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|Publication number
|Publication type
|Publication date
|Mar 11, 1969
|Filing date
|May 2, 1966
|Priority date
|May 6, 1965
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|Publication number
|Osgan Maseh, Silly Jean-Pierre, Teyssie Philippe
|Original Assignee
|Inst Francais Du Petrole
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|Non-Patent Citations (1), Referenced by (29), Classifications (59)
|External Links: USPTO, USPTO Assignment, Espacenet
Unite States Patent us. or. 260-2 Int. Cl. CllSg 23/06, 23/14 14 Claims ABSTRACT OF THE DISCLOSURE For the polymerization of cyclic ethers, there is empolyed at the catalyst a reaction product prepared by contacting:
(a) A trivalent metal compound having the formula (b) A bivalent metal compound having the formula YOMZ wherein M is a trivalent metal, M is a bivalent metal, Z is selected from the group consisting of CR and acyloXy groups; X and Y are different, one of which is R, and the other is an acyl group, said groups R R R and R being monovalent hydrocarbon groups, and separating at least 1% of the theoretical amount of the ester byproduct XOY of the reaction of (a) with (b).
The present invention relates to catalyst compositions based on bivalent metals and the methods of applying the catalyst compositions to polymerization processes, particularly the use of the catalyst compositions in the methods of polymerizing cyclic ethers.
The catalyst compositions of the present invention are particularly useful in the polymerization of the 12 and l-3 epoxides and the polymers obtained are useful in elastomers, films, plastics, fibers and surface coatings.
It is an object of the present invention to provide a catalyst composition based on bivalent metals.
It is another object of the invention to use the catalyst composition based on bivalent metals for the polymerization of cyclic ethers.
A particular object of the present invention is to obtain a new catalyst by reacting a trivalent metal compound with a bivalent metal compound.
Another particular object of the invention is the catalyst complex obtained by the reaction of a trivalent metal trialcoholate with a bivalent metal carboxylate.
Still another particular object of the invention is the catalyst complex obtained by the reaction of a carboxylic acid or anhydride with a trivalent metal trialcoholate or dialcoholate-carboxylate and a lbivalent metal alcoholate or phenolate.
Still a further particular object of the invention is the catalyst complex obtained by the reaction of a trivalent metal dialcoholate-carboxylate and a divalent metal dialcoholate.
Upon further study of the specification and claims other objects and advantages of the present invention will become apparent.
3,432,445 Patented Mar. 11, 1969 ice The catalysts of the present invention are obtained by the reaction of a trivalent metal compound of the formula MOX R20 with a bivalent metal compound of the formula:
(B) YOMZ where M' is a trivalent metal, M a bivalent metal and Z a radical OR or an acyloxy radical derived from a mono or polycarboxylic acid. One of the radicals X or Y is a radical R the other being an acyl radical derived from a monoor polycarboxylic acid.
The radicals R to R identical or different, are monovalent hydrocarbon radicals.
The radicals R to R and likewise the acyl and acyloxy radicals can contain from 1 to 20 carbon atoms, but preferably from 1 to 6 carbon atoms in order to facilitate the distillation of the XOY ester.
The temperature of reaction is usually between 50 and 300 0, preferably between 180 and 230 C., and the reaction time about 1 to 15 hours, but these limits are not imperative.
The reaction proceeds by the formation of an ester of the formula XOY in the amount of at least 1%, preferably at least 60% of the less abundant reagent (A) or (B).
The molar ratio A/B of the reagents is generally between 0.01 and 100, preferably between 0.1 and 10.
Preferred embodiments for practicing this invention are the following:
(1) The catalyst of the present invention is obtained by heating a carboxylate of a bivalent metal with a compound of the formula:
in which M is a trivalent metal. The radicals R, identical or different, represent monovalent alkyl, alkenyl, cycloalkyl, cycloalkenyl or aryl hydrocarbon groups, and especially those which contain 1 to 20 carbon atoms, preferably alkyl or alkenyl groups containing 1 to 4 carbon atoms. The metal M is preferably aluminum. Other trivalent metals which can be used are iron, molybdenum, chromium, vanadium, titanium, zirconium, boron, gallium, indium, thallium and bismuth. These metals are in groups III and VI and VII of the Periodic Table.
Examples of carboxylates of bivalent metals are especially those which correspond to one of the following formulas:
(II) (RCOO) M (III) R'-CO O-MOOCR" (IV) o o o in which R=hydrogen or a monovalent hydrocarbon radical of 1 to 20 or more carbon atoms, preferably 1 to 5.
R=monvalent hydrocarbon radical of 1 to 20 or more carbon atoms, perferably 1 to 5,
n=a positive whole number or zero, preferably 1 to 4.
The reaction produces an ester of the formula:
(V) R'COOR (VI) R"COOR and/or (VII) C O O R CnHZn C O O R To obtain the catalyst according to this invention, it is necessary to form at least 1% of the theoretical amount of ester, preferably at least 60%, based on the less abundant reagent. For example, if one mole of Compound I is used and moles of Compound II, the theoretical amount of ester RCOOR would be equal to 3 moles.
The work is preferably done in the absence of both humidity and oxygen.
The trivalent metal compound is preferably used in the amount of 1.8 to 2.2 moles per mole of the divalent metal carboxylate, but these proportions can vary widely, for example between 0.1 and 50, especially between 1.4 and 5, the catalyst obtained having an atomic ratio of trivalent to divalent metal preferably equal to or close to- 2. It is possible however to have active catalysts whose trivalent metal to bivalent metal ratio is as high as 50 or as low as 0.33.
The synthesis of these catalysts can be effected by heating an intimate mixture of a compound of Formula I with a metal carboxylate without adding any other substance. However, the work is preferably done in the presence of a liquid which permits better control of the temperature and which also facilitates the removal of the ester that has been formed. As a suitable liquid, use can be made of a diluent or a mixture of inert organic diluents, namely those which do not destroy the catalyst, selected especially from the paraffinic, alicyclic or aromatic hydrocarbons or their halogenated derivatives. As examples can be cited the aromatic and/ or aliphatic petroleum fractions preferably distilling between 190 and 250 C., octane, iso-octane, toluene, xylene, cumene, pseudocumene, tetrahydronapththaline, decahydronaphthalene, o-di-chlorobenzene, trichlorobenzenes, a-monochloronaphthalene, nand isoamyl benzenes, dipropyl benzenes, triethyl benzenes, ethyl naphthalenes, etc.
To obtain a very active catalyst, it is necessary during and/ or after the reaction to expel the ester that is formed. This is preferably done by distillation under atmospheric or reduced pressure. A preferred method consists of using a mixture of diluents, one of which will permit heating to the highest desired temperatures of the reaction, and another of which is added continually and in small amounts, especially toward the end of the condensation, and serves primarily as a vehicle for entraining the ester and secondarily to permit better control of the temperature of the reaction mixture.
Instead of using a low boiling solvent as the entraining agent, it is also possible to use a gas, e.g., nitrogen, argon, methane, etc. In certain cases it is preferably to add, either to the entraining solvent or to the entraining gas, various amounts of alcohol In such case it will be necessary to eliminate the excess of alcohol by distillation because any excess of free alcohol during the use of the condensation product as a catalyst reduces the molecular weight of the polymer, and also reduces to some extent the rate of polymerization.
At the end of the reaction it can be advantageous to drive off the last traces of the ester and of the solvent by heating under vacuum. Another method of separating the ester from the catalyst consists in rendering the latter insoluble in heptane or in another suitable diluent and to separate it from the liquid phase which contains the ester, such a separation being well known in the art. For example, by adding methanol it is possible to obtain a catalyst having methoxy radicals, insoluble in heptane, hexane, etc., and then to convert it into a soluble catalyst having, e.g., isopropoxy radicals by the method described hereinafter.
For synthesizing the catalyst an alcoholate of Formula I, e.g., an isopropylate can be used, and then to modify the nature of the radical R either partially or entirely by a simple exchange reaction to obtain the desired effect. For example, the catalyst can be treated by an alcohol or a phenol that is less volatile than ROH and the latter can then be eliminated by distillation, e.g., at 80 to 180 C. For example, use can be made of secondary octyl alcohol, allyl alcohol, methyl allyl carbinol, undecanol, undecenol, phenol, cresols, o-isopr-opyl phenol, o,o'-diisopropyl phenol, o-tert-butyl phenol, o,o'-di-tert-amyl phenol, o,o'-diisopropyl-pmethoxy phenol, o.o-di-tert-butyl-p-isopropoxy phenol, etc.
The preparation of the condensation product can be effected either in batch processes or continuously.
Generally at the beginning of the reaction the reaction mixture is not homogeneous, but tends to become homogenized during the course of the reaction so that there will be only one phase present at the end of the reaction.
The product obtained, which constitutes the desired catalyst, is generally in the form of a semisolid or solid mass or vitreous froth, depending partly on the nature of M and M and partly on the groups OR. The product is generally very soluble in heptane, usually in amounts of at least 1% and more often at least 50% by weight, and sometimes even in all proportions.
Under some conditions a small portion of the catalyst will be insoluble in heptane, but will likewise have certain catalytic properties.
Extraction of the main reaction product with heptane or other parafiinic hydrocarbons constitutes nevertheless a good method of isolation and characterization of the desired catalyst.
Of the carboxylates of the bivalent metals, preference is given to those which have the general formula:
where M is a bivalent metal and R a hydrogen atom or a monovalent hydrocarbon radical with l to 6 carbon atoms. Especially suitable are the formates, acetates, propionates, butyrates, isobutyrates, valerates, caproates and benzoates, and especially those of the following metals in their bivalent state, or complexes thereof: Be, Mg, Zn, Cd, Ca, Sr, Ba, Ti, TiO, Cp Ti (IV), V, VO, Cr, Mn, Fe, Co, Ni, Cu, ZrO, Mo, Pd, Sn, SnO, R Sn (IV), Pt, and U0 wherein Cp is a cyclopentadienyl radical and R is a monovalent hydrocarbon radical.
These metals are generally classified in Groups I, II, and IV to VIII of the Periodic Table.
As examples of compounds of Formula I are mentioned especially:
aluminum triethoxide aluminum monomethoxide-di-sec.-butoxide aluminum triisopropoxide aluminum tri-sec.-butoxide aluminum triisobutoxide aluminum di-sec.-butoxide mono-iso-proproxide aluminum di-sec.-octyloxide mono-iso-propoxide aluminum diphenoxide mono-isopropoxide aluminum di-(o,o-tert.-butyl-p-methyl-phenoxide) mono-isopropoxide gallium triethoxide gallium triisopropoxide gallium tri-sec.-butoxide gallium triisobutoxide gallium tri-n-butoxide gallium diphenoxide mono-isopropoxide boron triisopropoxide boron di(sec.-octyloxide) mono-methoxide boron di(sec.-octyloxide) mono-isopropoxide boron diphenoxide mono-methoxide ferric triethoxide ferric triisopropoxide ferric triisobutoxide ferric tri-sec.-butoxide ferric di(sec.-octyloxide) mono-isopropoxide ferric di(o,o'-di-tert.-butyl-p-methyl-phenoxide) mono-isopropoxide chromic triethoxide chromic triisopropoxide chromic tri-sec.-butoxide chromic tri-iso-butoxide titanous triethoxide titanous triisopropoxide titanous tri-sec.-butoxide The metals of these compounds are generally from Groups III to VIII of the Periodic Table. Aluminum isopropoxide (aluminum isopropylate) is prepared for example as disclosed in Kirk & Othmer, Encyclopedia of Chemical Technology, 2nd ed., vol. 1, pp. 844-845 (1963) and one method of preparing the alkoxides of the higher boiling alcohols is by heating the aluminum isopropoxide with the stoichiometric quantity of the desired alcohol and by distilling off the liberated isopropyl alcohol.
(2) Another method of preparing these catalysts consists of using a carboxylic acid or anhydride, a compound of Formula I, and an alcoholate or phenolate of a bivalent metal, M(OR) the group R being identical to group R of Compound I, or different therefrom.
The carboxylic acid or anhydride is preferably used in the proportion of 2 moles per mole of the compound M(OR) Generally for 1 mole of acid or anhydride, 0.01 to 100 moles of each of Compounds I and M(OR) are used.
Instead of these latter compounds, the corresponding Meerwein complexes can be used such as disclosed in Kirk & Othrner, Encyclopedia of Chemical Technology, 2nd ed., (1963), vol. 1, p. 835, and Liebigs Ann. Chem. vol. 476, 113 (1929).
It should be understood that the reagents can be formed in situ. For example, instead of a carboxylate of the Formulas II, III, or IV, a mixture of an alcoholate or phenolate of a bivalent metal and a carboxylic acid or anhydride can be used. In this case, in the presence of a compound of Formula I, a Meerwein complex can be formed, although the Meerwein complex can also be formed by an other known method.
(3) It is also possible to react a dialcoholate-carboxylate of a trivalent metal of the formula:
in the proportion of e.g., one mole thereof with 0.01 to 100 moles, preferably /2 mole, of a dialcoholate of a divalent metal, (RO) M, the various symbols of which have the same meanings as heretofore and can be alike or different.
Everything that was stated in the description of the (VIII) (RO) M'OM-OM'(OR) where M represents the bivalent metal, M the trivalent metal, and R is defined as above.
When the ester V, VI and/or VII is only partly formed, the catalyst can correspond to a formula such as (IX) (RO) M-OM-OCOR Those catalysts which contain a considerable proportion of acyl groups R-CO tend to produce polymers of lower molecular weight than are produced by catalysts of Formula VIII.
The cyclic ethers that are polymerizable by this invention are especially those in which the ring contains 3 or 4 atoms, including especially the 1-2 and 1-3 epoxides (oxethanes or oxacyclobutanes). These compounds contain generally 2 to 20, preferably 3 to 12 carbon atoms per molcule.
Of the epoxides, preferred are those of the following formula:
wherein the groups R to R represent hydrogen atoms and/or hydrocarbon groups which may be substituted by atoms or radicalst hat do not interfere with the polymerization, among which may be mentioned alkyl, cycloalkyl, aryl, alkenyl, and haloalkyl groups.
Examples of the 1,2-epoxides are the following compounds: epoxyethane, epoxypropane, 1,2-epoxybutane, 2,3-epoxy butane, epoxy-isobutane, epichlorohydrin, styrene oxide, m-chloro styrene oxide, a-methyl-styrene oxide, cyclohexene oxide, phenyl-glycidyl ether, chlorophenyl-glycidyl ethers, methoxyphenyl-glycidyl ethers, methylglycidyl ether, isopropyl-glycidyl ether, allylglcidyl ether, butadiene monoxide, vinyl-cyclohexene monoxide, dicyclopentadiene, monoxide, cyclooctadiene monoxide, and isooctene oxide.
Examples of the oxethanes are especially: 3,3-bis (chloromethyl)oxacyclobutane, 1,3 epoxypropane, 2- methyl-oxethane, 3-methyl 3 propyl-oxethane, 3-eth-yl- 3-butyl-oxethane, etc.
The various monomers cited above can be used alone or in mixtures. Two, three, four or more of them can be eopolymerized to obtain copolymers with specific properties.
The polymerizations can be performed in a large range of temperatures, e.g., between and +200 C., preferably between 20 and 120 C.
The work is preferably done in the almost total absence of oxygen and water or humidity by methods generally known in the art.
The proportion of catalyst can be, e.g., between 0.001 and 30 gram-atoms (totality of M-i-M) per moles of monomer. It depends on the rate of polymerization that is desired, and also on the purity of the monomers. The catalyst can be added either before or after the monomer. Either the catalyst or the monomer can be added all at one time or continuously in small amounts. A preferred method is to add about 2 to 15% of the total amount of monomer (or mixture of monomers) to a diluted solution of the catalyst, and after a polymerization of about 10 to 30%, to add the remainder of the monomer or monomers.
The polymerization can be effected either in mass or in solution. Sometimes it is advantageous to do it in solution. All water-free diluents which do not function as alcohols, aldehydes, acids or ketones can be used, preferred examples being heptane, hexane, pentane, butane, petroleum ether, cyclohexane, benzene, toluene, dioxane, ethyl ether, isopropyl ether, methylene chloride, ethylene chloride, etc.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the specification and claims in any way whatsoever.
In the following examples, all temperatures are in degrees centigrade.
EXAMPLE 1 In a reaction apparatus equipped with a mechanical agitator, a fractionating column and a thermometer, 45 g. anhydrous zinc acetate are added (all operations with anhydrous products are performed under an argon atmosphere, free from moisture and all the solvents have been previously dried over calcium hydride).
The anhydrous zinc acetate of this example was obtained from crystalline zinc acetate dihydrate by heating the addition of aluminum isopropylate was commenced. During the time (3 hours) of such addition, the distillation of volatile products was observed, and after the addition of half of the aluminum isopropylate the zinc acetate was observed to become soluble.
under reflux with an excess of acetic anhydride, followed After all the aluminum isopr-opylate has been added by repeated washings with toluene, and a final drying at (3 hours) the mixture is heated another 2 hours at 200 80100 C. under vacuum. C. and the tetrahydro-naphthalene is then distilled at 190- Under mechanical agitation and at room temperature, 195 C. under reduced pressure down to 0.05 torr (mm. the zinc acetate has added to it 102 g. aluminum isopro- 10 Hg). pylate dissolved in 250 cm. Decalin. After the product has been cooled, about 600 cm. an-
The apparatus is then immersed in an oil bath heated hydrous n-heptane are added to it. After decantation from to 230 C. while the temperature of the reaction mixture a trace of insoluble material, the limpid heptane solution is kept at 170175 C. The heterogeneous mixture first is decanted and kept in a bottle under pressure of argon. thickens and then all the zinc acetate is dissolved in about Analysis by complexometry gives the following results: 15 to 30 minutes while at the head of the column is ob- M at /Cm 3 served the distillation of an efiiuent with a boiling point Zn of 885 C. under 760 mm. Hg. As soon as the zinc ace- A1 0'740 tate is dissolved, the temperature of the reaction mixture I "i "f is raised to 1954980 and the heating continued up to Chromatograpmc analysis of the dlstillant gives the 198200 C. under agitation for 8 hours (up to a total of followmg results: 8 hours 30 minutes) until 55 cm. of distillate have been colleeted, the temperature at the head of the column Isopropyl acetate 43 commencing to drop from 88 to 73 C. toward the end [sopropyl alcohol of the reaction. Acetone The contents of the reaction vessel had the appearance EXAMPLE 3 of limpid yen OW 1iquid Y P a green An apparatus similar to that of Example 1 is used, but The Decahn then dlstlned under dnmmshed pres provided with a device for adding solids under the argon. Sure at 180-190 and toward the Process A solution of 210 g. aluminum isopropylate in 515 cm. under The resldue penning to Decalin is placed in the apparatus and the mixture heated cool under vacuum. The flask then contams a reslnous to 190 195o 92] Zinc acetate am then added in frothy Product small quantities under vigorous stirring. During this addi- After the product. has to tempeiamre tion the zinc acetate becomes soluble and a distillation of hydrous n'heptane 1S addad m p i qu.ant1ty to provolatile products is observed. After all the Zinc acetate has dues 500 Cm? of yellow 501mm Whlch kePt under been added 3.5 hours) the mixture is heated to 195- argon- 198 C. another 3 hours. A total of 130 cm. of distillate Analysis by the method of complexometry (ethyleneis obtained diamino tetr acetic acid) as disclosed The product dissolved in heptane is isolated in a man- Analytlcal Uses Ethylene Dlamme Tetraacetlc ner similar to the methods described in the preceding Acld Van Nostrand Princeton 1958 i examples. The solution is pale yellow with a strong green i 168 9 220-1 241-2 glves the folfiuorescence. The Al/Zn ratio is 2.09 by complexometry. lowmg results: Analysis of the distillate by gaseous chromatography gives Milliatoms/cm. the following results: Zn G./100 Cm. Al 1.01 5 Isopropyl acetate 68.5 Atomic ratio Al/Zn=2.03. Isopropyl alcohol 6.15 I f h d H b h h Acetone 10-8 Ana ysis o t e isti ate y gas c romatograp y gives the following results: EXAMPLES 4 To 6 G./100 CHI- In these examples the work is done b the method of Isopropyl acetate Example 1, but using dififerent molar ratios of aluminum Isopropyl alcohol 6.4 isopropylate to zinc acetate. The details are indicated in Acetone 8-6 Example 1.
TABLE I Starting products Duration Distillate Ex. Ratio of the Weight Isopropyl Ratio Zinc Aluminum Al/Zn reaction percent acetate Al/Zn acetate isopropylate (hou (E) 1 Quantity of isopropyl acetate eliminated by distillation, expressed in percent of the initial zmc acetate.
2 Atomic ratio found in the heptane solution by eomplexometric dosage.
EXAMPLE 2 The same apparatus is used as in Example 1. 250 cm. tetrahydronaphthalene are added to 46.13 g. anhydrous zinc acetate. The apparatus is immersed in an oil bath heated to 230 C. and as soon as the temperature inside the apparatus has reached l95200 C. (within a few minutes) a hot solution of 106 g. aluminum isopropylate in 200 cm. toluene is added droy-by-drop in such a manner that the temperature of the reaction mixture remains between and 198 C. The contents of the flask had the characteristic yellow color of the catalyst, ever since 75 distilled 1 hour at 200 The same apparatus is used as in Example 1. 42.6 g. anhydrous zinc acetate, 55.7 g. aluminum isopropylate and 300 cm. anhydrous toluene are introduced into the apparatus.
The mixture is slowly heated over 2 hours up to 200 C., and the mixture is then kept at 200 C., during the distillation which continues 4 hours. It is noticed that the zinc salt does not completely dissolve. The mixture is then C. under vacuum down to 0.05
torr (mm. Hg) to remove the last traces of volatile product.
After cooling, about 350 cm. anhydrous n-heptane are added and the mixture decanted.
The limpid solution is kept in a bottle under pressure of 10 The product is heated 4 hours to 195-198" C. with distillation of the volatile products (mainly isopropyl acetate), and the reaction is then terminated as in Example I.
The product obtained is similar to the preceding products. 120 cm. of anhydrous n-heptane are then added,
argon. 5 in which the product is almost completely soluble. Anal- A complexometric analysis of the heptane solution gives ysis by complexometry gives the following results: the following results: MI atl/cma M. at./cm. Zn 0.37 Zn 0.22 A] 0.78 Al 0-45 Al/Zn=2.l. Al/Zn==2.04.
EXAMPLES 8 TO 10 EXAMLES 13-16 In these examples difierent anhydrous carboxylates of r In these examples the aluminum alcoholate is varied. zinc are used. These Zinc carboxylates have been pre- The method of operation is the same as in Example 1, pared from zinc oxide and the anhydride of the correwith the details and modifications as indicated in Table sponding carboxylic acid, using a slight excess of an- III.
TABLE III Ex Roi the Al(OR) Zn(OAc)2, Diluent, T., 0. Duration, Percent Al/Zn Al(OR)3 g. g. cm. 0 11. 0A0 B t: 17. 07 9. so 250 l-100 10 73 1. e5 n-Bu 24. 6 9.8 150 175-195 5 e 1. sec-Bu"... 19.0 7. 44 -1ns 5 2.0 16 tert.-Bu 33.2 12. 57 250 160490 8 so 2.12
Quantity of ester eliminated by distillation expressed in percent of the initial acetate (zinc acetate). b The atomic ratio found in the heptane solution, by complcxometric dosage.
O Petroleum fraction minimum 90% aromatics. 10% aliphatics, Distillation range -205 C.
d In this example, (n Bu 0)9Al (O-isoPr) is used.
* Analysis by gaseous chromatography indicates that it is isopropyl acetate.
hydride, by heating under reflux in the presence of toluene as a diluent. The carboxylates are then purified by repeated washings with hot toluene (at 100-105 C.).
The condensation reaction is performed as in Example 1, but with the modifications indicated in Table II.
EXAMPLE 17 In this example it is shown that the condensation prodnot obtained from aluminum isopropylate and zinc acetate is stable in the presence of an excess of alcohol,
TABLE II Startin roduets (g.) Step I 1 Step II 2 g p Diluent I Al/Zn (iProhAl Zn(RCOz); RCOO- I. 0. Duration T. 0. Duration (hours) (hours) 43 25 n-Butyrate TC ]3 175 1 200 4 2. 2 53 31 Isobutyrate. T C B 175 1 200 4 2. O 32 23 Benzoate a-Cl-N 5 200 a 2 2. 48
l Step of dissolving the anhydrous zinc carboxylate. sponding ester.
analysis (EDTA). 4 Mixture of technical trichlorobenzenes.
2 The step Where the reaction is ended, with the elimination of the cone 3 The ratio is of the product in heptane solution (after decantation if necessary) determined by complcxomctric 5 a-chloro-naphthalene.
5 Step II performed under reduced pressure, after distillation, 3O cm. fresh a-chlero-naphthalene at the same time added and distilled at 195198 C. with the pressure reduced to 0.05 torr (mm. Hg), and this last operation repeated three tunes.
EXAMPLE 11 The apparatus of Example 1 is used, 29.4 g. solid aluminum isopropylate are added to 15.72 g. anhydrous zinc acetate. The mixture is heated. With the melting of the aluminum isopropylate at 120 C., the beginning of the reaction is observed at that temperature. There is a liberation of vapors of isopropyl acetate whose distillation is accelerated as the temperature increases.
After having heated the product 4 hours at 200 C. under mechanical agitation and then 1 hour at 195200 C. under vacuum down to 0.05 torr (mm. Hg), with distillation of the volatiles, the remaining product has an appearance similar to the products of previous examples. It is dissolved in anhydrous n-heptane, leaving a slight residue. The limpid heptane solution is kept in a bottle under argon.
Analysis by complexometry gives the fOllOWing results:
M. at./cm. Zn n 0.29 Al 0.59 Al/Zn=2.04.
EXAMPLE 12 which can be made use of here for the preparation of different catalysts by varying the group OR, and finally the treatment described below produces in some cases a catalyst that is more active than its precursor.
(A) To a solution in Decalin containing the condensation product of Example 1 is added some isopropyl alcohol in the ratio of two moles of alcohol per atom of aluminum. The mixture is heated 1 hour to 180 C., the volatile products then evaporated at ISO-180 C. with the pressure reduced to 0.05 torr (mm. Hg), and the resinous residue dried 1 hour at l80-185 C. under the same reduced pressure. Heptane is then added, in which the product dissolves completely, producing a yellow solution with a strong green fluorescence.
(B) The procedure of Example 17A is repeated, but with the use of secondary octyl alcohol instead of isopropyl alcohol. After distillation and drying there is obtained a very viscous residue of vitreous appearance, very soluble in heptane.
EXAMPLE 18 1 1 total time of reaction is 3.5 hours. The yield of acetone is 92% of the theoretical. The volatile products are then distilled under a vacuum down to 0.05 torr (mm. 'Hg) and the distillation repeated 3 times with 3 cm. a-chloronaphthalene per milliatom aluminum added before each by one of the following carboxylates and a catalyst obtained in a similar manner for the polymerization of cyclic ethers:
stannous diacetate 5 dibutyl stannic diacetate 21812311311011. The residue 1s moderately soluble in n-hepdiphenylstannic diisobutylrate titane (II) diacetate EXAMPLE 19 titanyl dibenzoate Into the apparatus of Example 1 are placed 45 g. anvanadium (II) diacetate hydrous zinc acetate and 136 g. ferric tert.-butoxide dis l vanadyl diacetate solved in about 300 cm. of a petroleum fraction (of. note chromous diformate (c) of Table III). The mixture is gradually heated to 150- Zirconyl di-n-propionate 175 C. until all the zinc acetate is dissolved (1 hour). palladous diacetate The temperature is then raised to 190 C. and heatplatinous diacetate ing continued hours. Then at 130 C. 150 cm. securanyl diacetate ffil octylt i f f rllnhe mlxturedls fi i at In the preceding examples the trivalent metal comg f ulntl t g lshno i g Y lstl anon pound, i.e. aluminum isopropylate, and ferric tert-butan s g t e v0 a ag oxide can be replaced by one of the following alcoholates move a prvessure re uce to and a catalyst is obtained in a similar manner for the (mm. Hg). The residue is almost completely soluble in polymerization of cyclic ethers. heptane. It has a very dark brown color. Tltrimetnc analysis gives an atomic Fe/ Zn ratio=2.1. aiummum tl'lethoxldlel d d b d auminum monomet oxi ei-secutoxi e EXAMPLES 20 to 32 aluminum triisopropoxide In these examples the divalent metal is varied. The aluminum tri-sec-butoxide anhydrous acetate has been prepared from the hydrated aluminum triiSObutOXide salt by heating under reflux with acetic anhydride. The aluminum di-sec-butoxide mono-iso-propoxide method of preparation and the conditions of reaction aluminum di-sec-octyloxide mono-iso-propoxide are set forth in Table IV. aluminum diphenoxide mono-isopropoxide TABLE IV Starting substances Method Divalent metal (M) of prepara- Quantity, g. Al(iPro) g. Diluent tion Al/M Color Nature Composition as in Example 40 7O 1 7.2 Pale yellow. 28 81.6 12 2.3 Do. 22 .8 e4 1 3.0 Do. 20 41 1 2.17 Orange yellow. 25 64.5 12 2.0 Do. 11 16 .4 1 4 .3 Yellow. 48 .7 114 1 2 .0 Pale reddish brown. 41.8 as 2 2.0 Do. 45.3 107 2 2.8 Very pale green. as .6 86 1 2.3 Reddish violet. 52 120 7 3.0 Do. 25 7 2.3 Violet. 31 69 .5 7 2.6 Reddish brown.
THN=tetrahydronaphthalene, CP=petro1eum fraction; minimum 90% 3 Of the product in heptane solution, after decantation it necessary. M=divalent metal.
range 190-205" 0.
EXAMPLE 32 Into the apparatus of Example 1 are placed 27.4 g. aluminum di(sec.-octyl oxide) mono-isopropoxide and 400 cm. Decalin. To this solution is added, dropwise with agitation at room temperature, 4.75 g. acetic acid dissolved in 50 cm. toluene. The isopropyl alcohol that is formed, and also the toluene, are distilled under 0.5 torr (mm. Hg), at temperatures not above 25 C. 3.58 g. magnesium isopropoxide are then added and the mixture heated gradually to 160 C. during 4 hours until a viscous but almost homogeneous mixture is obtained. The temperature is then raised slowly to l90-l95 C. (2 hours) and then to 200 C. for 7 hours, with distillation of the ester that is formed. The resulting condensation product is decanted and the limpid light yellow and fluorescent solution is transferred to a distillation flask from which the Decalin is distilled under 0.05 torr (mm. Hg). 400 cm. n-heptane are then added in which the contents of the flask are almost completely soluble.
Complexometric analysis gives the following results.
Atomic ratio Al/Mg.=2.25.
It should be mentioned that in any of the preceding examples the bivalent metal carboxylate can be replaced aromatics, maximum 10% aliphatiw. Distillation aluminum di(0,0-tert-butyl-p-methyl-phenoxide) mono-isopropoxide gallium triethoxide gallium triisopropoxide gallium tri-sec-butoxide gallium triisobutoxide gallium tri-n-butoxide gallium diphenoxide mono-isopropoxide boron di(sec.-octyloxide) mono-methoxide boron di(sec.-octyloxide) mono-isopropoxide boron diphenoxide mono-methoxide ferric triethoxide ferric triisopropoxide ferric triisobutoxide ferric tri-sec.-butoxide ferric di(sec.-octyloxide) mono-isopropoxide ferric di(o,o-di-tert.-butyl-p-methyl-phenoxide) mono-isopropoxide chromic triethoxide chromic triisopropoxide chromic tri-sec.-butoxide chromic tri-iso-butoxide titanous triethoxide titanous triisopropoxide titanous tri-sec.-butoxide vanadous triisopropoxide vanadous tri-sec.-butoxide As specific mixtures of reactants which can be used to prepare the catalysts of this invention, according to the preceding examples, the following are given by way of examples:
Aluminum triisopropoxide and strontium diisopropylate with acetic anhydride; aluminum tri-sec-butoxide and strontium diisobutylrate; aluminum triisopropoxide and dibutyl-tin-diacetate; aluminum tri-sec-butoxide and stannous diacetate; aluminum-tri-isopropoxide and titanium (II) diacetate; aluminum triisopropoxide and dicyclopentadienyl titanium (IV) diacetate; aluminum tri-sec.- butoxide and titanyl diacetate; aluminum triisopropoxide and chromium (II) diacetate; aluminum triisopropoxide and molybdenum (II) diacetate; boron monomethoxide di(sec-octyloxide) and di-phenyl-tin (IV) diacetate; boron monomethoxide di-sec-octyloxide and barium diacetate; boron tri-isopropoxide and calcium di-isopropoxide with acetate; gallium triisobutoxide and ferrous diacetate; oxide and stannous diacetate; gallium tri-isopropoxide and zinc diacetate; gallium tri-sec-butoxide and magnesium diacetate; gallium triisobutoxide and ferrous diacetate; indium tri-isopropoxide and Zinc diacetate; indium triisopropoxide and zinc dibenzoate; indium tri-sec-butoxide and cadmium diacetate; ferric tri-isopropoxide and cadmium diacetate; ferric triethoxide and calcium diacetate; ferric tri-sec-butoxide and ferrous diacetate; ferric tri-isopropoxide and cobalt diacetate; ferric monoisopropoxide di-sec-octyloxide and manganese (II) diacetate; ferric triisobutoxide and zirconyl diacetate; chronmium tri-isopropoxide and zinc diacetate; chromium tri-isopropoxide and calcium diisopropylate with acetic anhydride; chromium tri-sec-butoxide and ferrous diacetate; chromium triethoxide and cobalt diacetate; chromium tri-ethoxide and molybdenum (II) diacetate; titanium (III) triisopropoxide and chromium (II) diacetate; titanium (III) tri-isopropoxide and vanadyl diacetate; vanadium (III) tri-sec-butoxide and molybdenum (II) diacetate; vanadium (III) tri-isopropoxide and palladium (II) diacetate; scandium tri-isopropoxide and platinum (II) diacetate; scandium tri-isopropoxide and uranyl diacetate.
Further, within the scope of this invention, one can first prepare a product according to Example 4 and then further react it with a second trivalent metal alcoholate.
The catalyst obtained in this way contains three different metals. Specific mixtures of reactants which can be used, are given by way of examples.
Aluminum triisopropylate and zinc diacetate according to Example 4 and then further contacted with chromium triisopropoxide acocrding to Example 1 or 2; aluminum tri-sec-butoxide with cobalt diacetate; and then further reacted with titanium (III) triisopropoxide; vanadium (III) triisopropoxide and manganese diacetate and then further reacted with boron mono-isopropoxide di-secoctyloxide; chromium tri-isopropoxide and molybdenum (II) diacetate and then further reacted with scandium triisopropoxide.
EXAMPLES 33 TO 66 In these examples is shown the polymerization of epoxy-propane with the catalysts of Examples 1-32. The polymerizations are performed in glass tubes, previously flushed with argon. Into these tubes the catalyst, the solvent and the monomer are placed in the absence of humidity, the order being reversed in cetrain cases. The tubes are then sealed and agitated 8 hours at 50 C., except in Examples 56-58 where the time was 44 hours and Examples 64 and where the time was 72 hours. A tube is then opened and the polymerization stopped by adding a small amount of isopropylamine (about an equimolecular amount relative to the bivalent metal) and some Santowhite Powder (about 0.5 to 2% of the weight of the polymer) as antioxidant. The contents of the tube are dissolved in a sufficient amount of toluene and the catalyst removed by washing with a dilute aqueous solution of citric acid, then with sodium bicarbonate, and finally with water. The toluene solution is then dried in crystallizers and the polymer then obtained in the form of a film. The percent of conversion is then calculated from the weights of the films after a correction for the antioxidant.
The intrinsic viscosities have been determined in toluene solution containing about 1% Santowhite Powder at 30 C. (The same method has been used in all the examples of the present invention.) Viscosimeters of dilution type ASTM D445 are used. The specific viscosity is determined at 4 different concentrations, and the intrinsic viscosity then determined by extrapolation in dl./g. (see P. J. Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, pp. 309-310).
The examples are reassembled in Table V. For those marked A, use was made of 1.16 parts by weight of epoxypropane and 12.5 parts by weight of heptane, while for those marked B, use was made of 8.17 parts of epoxypropane and 6.84 parts of heptane.
TABLE V Prepared Percent in Percent Ratio according atoms per conversion [1;] Remarks to the mole of the into (IL/g. Example monomer polymer 2.03 1 1.5 71 7 .0 Snappy rubber. 1 .97 2 1 .12 62 7.7 Do. 1 .07 2 0.43 85 8.3 Rubbery, very tough. 2 .09 3 1.0 60 7 .6 Snappy rubber. 1 .08 4 3 .2 74 2 .3 Tacky gum. 1 .23 5 2 .9 4 .7 2 .95 6 3 .0 83 .5 6 .4 2 .04 7 2.90 71 5 .8 2.2 8 2 .5 63 3 .4 2 .0 9 2 .5 09 3 .7 2 .48 10 2 .5 92 .5 7 .9 Snappy rubber. 2.03 11 6.0 64 .5 3 .7 Gummy. 2 .1 12 6 .0 09 .5 6 .6 1 .95 13 3 .0 5O 1 .95 14 4 .1 37 2 .0 15 2 .2 77.5 2.12 16 5 .0 38 2.04 17A 1.0 79 2.02 17B 1.0 82 2.0 18 3 .0 47 .5 2 .1 19 1.5 71.5 7 .2 20 6.0 83 2 .3 21 6 .0 6.1 3 .0 22 0 .0 4 .5 2 .17 23 6 .0 58 2.0 24 G .0 68
TABLE VCo11tinuod Prepared Percent in Percent Catalyst Ratio according atoms per conversion [1;] Remarks MlM to the mole of the into dlJg.
Nature Example monomer polymer Al/Ba 4 .3 25 6 .0 60.7 3 .8 Al/Mn 2 .0 26 3 .0 66 .3 5 .8 Al/Mn 2 .0 26 .43 44 .5 6 .9 Rubbery. Al/Mn 2 .0 27 3 .0 47 .7 6 .6 Do. Al/Fe 2.8 28 2.5 51 7.1 Very tough. All Go 2 .3 29 2 .5 53 .8 .3 Rubbery. Al/Co 2.3 29 0 .4 27.4 6 .5 D0. Al/Co 3 .0 30 2 .5 73 .5 3 .9 Gummy. Al/Co 3 .0 30 0.4 47 .5 4 .4 Al/Ni 2 .3 31 0 .0 20 Al/Cu 2.6 32 6 .0 12 Al/Mg 2 .25 l 32 3 .0 4 .2 1.8
EXAMPLES 67 TO 79 In these examples is shown the use of different diluents, and also the polymerization of different monomers. The catalyst of Example 1 is used. The polymerizations have been performed at 50 C., except for Examples 75 and 76 where the polymerization temperature was 90 C.
The polyphenyl-glycidyl ether being insoluble, it was first washed with toluene, then with methanol containing 2% H01, and finally with methanol.
The polyepoxy-butane (1,2), the pfoly-LZ-epoxyisopropoxy-propane, the polyallyl-glycidyl ether, and the polystyrene oxide have been purified as the polyepoxypropane. The others have been treated with the diethyl ether and the soluble and insoluble parts purified separately.
The results are summarized in Table VI.
EXAMPLES 80 TO 88 In these examples is shown the copolymerization of epoxypropane with different monomers. The copolymerizations and the isolation of the copolymer have been performed as described in Examples 33 to 66.
The percentage of co-monomer for epichlorhyclrin has been calculated from the analysis of the copolymer in chlorine. For the copolymerization with allyl-glycidyl ether or 1,2-epoxy-4-vinyl-cyclohexane, the percentage of copolymer has been determined by dosage of the unsaturation by the method of Kempf (Kempf and Peters, Ind. Eng. Chem. Anal. Ed. 15, 453 (1943)).
The solvent that was used to dissolve the copolymer as Well as the iodine monochloride Was carbon tetrachloride.
The results are given in Table VII.
TABLE VI Monomer Parts Catalyst/ Time 01 Percent Percent Dlluent Nature by Parts Monomer, polymerconversion insoluble 1 weight Nature by percent ization in polymer weight Example:
67 n-Heptane 6.84 Epoxypropane 8 .14 0 .4 15 82 68 Heptane-dioxanc (8:1 v./v.) ....-d0 3 .34 0 .82 88 69. Diethylethcrhcptane (10:4 v./v.) 12 3.34 0.82 15 34.4 70- Toluenc-heptano (10:4 v./v.). 16 .(l0.. 3 .34 0 .82 15 85 71 n-Heptane Butadiene-monoxlde- 1 .42 5 .0 87 .2
Epoxybutane (1, 2) 1.42 5 .0 6% 50 1,2-epoxy isopropoxy propane 2 .3 5 .0 25 39 Phenylglycidyl ether 3 5 .0 6 2 87 do 44.6 1.65 24 94 Styrene oxide. 2.5 5 .0 36 61 0 2.5 5.0 11 5 Epichlorohydrine 1 .3 5 .0 15 23 Allylglycidyl ether 4 .56 0 .0 15 .5
1 For poly(epoxypropane): 1n acetone at 20 (3.; For poly(phenyl-glycidyl ether): In toluene at room temperature; For the others:
at room temperature.
in ethyl cthe TABLE VII Comonomer Epoxy Catalyst Heptane, Propane, Atoms Percent Comonomer parts by Parts parts percent Time conversion in he [1 d1. lg. Remarks weight Nature 1 by by mole (hours) into polymer weight weight 11(1onou11)er polymer by weight Example:
so 11 6.39 4.07 6.0 63 30 47 Rubbcry.
12 1.3 7 .15 6 .0 20 12 Do. 0.7 1 .93 18.7 0.35 1% 5 7 6 .2 Do. 0.7 7.73 33.2 0.37 2 5 11 5 .8 Do. 0 .7 9 .67 11 .6 0 .4 2% 5 25 5 .0 D0. 175 7.7 33.2 3.0 1 11 18 6.0 Do. 175 7.7 33.2 3.0 8 18 7.6 Do. 175 1.9 18 .7 3 .0 8 9 .4 8.5 Do. 11 EVCIL-.. 0.2 1 .1 6 .0 20 83 .5 9 .1 Do.
1 E OH Epichlorohydrin; A GE =A1lylglycidylether; EVCH= 1,2-ep0xy4-v lnyl-cyclohexane.
Into a polymerizaton vessel previously purged with dry argon, 600 parts of dry n-heptane are placed and 0.03 gram-atom (Al+Zn) of the catalyst of Example 1. The mixture is heated continuously at 70 C. and a mixture of 0.4 part allyl glycidyl ether, 5.6 parts propane epoxide and 41 parts n-heptane are added little by little in the course of 1 hour. Then there is added in a single portion a mixture of 50.4 parts propane epoxide and 3.6 parts allyl glycidyl ether. The polymerization is continued for 7 hours and is then stopped by the addition of a solution containing 0.58 part isopropylamine and 0.5 part Santowhite Powder in 34 parts heptane. The polymer is dried in a current of air and finally at 50 C. in a stove under vacuum. 44.6 g. of a gum were obtained (73% conversion). A small portion of this gum is redissolved in toluene, washed to remove the catalysts (see Examples 33-65) and dried. The intrinsic viscosity is determined and found to be equal to 8.8 dl./ g.
The remainder of the gum is vulcanized 40 minutes at 150 C. with the composition of Table VIII.
A very snappy rubber is obtained, whose properties are indicated in Table 1X.
TABLE IX Tensile strength (kg/cm?) 180 Percent elongation at rupture 790 Modulus at 500% (kg/cm?) 52 International hardness DIDC 47.5 Percent gel (a) 97 dry weight after extraction dry Weight before extraction Extraction in benzene at room temperature during 72 hours.
The preceding examples can be repeated with similar success by substituting the generically and specifically described reactants and operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Consequently, such changes and modifications are properly, equitably, and intended to be, within the full range of equivalence of the following claims.
What is claimed is:
1. A catalytic composition comprising the reaction product prepared by contacting:
(a) a trivalent metal compound having the formula percent gel: X 100 with (b) a bivalent metal compound having the formula YOMZ wherein M is a trivalent metal, M is a bivalent metal, Z is selected from the group consisting of CR and acyloxy groups, X and Y are different, one of which is R, and the other is an acyl group, said groups R R R and R being monovalent hydrocarbon groups.
2. A catalytic composition comprising the reaction product prepared by contacting:
(a) a trivalent metal compound having the formula with (b) a bivalent metal compound having the formula YO-MZ wherein M is a trivalent metal, M is a bivalent metal, Z is selected from the group consisting of CR and acyloxy groups; X and Y are different, one of which is R, and the other is an acyl group, said groups R R R and R being monovalent hydrocarbon groups, and separating at least 1% of the theoretical amount of the ester byproduct XOY of the reaction of (a) with (b).
3. A catalytic composition comprising the reaction product prepared by contacting:
(a) a trivalent metal compound having the formula:
(b) a bivalent metal compound having the formula YO-M-Z wherein M' is a trivalent metal, M is a bivalent metal, Z is selected from the group consisting of CR and acyloxy groups, X and Y are different, one of which is R, and the other is an acyl group, said groups R R R and R being monovalent hydrocarbon groups, and separating at least 60% of the theoretical amount of the ester byproduct XOY of the reaction of (a) with (b).
4. The catalytic composition of claim 2, wherein the ester by-product XOY is separated by distillation.
5. The catalytic composition of claim 2, wherein the molar ratio (a) to (b) is between about 0.01/1 and /1.
6. The catalytic composition of claim 2, wherein the molar ratio (a) to (b) is between about 0.1/1 and 10/1.
7. The catalytic composition of claim 2, wherein said groups R R R R acyloxy and acyl contain from 1 to 6 carbon atoms.
8. The catalytic composition of claim 2, wherein said reaction product is obtained at a temperature between about 50 and 300 C.
9. The catalytic composition of claim 2, wherein (b) is a bivalent metal carboxylate and (a) has the formula M'(OR) wherein M is a trivalent metal and the groups R are monovalent hydrocarbon groups.
10. The catalytic composition of claim 2, wherein (a) has the formula M'(OR) and (b) has the formula M(OR) wherein M is a trivalent metal, M is a bivalent metal and the groups R are monovalent hydrocarbon groups further comprising the addition of a compound selected from the group consisting of carboxylic acids and carboxylic anhydrides.
11. The catalytic compositions of claim 2, wherein (a) is a trivalent metal compound having the formula and (b) is a bivalent metal compound having the formula (RO) M wherein M is a trivalent metal, M is a bivalent metal, the groups R are monovalent hydrocarbon groups and R' is selected from the group consisting of hydrogen and monovalent hydrocarbon groups.
127 The catalytic composition consisting of the reaction product of zinc diacetate with aluminum triisopropoxide.
3,432,445 19 20 13. In a process for polymerization and copolymeriza- No references cited. tion of cyclic ethers in which one or more cyclic ethers are brought into contact with a catalyst, the improve- DANIEL E. WYMAN, Primary Examiner.
ment comprising the addition of a catalytic amount of the PHILLIP M FRENCH Assistant Examiner composition of claim 2.
US. Cl. X.R.
14. The process of claim 13, wherein for every 100 moles of cyclic monomer the catalytic amount of the composition of claim 2 is about 0.001 to 30 gram-atoms of 4295 438-5, 438-11 4293 mm 4292, 462, 2, 47, 88.3, 2; 2s2 431 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,432,445 March 11, 1969 Maseh Osgan et al.
It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 19, "polyed at" should read polyed as line 29, after "formula" insert with Column 2, line 46, "and VI and VII" should read to VI and VIII line 58, "monvalent" should read monovalent Column 5, line 43, "an" should read any Column 6, line 6, "molcule" should read molecule line 16, "radicalst hat should read radicals that line 26, glcidyl" should read qlycidyl Columns 7 and 8, TABLE I, second column, line 1 thereof,
"29" should read 39 Column 10, line 12, "Examles 13-16" should read Examples 13-16 Column 13, line 25, beginning with "boron tricancel all to and including "diacetate; same column 13, line 29,
and insert boron tri-isopropoxide and calcium di-isopropoxide with acetic anhydride; boron monoisopropoxide di-sec-octyloxide and stannous diacetate; gallium tri-isopropoxide and zinc diacetate; gallium tri-secbutoxide and magnesium diacetate; gallium tri-isobutoxide and ferrous diacetate; indium tri-isopropoxide and zinc diacetate; indium triisoprcpoxide and zinc dibenzoate; indium tri-sec-butoxide line 37, "chronmium" should read chromium Columns 15 and 16, TABLE VI fourth column, line 12 thereof, "Epichlorohydrine should read Epichlorohydrin same tab e, in the footnote, line 1, "ethe" should read ether Signed and sealed this 7th day of April 1970.
(SEAL) Attest:
Commissioner of Patents Attesting Officer
|Citing Patent
|Filing date
|Publication date
|Nov 24, 1967
|Jul 21, 1970
|Inst Francais Du Petrole
|Process for manufacturing new polymerization catalysts,the resulting new catalysts and their uses
|Oct 11, 1968
|Dec 8, 1970
|Rinse Jacobus
|Divalent metal oxide acylates
|Oct 23, 1968
|Nov 30, 1971
|Inst Due Francais Du Petrole D
|Manufacture of polymers and resulting polymers
|Jan 27, 1971
|Feb 20, 1973
|Hercules Inc
|Cross-linking epihalohydrin polymers
|Aug 21, 1974
|Oct 19, 1976
|Dynamit Nobel Aktiengesellschaft
|Process for the manufacture of vanadyl alcoholates
|May 13, 1977
|Sep 26, 1978
|Chemplex Company
|Method of polymerizing olefins
|Mar 26, 1976
|Oct 24, 1978
|M&T Chemicals Inc.
|Reaction products of specific antimony compounds with a carboxylate of zinc calcium or manganese and an alcohol or glycol
|Aug 13, 1979
|Jul 28, 1981
|Philippe Teyssie
|Lactone copolymers, process for their preparation and compositions containing them
|Dec 14, 1981
|Aug 2, 1983
|American Chemical & Refining Company, Inc.
|Gold plating bath and method using maleic anhydride polymer chelate
|Apr 3, 1986
|May 12, 1987
|Shell Oil Company
|Alkoxylation process using bimetallic oxo catalyst
|May 21, 1985
|Aug 11, 1987
|Phillips Petroleum Company
|Antifoulants comprising tin antimony and aluminum for thermal cracking processes
|May 19, 1986
|Nov 3, 1987
|Ethyl Corporation
|Metathesis of acetylenes
|Sep 30, 1988
|Aug 7, 1990
|Union Carbide Chemicals And Plastics Company Inc.
|Alkoxylation using a calcium sulfate catalyst
|May 15, 1989
|Aug 21, 1990
|Shell Oil Company
|Stabilized carbonmonoxide-olefin copolymer compositions
|Sep 20, 1990
|Apr 14, 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation of active hydrogen-containing compounds
|Sep 30, 1988
|May 12, 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation using modified group iia metal-containing bimetallic or polymetallic catalysts
|Sep 30, 1988
|May 12, 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation catalysis
|Sep 30, 1988
|May 19, 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation using modified calcium-containing bimetallic or polymetallic catalysts
|Sep 30, 1988
|Jun 2, 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation using modified group iiib metal-containing bimetallic or polymetallic catalysts
|Sep 30, 1988
|Jun 9, 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation using modified calcium-containing catalysts
|Jul 19, 1991
|Dec 8, 1992
|Akzo Nv
|Process for forming mixed bimetal alkoxide-carboxylate composition and novel compositions thereof
|Sep 20, 1990
|Mar 2, 1993
|Union Carbide Chemicals & Plastics Technology Corporation
|Alkoxylation of carboxylated compounds
|May 13, 1987
|Apr 9, 2002
|Pdm Holdings Corp.
|Antistatic plastic materials containing epihalohydrin polymers
|Oct 21, 1998
|Oct 1, 2002
|Bayer Aktiengesellschaft
|Method for producing partially crystalline polyether polyols
|Oct 2, 1985
|May 7, 1986
|Shell Internationale Research Maatschappij B.V.
|Alkoxylation process using bimetallic oxo catalyst
|Oct 2, 1985
|May 7, 1986
|Shell Internationale Research Maatschappij B.V.
|Alkoxylation process using bimetallic oxo catalyst
|Oct 21, 1998
|May 14, 1999
|Bayer Aktiengesellschaft
|Method for producing partially crystalline polyether polyols
|Nov 18, 2014
|May 28, 2015
|Dow Global Technologies Llc
|Zinc catalyst / additive system for the polymerization of epoxide monomers
|Nov 18, 2014
|May 28, 2015
|Dow Global Technologies Llc
|Zinc catalyst / additive system for the polymerization of epoxide monomers
|U.S. Classification
|528/92, 556/1, 556/131, 556/54, 556/80, 526/192, 556/55, 556/42, 556/78, 556/30, 528/416, 556/179, 528/412, 534/11, 556/149, 556/77, 528/417, 556/16, 556/31, 556/150, 528/411, 526/195, 526/118, 558/296, 556/7, 558/294, 556/57, 556/28, 502/170, 556/146, 556/76, 528/415, 534/13, 526/154, 526/117, 526/172, 987/1, 556/27, 556/15, 526/113, 526/123.1, 556/14, 528/410, 526/131, 556/182, 556/61
|International Classification
|Cooperative Classification
|European Classification


text:
I made this to cheer up my Brother, because he enjoys massive vehicles with wheels. He is melancholy because he has a mad wife who doesn't understand him. I hope that you enjoy this model, or empathise with my brother's plight, or perhaps even both.
LXF: http://www.brickshel...threeatonce.lxf
▲ The linked LXF looks like this, which is the livery of the "Arriva" fleet. They rule the roads around here with an aluminium fist.
▲ Their arch enemies are the "First" fleet, whose buses have a questionable paintjob. I'm told that these are called "Barbie buses". There are actually things like this!
I recoloured the original model to see if I could, but you could probably localise it.
Things I wanted to do but couldn't, because LDD 4.2.5 made a fool of me:
- There's a little machine next to the driver's seat, where he or she presses some buttons and the blessed thing pukes out a ticket. I don't know how to make that.
- I hacked something together to give the impression of tax discs on the windscreen, but there were collision issues.
- Even though I made a hinged engine flap on the rear of this behemoth, there's only a 1w space to fit an engine. So I didn't make one.
- The wheels look TINY. The next size up look too big. What am ah gonna do?
Things I actually did, and was really pleased with:
- The windows are those 1x4x6 things which are intended for buildings, placed sideways and secured by the seats. I actually started constructing the model with those.
- Harpoons for the windscreen wipers! When I rotated them in their holders, they became almost flush with the tapering windscreen!
- Actually making this thing. It seems I taught my Brother to bend the rules a bit with LDD.
EDIT: Oh cack, I may have posted this in the wrong place.
Edited by Rufus, 11 August 2012 - 11:10 AM.

subset: commoncrawl


text:
Extended Refreshable Tactile Graphic Display (with Linear Actuation Array)
Award Information
Small Business Information
ELIA Life Technology, Inc.
354 East 66th St., Suite 4A, New York, NY, 10065
Principal Investigator:
Andrew Chepaitis
(212) 327-2550
(212) 327-2550
Business Contact:
() -
Research Institution:
AbstractNew innovative technology for the visually impaired has been developed by NIST. If commercialized, it would provide refreshable tactile graphical information to the visually impaired, enabling them to compete on a more equal footing in the workplace and the education system.
* information listed above is at the time of submission.
An Official Website of the United States Government


text:
Ethno Tekh
In 2013 we started building our "Gravitate", an interactive audio/visual installation that puts the audience in control of a motion-controlled instrument to jam with another player.
Over the month-long residency at Fed Square during November/December 2013, the piece evolved into what you see in the video.
Since this, the piece has evolved - please check out gravitate.ethnotekh.com/ for the latest information.


text:
The fit is nice but the fabric is super thin. I bought the natural color and you can see your hand through it. If your couch is a solid white then this would be fine but if not, you should opt for a thicker fabric like a twill. I returned this slipcover.
This is a basic sofa slipcover - nothing special. It does not stay put and requires adjustments every time someone sits on the couch. It does hold up well in the wash. I ordered another sofa slipcover when I ordered this one because I needed to cover the sofa before guests arrived. I use the other one instead and this one remains in the linen closet. Try the Maytex 2 piece sofa slipcover if you want something that looks a little better and doesn't require as much adjusting,
I got these slip covers as a cheap alternative to the ugly couch I got as a hand-me-down. They do the trick...easy to put on and such. Of course you have to constantly tuck them back in place, but it's just me at my apartment, so it doesn't really matter. I ordered the Natural color, and they are a little bland, but just fine. I would recommend to others for an easy fix. If you want something a little nicer, spend the extra money. Otherwise they work just fine.
I rated appearance poor because the material wrinkles and when you smooth out the wrinkles it leaves a crease. It stains very easy and picks up all lint and dog hair. It needs cleaning every day. I do like the burgandy color it doesn't have the pink in it like the picture. The assembly is like any cover you just have to work with it. Though, I was unbable to get it to fit properly on the arms because they are overstuffed and don't extend to the end of the cushions. I would recommend that you look for another cover, I am doing that now.
I would NOT buy this again. I know that a slip over is less contoured that upholstery, but I could have draped a sheet over my soft and gotten better results. This was made ONLY for use in one of the super-puffy, over stuffed sofa with enormous sculptured arms. If you, like me, have a boxier sofa with square features, DO NOT BUY THIS PRODUCT. It will look like a stick man wearing a size 48 suit.
- How did the color on site compare with the actual product? Fine
- Please tell us about the quality of the product. Fine
- How accurate was the on site description of the product? Terrible
This is a nice slipcover! When it arrived (only 5 business days after I placed the order) I was initially concerned, because it had a strong odor, probably from the dye used (I ordered the indigo one in sofa-size), but when I machine washed and dried it as instructed, it came out beautifully and the odor was gone. It fits my sofa much better than my last slipcover, I think because of the combination of ties and elastic, and it dried in the drier much faster, too. I am buying a second one so that I always have a clean spare.
When you order something of "duck" fabric, you expect it to be thick and tough as nails. This fabric was horribly thin. Like, not even thick enough for a winter shirt in the Deep South kind of thin. Like, I could have torn it apart with my bare hands kind of thin. Don't waste your time or money ordering this. You'll simply re-tape the box and send it back as I did.
- How did the color on site compare with the actual product? Similar
- Please tell us about the quality of the product. The fabric wasn't even 1/3 the thickness I was expecting. "Duck" material is supposed to be really thick and tough as nails. Not so much here.
- How accurate was the on site description of the product? It is a brown sofa cover, so in that way, it's accurate.
I have purchased slipcovers before and this is definitely not like the others. The fabric is a good weight and hangs well on my sofa. I did iron it because I wanted it to look fresh and it did. With the elastic and the tie bands it was a perfect fit for my sofa. LOVE IT.
- Did the color match the color displayed onsite? yes
- How is the quality of the product? excellent
- Did the description onsite accurately describe the product? yes
I had never tried a furniture cover prior to this time. The item was as stated and arrived timely. The instructions were complete and our couch now looks great. I haven't washed the product yet but I believe it will wash fine just by the look and feel of the material. I would recommend this to anyone. Make sure you also purchase the Sure Fit piece of foam to put around the cushions in order to hold the cover in place!
I was so pleased with the covers and the quality. But, over and above that was the ease in which to put them on the furniture. I am not one who likes to assemble, put together, try to figure out, or to follow directions. These slipcovers were a snap to put on. Before buying the covers I read several of the reviews and one suggested to use rolled up magazines to keep the cover nice and tucked in. This hint really works!
The material is hard to iron and make presentable. Let's be honest, most people looking for slipcovers are trying to hide the ancient, off-colored, itchy couch beneath. I was looking for a cover that would easily smooth out and erase the past off my old couches. Though the material is very nice, these slipcovers do not create the facade I was looking for. I also think the price point is very high. Overstock, on the other hand, is great! Always prompt delivery and easy to work with.
Although I liked the color and style of this slipcover, the fabric was so thin that the pattern on my sofa showed through the slipcover (natural color slipcover). The fabric seemed like it would not be very durable with kids, pets, etc because it was so thin. I returned this slipcover and am going to buy one with heavier, more durable fabric.
The only reason I didn't give this natural cover 5 stars is because you can slightly see the plad pattern of my coutch through it. It was easy to put on, looks super cute and stays put. I have 3 boys and it still looks great at the end of the day. The one piece style is more user friendly than the two piece coutch covers (I have tried 2 others). I am pretty picky about things looking sloppy, this does not! It allows my kids to be kids, and i get my cream/natural coutch that i would never pay tons of money for. In the washer/dryer, brandy new again! Go for it!
- How did the color on site compare with the actual product? Very well
- Please tell us about the quality of the product. Washes well, remove promptly from dryer with minimal wrinkles.
- How accurate was the on site description of the product? Great
I am renting a furnished apartment and the sofa is quite old. I didn't want to buy one so I found this slipcover for a very good price. So far, although I have to adjust it often because the sofa is smallish, I am completely satisfied with this slipcover I don't think you could do better for the price.
I bought the natural colored slip cover. I have had it for about a month and you can already tell where everyone sits. It stays in place nicely but I would most definitly buy a darker shade.
The slipcover fits well once I figured out how to put it on. It looks nice but the material is light. I tried to put it over a floral print and the flowers showed through. The grey leather couch looked good with the slipcover (but not as good as the picture).
I have a Jack Russell Terrier who sheds terribly, digs at my furniture and who has springs in his backside. A slipcover is a must to protect my furniture. I wanted a light beachy feel for the spring and the slip covers have given me that feel. The slipcovers are of nice weight, seem durable and the selling point for me are that they are washable. I steam ironed my slip covers once in place to remove the creases from packaging and 2 weeks later they are still in place and loook nice.
In real life the color of the slipcover was very different from the photo online. Another irritation: these slipcovers aren't supposed to be ironed, but it is terribly wrinkly coming out of the package and looks awful. The fit of the cover is definitely NOT anything close to the photos online.
Really nice, but thought it would have been a thicker material
4 dog tested and washed repeatedly this cover is great once you get the hang of "tucking", once mastered I ordered different colors and completely change the look of my living room by changing out the covers!


text:
When you, as a parent, find your child in the back of her closet and she's rocking and banging her head on the wall, you might try talking to either the child or a doctor about what's happening in the mind of your child.
When you see that your child is not asleep after putting them to bed 3-4 hours prior, there might be a problem.
When you hear your child in the middle of the night and find them rocking and bouncing in the bed and not sleeping, there could be a problem.
When your child cries every time they are around certain people, investigate.
If you find your child asleep at the foot of your bed every morning. Don't punish them, investigate. Or at least ask them why.
If you find your child in the bathtub asleep with the light on and the door locked, ask some questions. At this point and after all these clues, try someone other than the child.
When your four year old consistently tells you she has vaginal pain, find a doctor.
When your child who is six can tell YOU what having sex is, find out why.
When your twelve year old tells you that grandpa is molesting her, believe her.
WHne she tells you, hug her.
Tell her she's never going to have to see them again and MEAN it.
When your child tells you they were messed with, find out how much.
When your child tells you about 1 molester, ask if there are others.
When you find out your child is molested, don't tell her to keep it a secret.
Don't tell her that dad will go to prison if you tell him about Grandpa because he'll kill grandpa.
If your child tells you they were molested, don't leave it up to them to tell the other parent, be an adult and take charge and handle it.
If your child tells you someone molested them, confront that person.
If your child tells you someone "messed with them" put someone's a$$ in jail.
When your child is hurting, hug them.
When your child tells you grandpa is "messing with me", AT ALL COSTS, keep her away from him. This would be where putting his a$$ in jail would help.
When your child gets drunk at the age of 13, time to intervene.
When your 14 year old child is bleeding profusely, has stomach pain so strong they can't stand up and them passes something in the toilet, take her to a doctor.
When your child miscarries, time to investigate and not act like it was a "bad period."
When your 15 year old daughter gets caught drinking at school, find out why instead of punching her in the face.
WHen your child is depressed for over 20 years, maybe you should encourage them to tell that secret.
When your child is hospitalized well into their adulthood because they want to kill them self, it's time for you to correct the mistake you made years ago and help them talk about that secret.
When your child finally tells the secret in their 40's, act like you care instead of being inconvenienced.


text:
Christians call for electoral change
Criticize the scandal-tainted 'small-circle election' of the new chief executive
ucanews.com reporter, Hong Kong
Hong Kong
March 1, 2012
Religious leaders have called for changes in the election process of the special administrative region's chief executive officer amid deepening scandals surrounding two of the leading candidates. "The congenital defect of the 'small-circle election' makes us angry and disappointed," leaders from various Protestant denominations, theological seminaries and Christian organizations said in a statement to be published tomorrow in two local newspapers. The statement has been signed by more than 800 people. Local media has described this year's election, to be held on March 25, as a contest between "the pig" and "the wolf" in reference to candidates Henry Tang Ying-yen and Leung Chun-ying respectively. Tang, a wealthy businessman turned civil servant who many believe is Beijing's preferred candidate, has been dogged by questions about his credibility over the building of an illegal luxury basement in his wife's home and marital infidelity. Leung, a surveyor and former Executive Council convener, leads Tang in public opinion polls despite recent allegations by local media of business irregularities and being a Communist Party member, both of which he has denied. Democratic Party chairman Albert Ho Chun-yan, the third candidate in the race, is widely thought to have little chance of winning. Reverend Lo Lung-kwong, director of the Divinity School at the Chinese University of Hong Kong, said the electorate deserves more from the political process. "We want to raise our fellow citizens' awareness that the distorted electoral system will only create greater conflict of interest and social divisions." He added that changes should be adopted before the next election. "We should cohere a consensus for universal suffrage in the 2017 chief executive election." Hong Kong's chief executive is elected by a 1,200-member Election Commission, which critics say favors candidates with close ties to Beijing and denies the public an adequate say in choosing their leaders. The statement further urges electors on the commission to follow their consciences in selecting the best candidate. "They must cut off any interest, listen to public opinion, study the candidates' platforms and have independent thinking," the statement said. Reverend Lo said whoever wins the election should be guided by what is in the best interests of the public. "He should abide by integrity, selflessness, tolerance and openness." Related reports HK voting committee to add religious electors HK Christians pledge to fight on as reforms pass
Caritas India meets to discuss funding challenges
The social service wing of the church wants India's burgeoning business sector to help out
Singapore church warns about Indian 'preacher'
A layperson has been taking donations for his 'charismatic healing ministry'
Priest echoes tribunal call for Indonesia to own violent past
Reconciliation is the most appropriate measure, says lecturer at Catholic University of Sanata Dharma
Brutal killing of French priest shocks Bangladeshi Catholics
Atrocity occurred same day as church officials in Dhaka discussed anti-terrorism safety measures
Sri Lanka's anti-terrorism law should end, says report
But even if controversial legislation was repealed, abuses may not end, says Catholic priest


text:
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There are 94 comments on the San Jose Mercury News story from Mar 31, 2006, titled Saratoga priest arrested on rape charge. In it, San Jose Mercury News reports that:A Saratoga priest was arrested Thursday for allegedly raping a 29-year-old Oregon woman in a Sunnyvale motel this week.
Join the discussion below, or Read more at San Jose Mercury News.
#63 Apr 11, 2007
catholic priest's as far as i can tell are extremely perverted. i was attending mass, in line for communion and i definately heard one of the priest say;
'f@@@ her in the a@@'
i was a little doumbfounded, but this incident is the straw that broke catholic's back
#64 Apr 11, 2007
a little doumbfounded, but not too suprised right, they are a bunch of hypocrates and are laughing at those of you that think there is some sort of god up in the sky.
United States
#65 Apr 17, 2007
Does anybody know what has happened in this situation ?
#66 Apr 20, 2007
Just the usual, a priest taking sexual advantage of somone in a weak vulnerable condition.. Why do the lying hypocrates still have any level of respect or status in todays modern society.
#68 Apr 27, 2007
I can't understand why people are still shocked to hear yet again another sex crime committed by a Catholic priest. What one should really be shocked about is all the billions of dollars that go in to the cover-ups for these sick individuals. They are not disfellowshipped but "relocated" to again find other innocent ones to defile. Shame on the church for the way it handles these situations. God's Holy spirit does not dwell within Catholicism. Not with its teachings....nor with what it allows to continue and hide.
#69 Apr 27, 2007
I have had recent conversations with many folks that equate the catholic church with only child molestation and all other organized religion with greed. And it just keeps coming, and I have to agree, hypocrates all.
#70 May 5, 2007
>> Does anybody know what has happened in this situation ?
He raped a woman with faith ...
#71 May 6, 2007
Father Randy was a kind and considerate man. He will sorely be missed by many. His 'little Johny Jones' humorous tales in Sunday mass will always be remembered.
#73 May 9, 2007
Father Randy was a kind, considerate creep. I am sure he had many stories he could not share at Sunday mass, about the woman he slept with...
#78 Jul 26, 2007
Do you still think he is capable of doing anything like this? He has admitted to having sexual relations with the girl.
#79 Jul 26, 2007
fr randy i don't thing you do this mestake you will be in my preyer forever god will ask you what you doon.
#80 Jan 29, 2008
A fraud has been revealed and to a certain extent, justice has been served. I only wish that the collection basket hadn't funded the defense and that the Randy had actually bought some well-deserved jail time. Randy Benas has been masquerading as a priest for years, but it appears that his preoccupation with women in "vulnerable relationships" has finally caught up with him. This was a single woman brave enough to bring her tragedy into the public eye for the sake of justice. God knows how many families and marriages Randy has helped to destroy and/or how many wayward women he has "comforted" into a hotel bedroom under the guise of the Gospel to feed his own lustful and selfish desires of the flesh. He is a simple a predator of the oldest sort. He is not worthy of the title Priest or "Father." Time to pay the fiddler Randy.
#81 Jan 29, 2008
Joel Ayel wrote:
So...what was the priest doing in a Sunnyvale MOTEL with a 29 year old WOMAN?
Reading her the bible?
are you certain that he was in the motel? were you there too? if it is true that he is there, who are you to judge him? you are the God? ye who has no sin, cast the first stone!
hahahaha, another priest, ANOTHER priest, this is the not the first, and surely not the last, perhaps the idiots showing support are surprised it was with a woman, instead of a helpless child,
perhaps this will enlighten all of you, and show you that your christianity and all your religions are based on SEX/FERTITLITY cult worship,
look at the numbers of all the priest molestations, there is a world wide campaign underway, and you are happily the victims,
drown him, burn him, crucify him for all the world to see,
and the reason for so many women here offering support, he has been working on getting the right one in the right situation at the right time,
Mississauga, Canada
#82 Apr 15, 2008
No,there must be a big mistake. I don't believe this... Father Randy?? Father Randy was our Religion/ Social Ethics Teacher when I was in High school.. and our assistant Parish Priest when I was a cathechist in Bangued, Abra. I know, I know that's a very long time but you see, if he is like this, he should have done it before when he was younger. This is a shock for me and NO... this is not true! There's no way he can do this. May we know the girl... what she is? NO... I don't want to judge him or the girl. Oh my God... what really happenned? Our prayers for him...may the truth prevail!!!
Mississauga, Canada
#83 Apr 15, 2008
May God bless your soul too!!
#84 Jun 17, 2008
don't forget that Brother Randy has a cock also. H e is still a human being.
Wake up America, don't be idiot about this. please be realistic when you speak. Ensure brain is engaged before engaging mouth. I sthis clear for everyone out there?
#85 Jun 18, 2008
or alternatively don't pass judgment at all.
Petrozavodsk, Russia
#87 Aug 20, 2008
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#90 Apr 14, 2009
Marcus: Spoken like a true poser. Perhaps you took the vow of celebacy too because the security it provides precludes you from the realities of day to day life, child rearing and supporting/managing a family. No matter, let me break it down to simple fundamentals for you though articulation cannot substitute for experience. I'll concede that God is love and Love is critical to child rearing. However, God helps those who help themselves. Love doesn't pay bills, doesn't prepare a child for negotiating day to day life, doesn't nourish your body, doesn't pay for college and doesn't even keep the lights on in the rectory. Your oversimplification is misleading. Besides, you might be suffering from ambiguity associated with the English word "Love." As you may know, fatherly love is described in the Bible as "Agape" which is derived from the Greek word meaning "A Father's Love." Be clear that this term is far different from the sort of love Fr. Randy was offering to a young lady at Motel 6. That's a whole different kind of "love." Maybe not even "love" at all. In fact, it probably crosses over to a whole new word which falls into the category of one of the 7 Deadly Sins. We Christians refer to it as lust. And when a priest abuses his influence and authority in an effort to meet his own personal needs, it breaches the trust offered by God and the Vatican. It is the spiritual equivalent of Corporate CEOs misleading the investors. Priests "caught" with thier proverbial pants down need to be severely punished as an example to others on the verge of similar abomination. This may prevent others from a similar path. For every soul lead to the Altar, a single event such as this drives hundreds or thousands away. Allow me to suggest that you minister to your flock about things you understand. Discuss Scripture. Discuss philosophy. But stay clear of family issues. You wouldn't understand fatherhood if it crept up and hit you in the head with Moses's staff. Ministering to young ladies in hotel rooms isn't quite your forte...unless it's a secret. Either way, we both know it didn't do the poor victim any good. I say that if priests want to take a shot a husbandry and fatherhood, want to be a "family expert," then don't be a coward. Step out from behind the cloth and take a shot at providing for yourself and those you brought into the world. Otherwise, stick to quoting Scripture and relying upon cliches for the money you get in the collection basket. Just do the world a favor and don't exercise your vice in front of people seeking guidance. Those people need instruction from a Teacher. The Bible clearly points out that not everyone can be a teacher. Teacher's need to set a standard a bit higher than the rest because thier example can have a powerful impact - either negative or positive. There are good priests in teh world. Let them do the heavy lifting. It is obvious that you are too close to Randy to be objective. He is a disgrace to priests everywhere and should be exiled from the Roman Catholic Church until he gets his psychological and sexual predator issues under control. He obviously has an inflated view of his contribution to the congregation. I'm in favor of second chances, but it would require significant remorse and conciliatory action on his behalf. Moreover, it merits severe and decisive action from the Diocese. Perhaps a demotion to Altar Boy is appropriate. Whatever will keep him from harming others. I've had my own run in with Randy Benas. All those who know his true character have a responsibility to protect others from the same outcome as this poor woman. Have the courage to step up and reveal the wolf in sheep's clothing.
#91 Apr 14, 2009
Marcus: Your comment is both short-sighted and condescending. Marriage and relationship/family management is difficult enough. When one partner or the other approaches a priest for guidance, the expectation is that the priest will offer insight and wisdom regarding how the partners can overcome challenges, offer advice regarding how to best remedy problems and offer prayer for strength and perseverance. It doesn't take a rocket scientist to discover that neither partner is approaching the priest for sexual gratification and if they are - it's definitely not in the priest's job description to fulfill that request. That's a scenario equivalent to someone going to the doctor with pelvic pain, asking the priest for advice and the priest does a digital exam himself. What in the world was he thinking? And what are you thinking? Your short-sighted defense of Randy's lack of discretion leads readers to believe that your response is more emotional than intellectual. As William Shakespeare offered "Me thinks you protest too much..."
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Canyons chief sees no need for survey, investigation
Scott G Winterton, Deseret News
Call renewed for investigation into Canyons school district
SANDY — Canyons School District Superintendent David Doty said he would not call for an investigation into complaints his administration had censured employees, and he does not support the suggestion employees be surveyed anonymously to see if they have complaints.
Both items came up at a school board meeting Tuesday night, where administrative culture in the district was both praised and criticized. The discussion remained lively Wednesday, with news coverage of the meeting attracting a significant number of comments both supporting and criticizing the district's administration and the call for an investigation.
Doty's comments came on KSL Newsradio's Doug Wright show Wednesday morning as Doty answered Wright's questions and presented his view of the controversy in a 30-minute live interview. Doty said he honors and respects teachers in the district and wants their feedback, but he said he doesn't believe a survey is necessary.
"I have a big problem with anonymous surveys," he said.
As for an investigation, "If the board feels that's necessary, of course I will be willing to do that," Doty said. "Am I going to initiate it myself? No."
The call for an investigation is into allegations of intimidation by the top management of Canyons School District. Former and current district employees have come forward criticizing Doty and accusing him of inappropriately reprimanding district employees and in some cases, threatening their employment to ensure silence.
The board issued a statement Tuesday in support of Doty: "We are his direct supervisors, and for four years have worked closely with him as he has led our district," the statement reads. "We believed he was the right person to lead this district when we hired him four years ago. And we are even more convinced now that he is the right person to lead Canyons School District."
Board member Paul McCarty read the statement at Tuesday's meeting. Unknown is whether there was any dissent by individual board members. And the board members are not talking.
The Deseret News spoke briefly on Wednesday with board member Mont Millerberg, who said he did not want to be interviewed. Board member Kevin Cromar said he would not comment. Phone calls attempting to reach McCarty, Kim Murphy Horiuchi, Tracy Scott Cowdell, Sherril Taylor and Steve Wrigley were not returned.
Cromar himself came under fire from the school board when it voted in September to censure Cromar, accusing him of undermining Doty and spreading allegations about a fellow board member. Cromar cast the only vote against the censure.
The request for the survey and investigation came from school board candidate Chad Iverson, who is running against McCarty, who, along with Millerberg, is seeking re-election this year. Cromar's seat is also up for election; he is not seeking another term.
Iverson started an online petition on Friday that spells out the requests. The petition had 949 signatures Wednesday afternoon.
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Don't stress... It's free and easy to setup.
The Somers Tuskers girls lacrosse team won Monday's away conference game against North Salem by a score of 10-2.
(May 14, 2012: North Salem, NY 10560) In Monday's league battle, the visiting Somers Tuskers lacrosse team scored a nice 10-2 win over the North Salem Tigers.
The Tuskers now have a 4-3 record.
In their next game, the Tigers face the Hendrick Hudson Sailors (Montrose, NY) in a Section 1 I-B battle, on Tuesday, May 15. North Salem will attempt to move on its 3-11 season record. The Sailors come into the battle with a 4-2 record after their 18-16 non-league loss to Ossining (Ossining, NY).


text:
Find a copy in the library
Finding libraries that hold this item...
|Suspense fiction
|Material Type:
|Document Type:
|Visual material
|All Authors / Contributors:
Stieg Larsson; Reg Keeland; Bettendorf Public Library.
|9780307473479 0307473473
|OCLC Number:
|Books: The girl with the dragon tattoo by Stieg Larsson : translated from the Swedish by Reg Keeland. 1st Vintage Crime/Black Lizard mass-market ed. New York : Vintage Crime/Black Lizard, c2009, c2008. 644, 12 p. ; 18 cm.
Discussion guide includes: discussion guides, book reviews, biographies and background information about the author from various sources and comments page.
Includes an excerpt from Stieg Larsson's new thriller The girl who played with fire (p. [1]-12, after p. 644).
|1 box containing 12 books, 1 discussion guide ; in container 32 x 25 cm.
|Series Title:
|Discussions in boxes.
|Other Titles:
|[compiled by Hedy N.R. Hustedde].
The disappearance forty years ago of Harriet Vanger, a young scion of one of the wealthiest families in Sweden, gnaws at her octogenarian uncle, Henrik Vanger. He is determined to know the truth about what he believes was her murder. He hires crusading journalist Mikael Blomkvist, recently at the wrong end of a libel case, to get to the bottom of Harriet's disappearance. Lisbeth Salander, a twenty-four-year-old, pierced, tattooed genius hacker, possessed of the hard-earned wisdom of someone twice her age--and a terrifying capacity for ruthlessness--assists Blomkvist with the investigation. This unlikely team discovers a vein of nearly unfathomable iniquity running through the Vanger family, an astonishing corruption at the highest echelon of Swedish industrialism--and a surprising connection between themselves.--From publisher description.
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Related Subjects:(14)
- Missing persons -- Investigation -- Sweden -- Stockholm -- Fiction.
- Journalists -- Sweden -- Stockholm -- Fiction.
- Hackers -- Sweden -- Stockholm -- Fiction.
- Rich people -- Fiction.
- Corruption -- Fiction.
- Sweden -- Fiction.
- Stockholm (Sweden) -- Fiction.
- Hackers.
- Corruption.
- Journalists.
- Missing persons -- Investigation.
- Rich people.
- Sweden.
- Sweden -- Stockholm.


text:
Build a plastic heat bender or Nichrome controller
August 26, 2013
I am attempting to build a thermal plastic bender to create mounts and parts for my robots. Basically a piece of nichrome wire heats up a small area of the plastic which allows me to bend/form it by hand. The nichrome wire I have, came out of an old space heater. It is formed into 1/4 inch coil. I don't have a clue to the metal contact or diameter (pretty darn thick since it was an old heater.)
I tried connecting it directly to a 12v 2.6 Ah SLA battery. A short section of about 6 inches coiled. The direct connection proved to be too much current and almost instantly brought it to a bright glow. Probably 2-3 seconds before I disconnected it for fear it would burn out. Much to hot to use for plastic forming... Smelting gold, maybe :-)
The examples of the bender I have seen use a variac transformer to control the current. I don't have one, so my question is, will an adjustable power supply using a variable resistor / lm350 circuit have the same type of control 'dimming'/reducing the heat (or am I way off on the concept here?) using a circuit such as this: http://diyaudioprojects.com/Technical/Voltage-Regulator/
I am learning as I go, so I may be totally off in this application. But it seems it would act the same for a dc battery driven circuit (instead of an ac driven variac transformer.)
Here is what I think needs to happen.
The original heater had a type of thermostat to control the heat. Heat sensitive wire would allow contacts to close and send power to the coils. A type of mechanical voltage control. I can't place this 'thermostat' into the project. It would interfere with the plastic being above the heat source. So I am attempting to control the heat radiated by reducing/increasing the voltage to the heating element.
Thanks for any assistance.
It occurs to me...
You may want to take a look at 3d printer software. Its a bit overkill, yes, but something like Teacup will run on a regular arduino (328), can read a thermister (2, actually) and also control 2 mosfets to control the heat. All the PID stuff is done, it works great to control the temp of extruders and heated beds.
Again, overkill in that you would not be using any of the "CNC" part of the firmware, but it is an off-the-shelf solution, free, well documented and will do what you need it to.


text:
Alternative Titles
Japanese: D-1 デバステイター
Type: OVA
Episodes: 2
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Aired: Dec 11, 1992 to Feb 26, 1993
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