg./m.
These Examples C and D clearly exhibit that it is not advisable to use the titanium compounds which are disclosed as being highly suitable in the manufiacture of the present process in a procedure leading to porous polyurethanes. In fact, if no catalyst at all is involved in the foaming process the effect would be the same as in case of addition of titanium tetrabutylate.
It has already been proposed to use beryllium hydroxide as curing catalyst for isocyanate-based elastomers. Beryllium hydroxide, however, cannot compete with the new catalyst disclosed in the present specification as illustrated in Examples E and F. Example E shows the preparation of an isocyanate-based elastomer without a catalyst, Example F is related with the same elastomer manufacture in the presence of beryllium hydroxide.
Example E 500 parts of the polyester identified in the above Example 1 are mixed with 90 parts of 1.5naphthylene diisocyanate at 125 C. After 16 minutes the reaction temperature does no longer rise, i.e. reaction is practically complete. 10 parts of a mixture consisting of 4 parts of trimethylol propane and 6 pants of 1.4-butane diol are added. Casting time of the reaction mixture is minutes. A test plate can be taken from the mold after 70 minutes and is heated for 24 hours at 110 C.
Example F The procedure of Example E is repeated in the presence The reaction rate that beryllium hydroxide does not act as reaction accelerator. A test plate shows undissolved particles of beryllium hydroxide being distributed within the elastomer which clearly indicate that a higher reaction rate and a shorter casting time is observed when using the new catalysts claimed with the present application instead of beryllium hydroxide.
Still another kind of reaction mechanism is involved when in organic solvents soluble isocyanate-based polyaddition products are to be prepared. In such cases it is .known to use a combination of an acid medium and a metal compound for regulating the reaction mechanism It has been tem is inoperative in the manufacture of homogeneous polyurethane plastics of non-porous rubber-like polyurethane plastics of the present process. Example G shows the additional use of terephthalic acid chloride as acid medium in the manufacture or" isocyanate-based elastomers.
Example G from the mold after about 1 hour and a half. The physical properties of the product are 8 Tensile strength "kg/caulk- 240 Elongation at break percent 650 Structural strength kg./cm 71 Shore hardness at 20 C "degrees" 94 Shore hardness at 70 C do Elasticity percent 39 Permanent elongation do 35 Example H is concerned with the same ingredients as Example G. The only difference consists in using a mixture of terephthalic acid chloride and titanium tetrabutylate. There is no difference in the reaction times and the casting times. The physical properties are substantially the same in both the cases of Examples G and H. In any case, they are inferior to the physical properties of a non-porous rubber-like polyurethane plastic prepared only in the presence of a metal catalyst of the present application.
Example H The same ingredients and the same amounts are employed as in Example 1 and Example G. Instead of 0.6 part of terephthalic acid chloride a mixture of 0.6 part of terephthalic acid chloride and 0.05 part of titanium tetrabutylate is added to each 1000 parts of polyester. After about 6 minutes the reaction of the polyester and the diisocyanate is practically completed, i.e. the temperature of the reaction mixture does not rise any further. After adding the 1.4-butylene glycol the time available for the casting operation is about 3.5 minutes. A standard molded element can be removed from the mold after about 6 minutes. The physical properties of the rubber-like elastomer are Tensile strength "kg/cm? 245 Elongation at break percent.-- 640 Structural strength kg./cm 70 Shore hardness at 20 C degrecs 93 Shore hardness at 70 C do 81 Elasticity "percent" 40 Permanent elongation do-. 35
Although the invention has been described in considerable detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for this purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as is set forth in the claims.
What is claimed is:
1. In the preparation of a substantially nonporous, rubber-like polyurethane plastic by a process which comprises reacting an organic polyisocyanate with an organic compound having reactive hydrogen atoms, a molecular weight of at least about 500, an acid number of not more than about 2, and a hydroxyl number of not more than about 224, said organic compound having reactive hydrogens being capable of reacting with said organic polyisocyanate to form a polyurethane, the improvement which comprises effecting the reaction between the said organic compound having reactive hydrogens and the organic polyisocyanate in the presence of a catalytic amount of a catalyst selected from the group consisting of metallic gold, zinc, cadmium, titanium, antimony, bismuth, aurochlorohydric acid, bismuth nitrate, cadimum chloride, gold trichloride, bismuth trichloride, titanium tetrabutylate, zinc adipate, antimony oxide, disalicylal ethylene diirnine-titanium hydroxy chloride, and antimonic acid triethyl ester.
2. The process of claim 1 wherein the organic compound having reactive hydrogen atoms, a molecular weight of at least about 500, an acid number of not more than about 2, and a hydroxyl number of not more than about 224, is a member selected from the group consisting of a hydroxyl polyester prepared by esterification of a polycarboxylic acid with an excess of a polyhydric alcohol, a polyhydric polyalkylene ether, and a polyhydric polythio ether.
3. The process of claim 1 wherein the organic polyisocyanate is 4,4-diphenyl methane diisocyanate.
4. The proces of claim 1 wherein the catalyst is antimony oxide.
References Cited in the file of this patent UNITED STATES PATENTS Rothrock Apr. 17, 1945 Buist et a1. July 29, 1947 Simon et a1 Nov. 27, 1956 Hampton et a1. July 16, 1957 10 Brochhagen et a1. Aug. 5, 1958 Tischbein Sept. 16, 1958 Burkus Mar. 10, 1959 Seeger et al. Mar. 24, 1959 Windermuth July 28, 1959 Nesty et a1. Aug. 11, 1959 Kehr Jan. 19, 1960 Csendes Jan. 19, 1960 FOREIGN PATENTS Australia Nov. 19, 1953 Great Britain July 24, 1957 France July 15, 1953 OTHER REFERENCES Windemuth, German patent application, No. F12977 printed Oct. 25, 1956 (KL IVb 39c).
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|Filing date
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|Du Pont
|Catalytic reaction of isocyanates with organic compounds
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|Ici Ltd
|Paraformaldehyde treatment of reaction products of diisocyanate with linear polyesters and linear polyester-amides and products resulting therefrom
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|Nov 27, 1956
|Lockheed Aircraft Corp
|Resilient cellular resin products
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|Jul 16, 1957
|Ici Ltd
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|Aug 5, 1958
|Bayer Ag
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|Sep 16, 1958
|Bayer Ag
|Method of coating rubbery materials
|Nov 26, 1956
|Mar 10, 1959
|Us Rubber Co
|Polyurethane polymer containing a metallic dicyanamide
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|Mar 24, 1959
|Goodyear Tire & Rubber
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|Jul 28, 1959
|Bayer Ag
|Production of polyurethanes
|Jul 1, 1955
|Aug 11, 1959
|Allied Chemi
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|Jan 19, 1960
|Du Pont
|Improved process for sulfur-curing polyurethane elastomers
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|Jan 19, 1960
|Du Pont
|Process for curing a sulfur-curable polyalkyleneether polyurethane elastomer
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|Feb 15, 1966
|Union Carbide Corp
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|Jul 2, 1968
|M & T Chemicals Inc
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|Aug 12, 1969
|Tenneco Chem
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|Jan 27, 1970
|Allied Chem
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|Dec 30, 1975
|Beiersdorf Ag
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|Atlantic Richfield Company
|Catalysts for the reaction of cyclic nitrile compounds with nucleophilic compounds
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|Sep 16, 1980
|Ppg Industries, Inc.
|Polyester diol extended uralkyd resin and coating compositions containing the same
|Aug 16, 2006
|Mar 13, 2012
|Akzo Nobel Coatings International B.V.
|Coating composition comprising a polyacrylate polyol, a polyester polyol, and an isocyanate-functional crosslinker
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|Feb 17, 2005
|Walters David N.
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|U.S. Classification
|528/55, 528/57, 528/906, 528/83, 528/74, 528/53, 528/48, 528/80, 528/81, 528/44, 528/52
|International Classification
|Cooperative Classification
|European Classification


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- Ability to automate AirPlay permissions for Apple TVs.
- The Healthcare Listener, a new Jamf Pro add-on for the Healthcare customers, automates remote commands to mobile devices triggered by ADT messages from healthcare management systems. For more information and access to the Healthcare Listener installers, please contact your Jamf SE.
How else can Jamf be used to expedite the Apple experience?
An array of Jamf resources await.
Select your vertical to access the materials that matter to you and your customers.
Customer Success Story: Crane School District
Customer Sucess Story: Aquent

subset: commoncrawl


text:
How Will The Final U.S. Olympic Triathlon Spots Be Decided?
There's one Olympic spot left for the women and at most three spots left for the men. So how exactly will the other spots be filled?
There's one Olympic spot left for the women and at most three spots left for the men. So how exactly will the other spots be filled?
"I helped the U.S. earn a spot on the Olympic start line... You're going to have to rip it out of my fingers to get it from me."
The penultimate round of the 2011 ITU World Cup series heads to Colombia this weekend, the first time the country has hosted a World Cup since 1992.
American Matt Chrabot overcame a bike crash and came from behind on the run to ascend back to the top of the Huatulco World Cup podium today.
Brownlee's Grand Final dominance earned him the overall world title, with younger brother Jonny coming second and Gomez finishing third.
This is the race that all ITU athletes and fans have been waiting for all year—the best triathletes in the world will be peaked and ready to race their best at the ITU's Dextro Energy World Championship Series race in London this weekend as they chase Olympic spots and points for the overall world championship title.
Nine of the United States' top triathletes have earned the right to compete for a spot on the 2012 U.S. Olympic Triathlon Team next month at the International Triathlon Union World Championship Series event in London on Aug. 6-7.
Here's a list of some of the American men and women who have a shot at London in 2012.
Alistair Brownlee leads nearly wire to wire while reigning Ironman world champ Chris McCormack drops out.
ITU racer Matt Chrabot talks about why he never trains through a race.


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A look at drawings of well known artists from the past.
A chance to research the art of drawing.
An opportunity to appreciate the place of drawing in the creative paths of the artists.
An opportunity to see and learn technical drawing skills from some of the masters.


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Subscribe to Men's Fitness and get up to 80% OFF the newsstand price!
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And the workout routines that got her there.
KO in 48 seconds.
Take a look at those bulletproof abs.
10 moves that helped the Giants WR recover.
The player values you need to know to win the playoffs.
The hidden winners you need to dominate the fantasy playoffs.
The players to help you win your fantasy championship.


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Minka Aire
Matthews Fan Co.
Savoy House | Vaxel Lighting | Modern Fan | Concord | Meyda Tiffany | Tommy Bahama
Each of the fan models below are sorted by the order in which they were added to our website from each brand. Some models have other finish options that are not shown. If no new models were added this year, the latest models that were added in the past will be shown.
Ceiling Fan Experts...Online since 1995!
Hansen Wholesale created the very first ceiling fan website back in 1995. So we are the oldest ceiling fan company on the Internet and have been helping people find ceiling fans online for over 11 years.
If you are just starting your research, we have lots of answers to questions about ceiling fans on our Ceiling Fan FAQs Page. However, you'll learn much more if you call and talk to one of our ceiling fan experts.
Our team of Ceiling Fan Experts is here to answer all of your questions, help you compare the various fan brands and models and let you know which ceiling fans are the best value. We believe in doing business on a personal level, so we quote all prices and take all orders over the phone. We will save you time and money by customizing our ceiling fans to fit your needs...at Guaranteed Lowest Discount Prices. So give us a call...we look forward to sharing our knowledge of ceiling fans with you and providing you with the most excellent service you've ever had with any ceiling fan dealer.
Our experts would love to answer your questions and help you find what you need!
QUESTION: Are the Tommy Bahama Fans availble for a voltage of 230V ? Do you deliver to Germany? Thank you!
QUESTION: are these blades adptable to any 52 inch fan? Ihave a fan and would like to change out the blades with yours.
QUESTION: What buying recommendation would you make on a covered porch outdoor ceiling that may be subjected to 60 mph winds. We are looking at a tropical look. thanks, Jason
QUESTION: Can you obtain the replacement glass globe for this fan, TB306MAB? If so, how much shipped to Palm Coast FL 32137?
QUESTION: Was wondering how bright the 50 watt halogen light is? Looking for a fan - light combo for the morning room. 50 watts is less than most ceiling fan lights but was wondering if the fact the light is halogen based makes it brighter? Thanks Brian
QUESTION: Are the up-lights and down lights controlled simultaneously by the same dimmer on the remote? Can the be adjusted individually? Can one be on and the other off? What is the smallest down rod this fan can use? Thanks again Brian
QUESTION: Is the airflow still a 5 with the narrow medium antique blades. How about with the tropical blades ? Or is the airflow best with the pineapple lane with standard looking wood blades? I prefer the lookd of the tropical blades or narrow antique blades, but need really high airflow.
QUESTION: Is the airflow rating really a 5 with the bamboo or rattan blades, or is there better airflow with the wood blades. I have a large hot room. Although I love the rattan blades, if the wood move more air, I will get the wood. THanks,
QUESTION: Are the lights (controlled via the remote) dimmable?
QUESTION: Is there any concern with cutting the down rod (and re-drilling the set-pin hole) of either the TB-TB344CC or TB-TB344CW? While I know that other flush mount fans exist I would like to use one of these fans. Obviously if a flush mount kit exists I would use that instead.
Consumer Sales
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Hansen Wholesale 11132 Winners Circle Suite 100, Los Alamitos, CA 90720
Thanks for choosing Hansen Wholesale
Copyright © 1994-2017 Hansen Wholesale
The End


text:
Sweet Sweet Snow
Written by Bwog Staff
January 25, 201110:50 am 2 Comments
Good morning! Bwog's pal at CUPS, Shamm Petros, shot this picture of your classmates hurrying to class through the thick flurries. Please please wear earmuffs today, and keep sending snowshots to [email protected].
Tags: Bwog got kissed by a snowflake, this week in alliteration, yay snow!


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4 Serums for Oily Skin
Best Skin Care Routine For Sensitive Skin
The #1 Ingredient You Probably Aren't Using for Your Dry Skin, But Should
Our Go-To Eye Creams For Dark Circles, Puffiness, and More!
4 Products People With Acne-Prone Skin Need...Now!
6 Things That Can Age Your Skin Prematurely
The Single Worst Place to Stash Your Skin Care
Inside Look: How Actress Greer Grammer Cares For Her Skin
A Makeup Artist's Secret to Getting Truly Flawless-Looking Foundation Coverage
What to Expect From Your First Massage
How to Bronze Your Legs in Winter
5 Moisturizing Shampoo & Conditioner Duos for Winter
The Ultimate Skincare Packing Guide For Dry, Desert Climates
Stressed Out Skin? 4 Tips & Tricks To Help Calm Things Down
The Coolest Beauty Ingredients Really Do Grow On Trees
Are Those Fancy Water Sprays Actually Worth It?
4 Products to Start Using This Winter
Editor's Pick: The Body Shop Tea Tree Oil Review
A semi-abrasive cosmetic product applied to the face or body to cleanse or exfoliate the skin.


text:
- Gentle, pH-balanced formula that keeps hair clean and manageable. Use every day, even on permed or color-treated hair. (from Head & Shoulders)
Head & Shoulders Classic Clean 2in1 Shampoo Plus Conditioner
14.2fl oz
Like That? You'll Love This.
- $6.59/ea($0.46/oz)
- Irish SpringOriginal Bar Soap3ct, 5oz ea$3.39/ea($0.23/oz)
- Bounty2-Ply Paper Towels, Select-a-Size8ct, 63 sheets ea$13.99/ea($1.75/ct)
- Clif KidOrganic ZBar, Chocolate Chip6ct, 1.27oz ea$4.99/eaAny 2 Clif Kid for $8.00($10.40/lb)
- $5.99/ea($0.75/oz)
- DoveBar Soap, White2ct, 4.5oz ea$4.99/ea($0.55/oz)
- $4.99/ea($0.33/oz)
- Clif KidOrganic ZBar, Chocolate Brownie6ct, 1.27oz ea$4.99/eaAny 2 Clif Kid for $8.00($10.40/lb)
- $7.99/eaAny 2 select Aveeno products for $14.00($0.76/oz)
- $3.99/ea($9.07/lb)
- PanteneClassic Care Conditioner12.6fl oz$5.99/ea($0.48/oz)
- QuestBarProtein Bar, Chocolate Chip Cookie Dough12ct, 2.12oz ea$27.99/ea


text:
Chateau 30 Rooms • 1300 m² Amiens
1,350,000 €
12 bedrooms Land 25000 m²
In the Picardy countryside, a few kilometers from Amiens, in absolute calm, this 18th century chateau with architectural features Louis XIII, comprises a mezzanine, a ground floor and a floor, attic space and attic to be converted. The total habitable surface is 1300 m² with possibility of extension. This castle has been divided into 9 apartments of 2, 4 or 5 rooms. These apartments, which are habitable in the state, deserve a refreshing taste of the current rental market. The apartments were released for sale. In 2016, land income was e 76,800. The amount of the property tax is: e 2,800. The property benefits from an orangery of 280 m² The castle was raised in the middle of the park of 25 000 m² This property would be suitable for a single owner or as a building of report or as owner's house on the ground floor and floors for rent or such as a reception room, a restaurant, a training center, a head office, etc... This is a great opportunity to acquire a sumptuous heritage.


text:
Rising junior attacker Connor Turnbow-Lindenstadt of Corona del Mar has transferred to Newport Harbor, his father, Glen, confirmed.
Turnbow-Lindenstadt emerged as a player to watch over the summer in helping San Diego-based Del Mar finish second to Northwood in the 16-and-under Junior Olympics.
Please send water polo news to Dan Albano at firstname.lastname@example.com


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Jordan Hill Results
Jordan Hill
American basketball player
Jordan Craig Hill is an American professional basketball player who has most recently played for the Los Angeles Lakers of the National Basketball Association. He was drafted 8th overall in the 2009 NBA Draft by the New York Knicks. He played college basketball for the University of Arizona Wildcats. His cousin Trevor Booker plays for the Washington Wizards.
Jordan Hill's personal information overview.
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April 05, 2013
NBA star Jordan Hill leaves Mastro's Steakhouse in Beverly Hills
View family, career and love interests for Jordan Hill
News abour Jordan Hill from around the web
Four charged in Chicago over beating broadcast on Facebook
Yahoo News - about 2 months
The victim, who was not identified, was picked up on Saturday by one of his abductors in a northwestern suburb of Chicago where his parents had dropped him off at a McDonald's restaurant, police told a news conference. Jordan Hill, Tesfaye Cooper and Brittany Covington, all 18, were each charged with aggravated kidnapping, hate crime, aggravated unlawful restraint, aggravated battery with a deadly weapon and residential burglary, prosecutors said. Tanishia Covington, 24, faces the same charges, except for residential burglary.
Article Link:
Yahoo News article
Hill Scores 20 Points to Lead Pacers Over Raptors 106-90
NYTimes - about 1 year
Jordan Hill had 20 points and 13 rebounds, Monta Ellis had 18 points and the Indiana Pacers beat the Raptors 106-90 on Monday night to end Toronto's four-game winning streak.
Article Link:
NYTimes article
George powers Pacers to win over Clippers
Yahoo News - about 1 year
(The Sports Xchange) - Forward Paul George scored 31 points and grabbed 10 rebounds, and the Indiana Pacers won their sixth in a row with a 103-91 victory over the short-handed Los Angeles Clippers on Wednesday at Staples Center. Reserve guard Rodney Stuckey added 18 points, center Ian Mahinmi chipped in 14 points and seven rebounds and forward Jordan Hill contributed 13 points and eight rebounds for the Pacers (12-5), who have captured 12 of 14 after an 0-3 start. Forward Blake Griffin and reserve guard Lance Stephenson, the former Pacer, scored 19 points apiece for the Clippers (10-9), who had a three-game winning streak snapped.
Article Link:
Yahoo News article
NBA-Highlights of Wednesday's NBA games
Yahoo News - over 1 year
Nov 4 (The Sports Xchange) - Highlights of Wednesday's National Basketball Association games. - - - - Pacers 100, Celtics 98 Guard Monta Ellis made two free throws with 13.7 seconds remaining as the Indiana Pacers rallied for a 100-98 victory against the Boston Celtics. Boston had an opportunity to win on its final possession, but guard Avery Bradley missed a three-pointer. Paul George scored 26 points and grabbed 10 rebounds, while Jordan Hill added 16 points for Indiana. - - Wizards 102, Spurs 99 Bradley Beal scored 25 points, including the winning three-pointer with 0. ...
Article Link:
Yahoo News article
Jordan Hill: Lakers Coach Byron Scott 'disappointed' with his season
LATimes - almost 2 years
Jordan Hill spoke to the media on Thursday after his exit interview with Coach Byron Scott and General Manager Mitch Kupchak.
Article Link:
LATimes article
Jordan Hill to play a big part in Lakers' free agency plans
LATimes - almost 2 years
Jordan Hill hadn't appeared in many games lately, exiled to the end of the bench as the Lakers went with younger, less experienced players.
Article Link:
LATimes article
Why the Los Angeles Lakers hit the 50 loss mark
isports web - almost 2 years
Nick Young For only the fifth time in franchise history, the Los Angeles Lakers hit the half-century mark, in losses. With a loss to the Utah Jazz, the Lakers lost for the 50th time this season. This is the second consecutive year that the Lakers have hit this dismal mark in a stretch that has seen the franchise fall apart. The blame for this season could easily be placed on the injuries suffered throughout the year, most notably to Kobe Bryant and Julius Randle, but the real reason the Lakers have been so bad is that their roster is entirely comprised of role players. The Lakers would actually be a decent team if they had a pair of go-to players. Everyone on their roster has a unique skill set that would compliment a star player on a complete team. The Lakers simply just do not have one of these players this year. Nick Young is probably the closest thing the Lakers have to a go-to guy, but he is too consistent and constantly in the doghouse with his coach. "Swaggy P" is a fun
Article Link:
isports web article
Lakers' Jordan Hill to show support at Komen Race for the Cure event
LATimes - almost 2 years
Jordan Hill will be busy Saturday, and it has little to do with the Lakers' practicing at their facility.
Article Link:
LATimes article
Boozer leads week's top fantasy waiver pickups
USA Today - about 2 years
Lakers forward should see more minutes with Jordan Hill out. He leads this week's pickups.
Article Link:
USA Today article
Lakers Beat Cavs 119-108 Despite Running Out Of Eligible Players (VIDEO)
Huffington Post - about 3 years
CLEVELAND (AP) — The Los Angeles Lakers left Robert Sacre on the court after he fouled out in the fourth quarter. Coach Mike D'Antoni felt it was the best move for his depleted team. It's been that kind of year for the short-handed Lakers. Los Angeles lost two more players to injuries on Wednesday night and had to go to a little-known NBA rule to hold on for a 119-108 victory against the Cleveland Cavaliers on Wednesday night. "That was, by far, one of the strangest games I've ever seen," D'Antoni said. Rookie Ryan Kelly scored a career-high 26 points and Steve Blake had his first career triple-double for Los Angeles, which snapped a seven-game losing streak. The Lakers set a franchise record for 3-pointers, going 18 for 37 from long range. But Los Angeles' first win in two weeks was overshadowed by a bizarre ending. The Lakers had eight available players coming into the game. Then Nick Young twisted his left knee in the first half and Chris Kaman fouled out early in the fourt
Article Link:
Huffington Post article
Related Articles:
National Basketball Association Game Capsules
Up next for the Lakers: Friday at Detroit
LATimes - about 3 years
The Pistons, a bizarre mix of players, lost to the Lakers almost two weeks ago at Staples Center, 114-99. Jordan Hill had a career-high 24 points and 17 rebounds for the Lakers in that game. When: 4:30 PST.
Article Link:
LATimes article
Pau Gasol's Philippines Pledge Raises $1,000 For Every Point He Scores
Huffington Post - over 3 years
LOS ANGELES (AP) — Pau Gasol and Nick Young did a remarkable job keeping the Los Angeles Lakers together without their two injured stars. The Golden State Warriors had better take notes, because their injury problems just got worse. Gasol had 24 points and 10 rebounds, Young scored 14 of his 21 points in the second half, and the Lakers took advantage of Stephen Curry's absence for a 102-95 victory over Golden State on Friday night. Jordan Farmar and Steve Blake scored 14 points apiece as Los Angeles returned from four days off to win consecutive games for the first time all season. Jordan Hill added 10 points and nine rebounds as the Lakers clicked even without Kobe Bryant and Steve Nash, hitting 11 3-pointers and outworking the prolific Warriors down the stretch. Los Angeles calmly maintained a big lead throughout the fourth quarter of its 11th straight home win over its upstate rival since March 2008. "We're finally finding some consistency," Gasol said. "We're finally putting
Article Link:
Huffington Post article
Jordan Hill Leads Lakers Past Pistons 114-99
NYTimes - over 3 years
Jordan Hill barely played for coach Mike D'Antoni when they were together with the New York Knicks four years ago, and he started this season on D'Antoni's bench again with the Los Angeles Lakers.
Article Link:
NYTimes article
Related Articles:
Hill, Lakers down Pistons
NBA-Highlights of Sunday's NBA games
Jordan Hill's career-high 24 points, 17 rebounds push Los Angeles Lakers past Pistons 114-99
Jordan Hill leads Lakers past New Orleans Pelicans, 116-95
LATimes - over 3 years
Hill scores career-high 21 points after being inserted into the starting lineup. Coach Mike D'Antoni collects win exactly one year after being hired.
Article Link:
LATimes article
Related Articles:
Jordan Hill Leads Lakers' 116-95 Rout of Pelicans
Jordan Hill scores career-best 21 points, leads Lakers' 116-95 rout of Pelicans
Learn about memorable moments in the evolution of Jordan Hill
Age 24
On July 25, 2012, Hill re-signed with the Lakers on a two-year $8 million contract.
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Again on the trade deadline, on March 15, 2012, Hill was traded to the Los Angeles Lakers for point guard Derek Fisher and a 2012 first-round draft pick.
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Age 22
On the trading deadline on February 18, 2010, Hill was traded along with Jared Jeffries to the Houston Rockets as part of a three-team deal that included Sacramento that saw the Rockets' Tracy McGrady go to the New York Knicks.
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Age 21
Hill scored his first regular season points for the Knicks against the Cleveland Cavaliers on November 6, 2009.
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Hill played five games in the 2009 NBA Summer League, where averaged 14.4 ppg, 8.2 rebounds, .6 assists, .8 steals and 1. block.
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His highest score was 21 points against the Washington Wizards.
Hill was drafted as the 8th overall pick in the 2009 NBA Draft by the New York Knicks.
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Hill earned about $4.3 million over the next two seasons.
When Hill entered the 2009 NBA Draft, many had him high up on the draft board, possibly a top 5 pick in the draft.
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As draft night went on and Stephen Curry was taken by Golden State, it left New York to pick Jordan Hill.
He was drafted 8th overall in the 2009 NBA Draft by the New York Knicks.
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He played college basketball for the University of Arizona Wildcats. His cousin Trevor Booker plays for the Washington Wizards.
Born on July 27, 1987.
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Is this restaurant good for large groups?
Does this restaurant have waiters and waitresses?
Is this restaurant family-friendly?
Does this restaurant specialize in Southwestern style food?
Is this restaurant wheelchair accessible?
Is this restaurant appropriate for Kids?
Are the prices at this restaurant low or inexpensive?
Is this restaurant good for dining on a budget?
Is this restaurant good for lunch?
Is this restaurant good for dinner?
Thanks for helping!
Good, basic Mexican dishes. Not fancy, but comfortable with good, friendly service. Their chili verde is excellent. Located directly across the road from Lake Isabella in Mountain Mesa.
Not a gourmet Mexican restaurant, but they serve great tasting food in abundant quantities. I personally dare you to try to finish a whole burrito grande! Full menu includes everything that most people would expect on a Mexican menu. We eat there frequently, if the tells you anythinh.
friendly, casual place where locals gather. food is freshly made and served hot. This is a regular stop for us when eating out.
I love this place!! always busy . . but always get a table, I live in Orange Co and come up here every other month and always make a trip for dinner or lunch here... the owner is bomb, always on top of everything... the Chili Rellano is what I always get... these are awesome!! Great cook and service, NEVER...
This is not a fancy place and is simply decorated, but the food is good. I had the vegetarian quesadilla and it came with a large dollop of sour cream. It was very good and filled me up. The complementary chips were excellent. The salsa was very watery, but it had good flavor and wasn't too spicy. Service was very...
There is nothing we have had that we wouldn't have again. The staff is friendly and accomodating. We have had take-out and eaten in as well. We always make it a point to stop here when we are in the area for lunch or dinner.
The El Portal Mexican Grill in Lake Isabella IS CLOSED PERMANENTLY. If you want to go to an El Portal, you'll have to get back on Hwy 178 and take it East for about 7 - 8 miles to Mountain Mesa --- You'll see it on the right just as you get into town.
We love this restaurant for a number of reasons. In the summer, nice and cool. Comfy booths. Winter? It can be windy out, but not in here! Only the smell of good food blows around inside, and lots of stories. The decoration or design is really cool too. Lots of seating, and room for big groups by combining tables. Prices...
We are locals and eat at El Portal regularly. Our daughter loves the chicken quesadilla, our son loves the shredded beef burrito (wet), my husband loves the chile verde pork burrito (it is pretty spicy all on its own), and I think their chile rellenos are some of the best I've ever had. The rellenos are small, so order more...
We work near this restaurant and it has great Mexican American food for reasonable prices. I would recommend this restaurant to everyone. Enjoy!!
Own or manage this property? Claim your listing for free to respond to reviews, update your profile and much more.


text: Jorge Heredia, former MundoFox TV personality Your Next Big Opportunity: The Growing U.S. Hispanic Market Today 10% of the Texas population is Hispanic. In less than 5 years it's estimated to double. "You don't have to be a fortune 500 company to go international" Jorge Heredia, who explains case studies of several companies that exploded after offering their services to the latin culture. Takeaways include: -How to more effectively interact with the Hispanic culture in everyday life -Communicating effectively with Latinos in the United States -Common mistakes companies make every day when trying to reach the Hispanic market -Cultural Do's and Don'ts About Jorge Jorge spent 17 years in TV broadcasting. He's worked with networks including Univision, CBS, SyFy Channel, GEMS Television and Mundo FOX. His awards include: two Emmy Awards and two PAOLI Award. He heads up the Hispanic Division for Real News PR, the first journalist-run Spanish language PR division in the country.


text:
Cal Med 421 - Chula Vista
Alternative Medicine, Natural Healing, Holistic Medicine
There is a synthetic version of marijuana, and it is called Marinol. It is the drug companies' answer to their desire, but inability, to sell marijuana. But Spice has absolutely no connection to the cannabis plant or Marinol. So why do reporters and others continue to make the correlation between the highly processed, chemical mashup that is Spice, and what we all know as the natural substance, marijuana? Your guess is as good as mine. But maybe my guess may be better.
Medical Marijuana#1. Marijuana sells.
More and more people are learning of its healing and therapeutic properties. Many states have medical laws in place allowing patients to use cannabis for medical conditions and the symptoms associated with many disease. And a couple of states have passed recreational laws.
#2. Marijuana has a reputation for being safe.
This correlation is dangerous because it sends the public, including children and teens, mixed and blatantly wrong messages about the 2 substances. Spice is highly dangerous and unpredictable. Because manufacturers are constantly changing the make-up of what is in Spice in order to avoid prosecution and continuing manufacturing it, there is no telling what is in one batch or the next. News stories highlight multiple overdoses in any given area based on a "bad batch." And because the truly non-toxic, non-addictive qualities of cannabis are known to many adolescents and adults, labeling something as "synthetic marijuana" has implied amounts of safety that simply aren't present in the unregulated product known as Spice.
#3. There is a public push to keep marijuana "off the streets" and out of the hands of minors.
All the while, the dangers of other substances are glossed over or ignored. The leftover reefer madness mentality does much more harm than good. While we, as a society, should be educating the youth about the truths of various drugs, we are failing then by perpetuating untrue myths and fabrications about the cannabis plant and not focusing enough on alcohol, prescription pain killers, and other harder drugs that can actually be lethal, and are highly addictive. Recently, I was on my daughter's high school campus and the only sign on a billboard was warning about the "detrimental" effects of smoking marijuana and no mention of help or education regarding any other drug.
Spice is in no way a form of marijuana. It is a dangerous mix of chemicals that bring on a range of dangerous and unpredictable symptoms in those who use it. Media and other outlets need to be more clear and honest, and perform their due diligence in efforts to disseminate correct, and not misleading, information.
Print this page
You hear about people getting cancer every day. Sometimes it's a co-worker, sometimes it's the parent of a friend, and in really heart wrenching circumstances, it might be a child.
Our mission at CAL MED 421 is to provide our current and future patient base with up to date information and education. Medical cannabis is at the forefront of changing healthcare and both federal and state regulations are constantly being debated and evolved.
While medical marijuana was once a taboo, highly misunderstood topic, one can see that the general consensus on the subject has slowly begun to change.
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English Historical Records
By (author) Alan MacFarlane
Format: Paperback
Normal Price: $56.95
Your Price: $51.26 AUD, inc. GST
Shipping: $7.95 per order
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English Historical Records by Alan MacFarlane
Book DescriptionThis book describes the nature of English historical records over the period 1200-1800. It surveys the records created by the state, the estates of landlords, and the Church. The work arises from an intensive research project (1973-81), which involved the manual and computerised analysis of all the surviving records for two parishes, in Westmorland and Essex, up to 1800. The book considers the administrative and judicial process, which led to the compilation of the documents, the survival and quantity of each class, the location and form of the material, and the hidden omissions, inaccuracies and deceptions.
Buy English Historical Records book by Alan MacFarlane from Australia's Online Bookstore, Boomerang Books.
Book DetailsISBN: 9780521079808
(228mm x 152mm x 9mm)
Pages: 152
Imprint: Cambridge University Press
Publisher: Cambridge University Press
Publish Date: 25-Aug-2008
Country of Publication: United Kingdom
Other Editions...
Books By Author Alan MacFarlane
Resources and Population, Paperback (August 2012)
This book, first published in 1976, utilises the tools of social anthropology and population studies to examine the causes and consequences of populations growth.
Nagas, Paperback (April 2012)
In the years before Indian Independence in 1947, the Nagas of Northeast India came to exemplify an exotic society. This title offers an examination of how the notion of tribes came to be applied to the Nagas"is linked to its subsequent importance in the development of contemporary Naga nationalism.
Reconstructing Historical Communities, Paperback (October 2008)
Alan MacFarlane has studied the parishes of Earls Colne in Essex and Kirkby Lonsdale in Cumbria.
Japan Through the Looking Glass, Paperback (July 2008)» View all books by Alan MacFarlane
Takes us on an exploration into the different aspects of Japanese society: from public to intimate. This title uncovers the multi-faceted nature of the country and people who are even more extraordinary than they seem. It includes religion, ritual, martial arts, manners, eating, drinking, hot baths, geishas, family, home, and singing.
» Have you read this book? We'd like to know what you think about it - write a review about English Historical Records book by Alan MacFarlane and you'll earn 50c in Boomerang Bucks loyalty dollars (you must be a member - it's free to sign up!)
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Holidays 2016 1080p WEB-DL DD5 1 H264 FGT
MovieFirstLetter: H
MovieGenre: Comedy, Horror |
ReleasedIn: 2016
MovieIMDB: 6+
Stars: Lorenza Izzo, Seth Green
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Question about Microsoft Windows XP Professional With Servise Pack 2 (e8503040) for PC
Posted by OLIVIACHERRY on
Generally this should'nt happen. You must be sure of password you would have assigned and perhaps fail to remember it now. If the system is shared then chances are there that it would be tampered. well try this:
1: go to bios and find it from there.
2: ultimately if nothing can be done than format it
Posted on Sep 03, 2008
SOURCE: I have freestanding Series 8 dishwasher. Lately during the filling cycle water hammer is occurring. How can this be resolved
a 6ya expert can help you resolve that issue over the phone in a minute or two.
best thing about this new service is that you are never placed on hold and get to talk to real repairmen in the US.
the service is completely free and covers almost anything you can think of (from cars to computers, handyman, and even drones).
click here to download the app (for users in the US for now) and get all the help you need.
Posted on Jan 02, 2017
Tips for a great answer:
Feb 09, 2011 | Computers & Internet
on Nov 22, 2010 | Computers & Internet
Dec 06, 2010 | Computers & Internet
There are three way for you.
Usually, we can recover Windows admin password in two traditional ways. The first is to change Windows password with another admin account; the second is to recover the previous password with the windows password reset disk that had been created before you forgot the password. Take Windows XP for example,
1 At the Windows XP login prompt when the password is entered incorrectly click the reset button in the login failed window.
2 Insert the password reset diskette into the computer and click Next.
3 If the correct diskette Windows XP will open a window prompting for the new password you wish to use.
However, we offen ignore the important of security until we have been locked out of computer. Fortunately, there is still the last way that can unlock your computer without reinstalling - erase Windows password with Windows password recovery CD, which can recover admin password for Windows 7/XP/Vista/NT/2000/2003.... Take Windows Password Recovery Tool 3.0 for example, followings are the steps to create the reset CD
1.Download Windows Password Recovery Tool 3.0 from Official site http://www.windowspasswordsrecovery.com
2.Decompress the Windows password Recovery Tool and note that there is an .ISO image file. Burn the image file onto an blank CD with the burner freely supported by PasswordSeeker
3.Insert the newly created CD into the locked computer and re-boot it from the CD drive.
4.After launched the CD, a window pop up with all your account names(if you have several accounts) select one of the accounts that you have forgotten windows password to reset it. Just one press, this software can remove screen password instantly.
Personally, I prefer to use the third way. It is fast and safe.
Oct 20, 2010 | Computers & Internet
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Official 'The Best Of BTS' Album CD (Japanese Ver.)
Warning: Last items in stock!
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Product Description
Official 'The Best Of BTS' Repackage Album CD – Japanese Version.
After just two and a half years since their debut in Japan (June 2014), the Bangtail Boys bring you their next album "THE BEST OF Bangtan Boys". The new BTS album is scheduled to be released on January 6, 2017, in both Japanese and Korean with 14 tracks and an optional DVD.
Album Specifications
Product Title: The Best Of BTS
Artist Name(s): BTS
Release Date: 2016-01-06
Language: Japanese
Disc Format(s): CD
Publisher: BigHit Entertainment
Official Album Information & Track List
1.NO MORE DREAM -Japanese Ver.-
2.BOY IN LUV -Japanese Ver.-
3.Danger -Japanese Ver.-
4.進撃の防弾 -Japanese Ver.-
5.MISS RIGHT -Japanese Ver.-
8.ホルモン戦争 -Japanese Ver.-
9.I NEED U (Japanese Ver.)
10.DOPE -超ヤベー!- (Japanese Ver.)
11.RUN -Japanese Ver.-
12.FIRE -Japanese Ver.-
13.Save ME -Japanese Ver.-
14.EPILOGUE : Young Forever -Japanese Ver.-
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Chris Webber in Golden State – Swan Song Sounds More like a Choking Crow
Posted by admin on January 30, 2008
It's true. The Warriors do not have the strongest frontcourt. In almost every game they play, the Warriors find themselves being outrebounded by their bigger, stronger opponents.
It's true. The Warriors need another big man to play alongside Andris Biedrins. And until Brandon Wright starts playing to his potential, there is going to be a gaping hole in the Warriors' lineup. A hole that frontcourt-dominated Western Conference teams will exploit night in and night out.
But what's not true is the notion that the recent signing of Chris Webber is going to resolve the rebounding situation. The Warriors are a quick, young, fiery team that like to run and gun, eventually tiring and outscoring their opponents. Chris Webber is literally the antithesis of the Warriors. He is old. He is slow. He is lackluster. Yes, Chris Webber is a big guy who can get a rebound every now and then. But, if you have watched him play over the last few seasons, he has become a perimeter player. Whereas with youth come speedy, explosive moves to the basket, with old age come lethargic, telegraphed ones. So, now Webber incresingly settles for the outside shot rather than banging in the paint. If you tell me that is what the Warriors need right now, you are out of your mind. Now, if the Warriors were able to pick up a quick, Shawn Marion type, that would be one thing. But I think we can all say with quite a lot of confidence that Chris Webber isn't that type of player.
Another reason why Webber is not and cannot be the solution to the problem is that he and Nellie don't exactly see eye to eye. I know, I know. Everybody is getting caught up in the nostalgia of it all, falling for the "I am glad I'm coming home" and "I started here, now I want to end here" lines. But the fact of the matter is that the Warriors are a team that is driven by comraderie and synergy. If Webber does anything to mess that up (history tells us that he might do just that), the Warriors may revert back to their old, losing ways. I do not want to see that happen. So singning Webber may not have been the brightest of ideas.
However, what I have written so far is a moot point seeing as how the Warriors have already signed Webber. The $1.2 million is already down the drain and it's now a thing of the past. As for the future though, Nellie needs to keep an eye on Webber. As a die-hard Warriors fan, I would rather waste $1.2 million and not play him than waste $1.2 million and have him bring the team down. Having a losing season again is just not an option. Like it or not, Webber is going to be a Warrior this season. But something tells me that Webber's swan song isn't going to pan out like he hopes.
Nishan Wilde is VP of Sales for Robbins Sports, an online resource for Baseball Uniforms, Track Uniforms and Punching Bags.


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We recently went on a trip to McLeod Ganj. The farmers' breakfast, the trek to Triund, and the coffee is what you must not miss out if you're there.
It's about 500km from New Delhi, so the best way to get there is a semi-sleeper bus, which has ample overnight services throughout the week. Those who love long drives could hit their gas pedals as well, since the highway is quite nice.
The place offers the perfect mix of hospitality and friendliness, and you'll find that the people there often let you have your 'me time'.
Nature-lovers are going to love the fresh air, and if one loves a bike ride, Dharamshala-Naddi-Dharamkot-McLeod Ganj is the perfect route.
The Triund trek. You can see the different shapes of the mountains and the changing views of the city as you climb {you move from 1,500m to 2,875m above the sea level}. The whole energy keeps you positive throughout the trek.
A waterproof jacket or windcheater if you're going around the monsoons. Sports shoes are a must, too. Other than that, carry casual, comfortable clothing.
The weather is amazing in the monsoon, if you don't mind the showers, of course. The summers are always a good time to visit, though.
Where: McLeod Ganj, Kangra district, Himachal Pradesh
Best Time To Visit: Jun – Sep
Featured Photo source: Ashish Gupta via Flickr [CC BY 2.0]


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The EU Energy Focus service is a free UK Government-funded service, that aims to ensure that UK organisations are well informed and have every chance of success in applying for and securing European funding for energy-related projects. It provides support for a range of European funding opportunities with a focus on Horizon 2020, but also covering opportunities such as the Fuel Cell and Hydrogen Joint Undertaking. The service includes confidential, one-to-one discussion of proposal ideas, webinars on upcoming and current Calls for Proposals, consortium building support and review of draft proposals.
A flow chart showing the Horizon 2020 application process can be downloaded from here.
The EU Energy Focus team in conjunction with the Enterprise Europe Network and Knowledge Transfer Network are delivering a proposal development workshop on the Energy Efficiency Call topics. The event will be held in London on Thursday 9th March 2017 at Digital Greenwich in east London. The event is being held near to the Ecobuild venue of the Excel Convention Centre to facilitate the participation of those visiting London to attend the matchmaking event at the Ecobuild conference and exhibition. The workshop will bring together organisations from around Europe to share proposal ideas and information on their capabilities to build consortia and commence proposal development. Details of the event and how to register can be found at here.
Recognising the importance of science and innovation to society, productivity and economic competitiveness, the government has now provided reassurance to UK participants of the European Union's Horizon 2020 Programme with a commitment to safeguard funding for research and innovation projects.
The Treasury has confirmed that it will underwrite funding for approved Horizon 2020 projects applied for before the UK leaves the European Union. As a result, British organisations have certainty over future funding and should continue to bid for Horizon 2020 calls while the UK remains a member of the EU. The Treasury will underwrite the payment of such awards, even when specific projects continue beyond the UK's departure from the EU.
The EU Energy Focus team coordinates stakeholder groups for bioenergy, solar, wind, CCS, smart cities, smart grids, ocean and a group on energy efficiency is in the process of being set-up. Stakeholder group membership is an opportunity to help influence future Work Programme content; receive the latest news on Work Programme development; and build your networks and knowledge to take advantage of these funding opportunities. Please contact the EU Energy Focus team if you would like more information or would like to join any of these groups.


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Centrally located hotel,very helpful staff
by drhelenperes on February 15, 2017
I stayed at this hotel from Jan 15 to Jan 30, 2017.The room was very comfortable with reliable air conditioning during a heat wave at the time.The shower was great,with a rainwater head and good water pressure.Toiletries were provided.Breakfast was included with a choice of Indian or continental options. What was truly exceptional was the service, from the gents at the front desk,to the bearers,Tapan and Mithun,who served breakfast each morning and Manoj the cook who provided toast , tea, and the most delicious plain omelette for my husband who went down with gastroenteritis .The staff went to the local market to buy fresh fruit for me,gave us advice on local sights,most of which were within walking distance or a short auto rickshaw ride away. The price was great considering hotels on the same street were twice the price. I was sincerely moved by how caring the staff were. I would return to this hotel on my next trip to Panjim.


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text: When you need to shop for Remington cleaning supplies, you won't find a better place to get things done than right here at Omaha Outdoors. Considering how long Remington has been working in the industry, it only makes sense that they would be producing some of the most reliable options on the market today. Their guns are made with great attention to detail and provide for some of the most accurate shooters out there. With both premium and budget options available, few who try a Remington ever regret the purchase. Of course, even the best firearm needs to be maintained if you want to ensure it continues to perform at its best. For some shooters, this just means cleaning after every time you use the weapon, but for those who don't use their weapons regularly it is important that they get attention as well. Regardless of how often you clean your guns, you will need to start by stocking up on all of the best cleaning supplies. This is why Omaha Outdoors offers a full selection of Remington cleaning equipment for your convenience online.


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Journal of Korean Dental Science
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Korean Academy of Dental Sciences
Editor in Chief :
Sung-Woon Pyo
Volume & Issues
Volume 5, Issue 2 - Dec 2012
Volume 5, Issue 1 - Jun 2012
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Overview of Gingival Overgrowth in Transplant Patients
Park, Seo-Jin ; Park, Jun-Beom ; Ko, Young-Kyung ;
Journal of Korean Dental Science, volume 5, issue 1, 2012, Pages 1~6
Patients with gingival overgrowth are easily seen in dental clinics. Cyclosporin-A (CsA), a widely prescribed immunosuppressant induces gingival overgrowth in up to 35% of patients with medical history of organ transplantation. The immunosuppressant CsA can transform genetic expression of gingival fibroblasts, resulting in gingival overgrowth. Meticulous plaque control is recommended for treatment of gingival overgrowth. Substitution of the drug or surgical procedures such as gingivectomy and periodontal flaps should be considered after re-evaluation. Azithromycin is often recommended as a supplementary drug to reduce this side effect. Recent studies show that tacrolimus can be a more economic, efficient and safe substitute for CsA.
In vitro Antibacterial Effect of Orthodontic Adhesives Mixed with Silver Nanoparticles
Choi, Kwon-Yong ; Lee, Jong-Chan ; Hwang, Yun-Chan ; Chang, Seok-Woo ; Kum, Kee-Yeon ; Bae, Kwang-Shik ; Lim, Bum-Soon ; Paeng, Jun-Young ; Kim, Eun-Cheol ; Kwon, Ho-Beom ; Kim, Young-Ho ;
Journal of Korean Dental Science, volume 5, issue 1, 2012, Pages 7~12
Purpose: To examine the antibacterial effectiveness of silver nanoparticles (SNP) mixed with commercial orthodontic adhesives. Materials and Methods: SNP was prepared by dissolving silver perchlorate in an organic solvent and reducing it with ultraviolet radiation. SNP was then mixed with four commercial orthodontic adhesives (Light Bond, Blugloo, Transbond XT, and Fuji Ortho LC) (0.05 wt %), which were then formed into disc-shape specimens (
). Commercial orthodontic adhesives containing no SNP were used as the control groups. Specimens of the four experimental and four control groups were incubated with streptococcus mutans and the medium turbidity was assessed at 3, 6, 9, 12, and 24 hours after incubation. The agar diffusion test was also performed to examine the growth inhibition zone of these groups. The data were statistically analyzed using a Wilcoxon rank sum test and t-test with a Bonferroni's correction (P<0.05). Result: The SNP containing groups had a superior antibacterial effect compared to the control groups. In the agar diffusion test, the control groups without SNP did not produce an inhibition zone, whereas the SNP containing groups showed inhibition zone of 10~13 mm. Conclusion: The incorporation of SNP into orthodontic adhesives can inhibit cariogenic bacterial growth.
Finite Element Analysis of Stress Distribution around Patterned Implants
Cho, Lee-Ra ; Huh, Yoon-Hyuk ; Kim, Dae-Gon ; Park, Chan-Jin ;
Journal of Korean Dental Science, volume 5, issue 1, 2012, Pages 13~20
Purpose: The purpose of this study was to investigate the effect of patterning on the stress distribution in the bone tissue using the finite element analysis (FEA) model. Materials and Methods: For optimal comparison, it was assumed that the implant was axisymmetric and infinitely long. The implant was assumed to be completely embedded in the infinitely long cortical bone and to have 100% bone apposition. The implant-bone interface had completely fixed boundary conditions and received an infinitely big axial load. von Mises stress and maximal principal stress were analyzed. Conventional thread and 2 or 3 patterns on the upper and lower flank of the thread were compared. Result: The surface areas of patterned implants were increased up to 106~115%. The thread with patterns distributed stress better than conventional thread. Patterning in threads may produce more stress in the implant itself, but reduce stress in the surrounding bone. Stress patterns of von Mises stress were favorable with patterns, while the maximal principal stress was increased with patterns. Patterns in the lower flank showed favorable stress distribution. Conclusion: The patterns in implant thread reduce the stress generated in surrounding bone, but the number and position of patterns were crucial factors in stress distribution.
Bone Healing Capacity of Demineralized Dentin Matrix Materials in a Mini-pig Cranium Defect
Kim, Jong-Yub ; Kim, Kyung-Wook ; Um, In-Woong ; Kim, Young-Kyun ; Lee, Jeong-Keun ;
Journal of Korean Dental Science, volume 5, issue 1, 2012, Pages 21~28
Purpose: In this study the bone healing ability of autogenous tooth bone graft material as a substitute material was evaluated in a mini-pig cranial defect model through histologic examinations and osteonectin reverse transcription polymerase chain reaction (RT-PCR) quantitative analysis. Materials and Methods: A defect was generated in the cranium of mini-pigs and those without a defect were used as controls. In the experimental group, teeth extracted from the mini-pig were manufactured into autogenous tooth bone graft material and grafted to the defect. The mini-pigs were sacrificed at 4, 8, and 12 weeks to histologically evaluate bone healing ability and observe the osteonectin gene expression pattern with RT-PCR. Result: At 4 weeks, the inside of the bur hole showed fibrosis and there was no sign of bone formation in the control group. On the other hand, bone formation surrounding the tooth powder granule was observed at 4 weeks in the experimental group where the bur hole was filled with tooth powder. Osteonectin gene expression; there was nearly no osteonectin expression in the control group while active osteonectin expression was observed from 4 to 12 weeks in the experimental group. Conclusion: We believe this material will show better results when applied in a clinical setting.
Effect of Anterior Guidance Change on the Condylar Path in Skeletal Class I Young Adult Women Using a Splint with Flat or Steep Anterior Guidance
Choi, Byung-Taek ; Baek, Seung-Hak ;
Journal of Korean Dental Science, volume 5, issue 1, 2012, Pages 29~36
Purpose: To investigate the effects of anterior guidance (AG) change on the working (WCP) and non-working condylar paths (NWCP), and lower incisor path (LIP) using a splint with flat (FAG) or steep AG (SAG). Materials and Methods: The samples consisted of six young adult women (mean age=
years). Inclusion criteria were skeletal Class I and normodivergent pattern, normal overbite/overjet, minimal slide from retruded cuspal position to intercuspal position, no temporomandibular disorder signs and symptoms, mutually protected occlusion, and minimal tooth wear. After the values of natural AG (NAG) were obtained as a reference for each patient, two types of splints (
flatter and steeper than NAG) were made. After insertion of the splints with FAG or SAG, the WCP, NWCP, and LIP were recorded five times for each patient using an ultrasonic AQR (SAM, Munich, Germany) and statistical analysis was subsequently performed. Result: NAG exhibited postero-superior movement in the WCP and did not show a noticeable immediate side shift (ISS) or difference between the eccentric (EP) and returning paths (RP) in the NWCP. FAG was associated with an irregular and excessive WCP, an increase in ISS, and a difference between EP and RP in the NWCP. SAG showed minimal WCP movement and a decrease in the extent of difference between EP and RP in the NWCP. LIP showed significant differences in EP and in RP (P<0.001, all; FAG
Tooth Movement in Demineralized Area by Etchant in Rabbits
Choi, Bohm ; Kim, Tae-Gun ; Han, Seung-Hee ; Park, Yoon-Hee ; Lee, Won ;
Journal of Korean Dental Science, volume 5, issue 1, 2012, Pages 37~44
Purpose: Among the facilitation of tooth movement in adult orthodontic treatment methods, surgical approaches are gaining popularity but complications following mechanical bone reduction are a problem. In this study, tooth movement was observed after alveolar bone was chemically demineralized to verify whether tooth movement had been facilitated. Materials and Methods: Twelve rabbits were used. In the experimental group, the alveolar bone of the left first molar area was exposed and demineralized. Thirty seven percents phosphoric acid was applied for 5 minutes for demineralization. The opposite first molar area was used as control. Two teeth were pulled with 200 g force and 4 rabbits each were sacrificed at 3, 7, and 14 days after the force was applied. Histologic examination was done with hematoxylin and eosin and tartrate-resistant acid phosphatase staining. Result: The histologic examination results revealed more bone resorption in the demineralized area. As time passed, the number of osteoclasts increased in the compressed area. The amount of tooth movement was larger in the experimental group compared to the control group but the difference was not statistically significant. Conclusion: The demineralization with etchant resulted in limited bone resorption, more tooth movement and less damage of the cementum after applied orthodontic force.
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