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subset: commoncrawl


text:
here the code first off:
It never loads the file even if its entered correctly. I did a test cout so i know its the infile line. My theory is that the FileLocation is taken as a literal not a variable because of the quotes. Problem is i cant built it without quotes, so how can i accomplish this? I know its a lame question but never tried it before.Code:
#include "stdafx.h"
#include <iostream>
#include <fstream>
#include <string>
using namespace std;
int main(int argc, char* argv[])
string FileLocation;
string Extension = ".cpp";
bool Quit = false;
ofstream outfile;
ifstream infile;
cout << "Enter path to file (no ext please): ";
FileLocation += Extension;
return 0;


text:
|Numķro de publication
|Type de publication
|Numķro de demande
|Date de publication
|23 janv. 1979
|Date de dķp¶t
|4 dķc. 1974
|Date de prioritķ
|4 dķc. 1973
|Autre rķfķrence de publication
|Numķro de publication
|George D. Appleyard, Anthony D. Caunt, Michael S. Fortuin, Thomas G. Heggs
|Cessionnaire d'origine
|Imperial Chemical Industries Limited
|Exporter la citation
|BiBTeX, EndNote, RefMan
|Citations de brevets (9), Rķfķrencķ par (47), Classifications (20)
|Liens externes: USPTO, Cession USPTO, Espacenet
The present invention relates to the polymerisation of olefine monomeres, and catalysts for use in such polymerisation.
According to the present invention there is provided an olefine polymerisation catalyst comprising
(a) a solid TiCl3 -containing component having a specific surface area of at least 50 meters2 /gm;
(b) at least one organo-metallic compound of aluminium or a non-transition metal of Groups IA or IIA; and
(c) at least one Lewis Base Compound.
The catalyst also preferably includes a substituted or unsubstituted polyene for example cyclic polyenes such as cycloheptatriene, cyclooctatriene or cyclooctatetrene.
The solid TiCl3 -containing component, which will hereafter be referred to simply as "TiCl3," has a high specific surface area and this is preferably at least 75 meters2 /gm and conveniently may be at least 100 meters2 /gm, particularly useful results being obtained when the specific surface area is from 150 up to 200 meters2 /gm. The term "specific surface area" as used herein is the surface area of one gramme of solid TiCl3, the surface area having been measured using the technique of BS 4359/1. The particles of TiCl3 can have a high porosity for example about 0.10 cm3 /gm, or greater. The term "porosity" as used herein is in the pore volume of pores of diameter less than 300A as measured by nitrogen adsorption using the technique described in "Advances in Catalyst," (1957), Vol. IX, pages 143 to 154. The particle diameter may be from 5 to 100 microns. Typically the particles are formed of micro particles which have a diameter of from 0.05 to 1 micron. The micro particles have a large pore volume which contributes to the overall porosity of the particles whilst the space between the micro particles contributes only a relatively minor proportion to the total porosity of the particles. The density of the TiCl3 particles is typically at least 0.6 gm/cm3 and is usually in the range 0.8 to 1.3 gm/cm3.
The TiCl3 component of the catalyst is conveniently prepared by reducing TiCl4 with an organo-aluminium compound, separating the reduced solid from the reaction medium, treating the reduced solid with a complexing agent, separating off any excess complexing agent, contacting the treated solid with TiCl4 and isolating the resulting TiCl3 component.
The various stages of the preparation of the TiCl3 are preferably effected in the presence of a suitable inert hydrocarbon diluent which is conveniently an aliphatic or cycloaliphatic hydrocarbon compound such as hexane, decane or dodecane.
The organo-aluminium compound used is conveniently an aluminum alkyl of formula AlR'x X"3-x where
R' is an alkyl group having 1 to 18 carbon atoms;
x" is a halogen atom; and
x is a number such that 0<x≦0<x≦.
It is preferred that x is from 1.5 up to 2.5 especially from 1.5 up to 2.0. The reaction between the TiCl4 and the organo-aluminium compound is preferably carried out by mixing the TiCl4 and the organo-aluminium compound at a relatively low temperature below about 20░ C, very conveniently at 0░ C. The time of mixing of the compounds will be dependent on the reaction conditions and the reactants used, however times of 30 minutes to 16 hours, preferably 2 to 10 hours can be used. When the organo-aluminium compound is a dialkyl aluminium halide, or a material including a dialkyl aluminium halide, we prefer to use from 0.6 up to 1.5 moles, for example 1.0 mole of the dialkyl aluminium halide for each mole of titanium tetrachloride. When the addition of the organo-aluminium compound has been completed, the reaction mixture containing the TiCl3 formed may be heated for a period of time, typically up to 4 hours, for example one hour, to a temperature in the range from 20 up to 120░ C, preferably from 20 up to 80░ C.
The complexing agent is one which is capable of forming complexes with one or more of the components of the reduced solid. Typical complexing agents are organic compounds containing one or more atoms or groups which have one or several free electron pairs capable of co-ordination with one of the constituents of the reduced solid. Such compounds conveniently include a non-metallic element of group V or VI of the Periodic Table, for example ethers, thioethers, thiols, phosphines and amines. It is particularly preferred to use as complexing agents ethers, thioethers and thiols of the formulae:
R"--O--R"'; R"--S--R"'; and R"--S--H
where R" and R"' which may be the same or different are hydrocarbyl groups having from 1 to 15 carbon atoms. We have found that the ethers, especially those wherein each hydrocarbyl group is an alkyl group containing from 4 to 10 carbon atoms, or particularly 4 to 6 carbon atoms, such as di-n-butyl ether or diiso-amyl ether, give particularly useful forms of TiCl3. The amount of complexing agent used will be dependent on the particular compound used but, in general, for each mole of TiCl3 which is present in the reduced solid, there is used at least 0.4 moles and preferably 0.8 moles, for example 1.0 mole, of the complexing agent. It is possible to use large proportions of the complexing agent, but no significant improvement in the catalyst properties are achieved when using proportions in excess of 3 moles of complexing agent for each mole of TiCl3.
The treated solid is finally contacted with TiCl4, this contacting being effected at a temperature of up to 100░ C, particularly from 40░ C up to 80░ C. The contacting with TiCl4 can be carried out in pure TiCl4 or in a solution of TiCl4 in a hydrocarbon medium, the concentration of TiCl4 preferably being from 20 up to 40% by volume.
The quantity of TiCl4 used should be at least 0.1 moles, and is preferably at least 1.0 mole, for each mole of TiCl3 present in the treated solid. The reaction of the treated solid with the TiCl4 is dependent on temperature of contacting and amount and concentration of TiCl4, but is generally between 30 minutes and 4 hours, preferably 1 to 3 hours.
Thus, a preferred form of TiCl3 is prepared by mixing together TiCl4 and an organo-aluminium compound of formula
AlR'.sub.x.sbsb.1 X".sub.3 -x.sub.1
at a temperature not exceeding 20░ C, heating the reaction mixture to a temperature of from 20░ C up to 80░ C, separating the reduced solid from the reaction medium, treating the reduced solid from the reaction medium, treating the reduced solid with an ether of formula
R.sup.1V --O--R.sup.V,
separating off any excess ether, contacting the treated solid with TiCl4 and isolating the resulting TiCl3 component, all stages being effected in the presence of an inert hydrocarbon diluent; wherein
R' is an alkyl group having 1 to 18 carbon atoms;
X" is a halogen atom;
RlV and RV can be the same or different and are alkyl groups containing 4 to 6 carbon atoms; and
x1 is from 1.5 up to 2.0.
It will be appreciated that the TiCl3 as prepared in accordance with the foregoing procedure is not pure titanium trichloride but also includes other materials complexed with the titanium trichloride, such other materials including aluminium halides and hydrocarbyl aluminium halides and residual amounts of the complexing agent.
The organo-metallic compound which is component b) of the catalyst may be a Grignard reagent which is substantially ether free, or Mg(C6 H5)2. Alternatively the organo-metallic compound may be complex of an organo-aluminium compound and an organo-metallic compound of a metal of Groups IA or IIA, such as, for example Mg(AlEt4)2 or a lithium aluminium tetraalkyl. It is preferred to use an organo-aluminium compound such as an aluminium hydrocarbyl sulphate, or an aluminium hydrocarbyloxyhydrocarbyl or particularly an organo-aluminium compound of the formula
AlR.sub.2 X
where R is a hydrocarbyl group and X is a hydrocarbyl group or a hydrogen or halogen atom. If desired a mixture of organo-aluminium compounds may be used such as a mixture of an aluminium trihydrocarbyl and a dihydrocarbyl aluminium halide, for example a mixture of triethyl aluminium and diethyl aluminium chloride. Very conveniently component b) of the catalyst is a halogen-free compound, particularly an aluminium trihydrocarbyl compound such as an aluminium trialkyl for example aluminium triethyl.
The Lewis Base which is component c) of the catalyst can be any Lewis Base which is effective to alter the activity and/or stereospecificity of a Ziegler catalyst system. A wide range of such Lewis Bases have been proposed which have such an effect and these include the amines, particularly the cyclic amines such as pyridine, quinoline, isoquinoline and alkyl substituted derivatives; diamines such as N,N,N',N'-tetramethylethylenediamine; alkanolamines such as N,N-dimethyl-N-ethanolamine; amides; urea and thiourea and the substituted derivatives thereof such as N,N,N',N'-tetramethylurea; orgao-phosphorus compounds including the phosphites, phosphates, phosphines and phosphine oxides, such as triphenyl phosphine oxide, bis(dimethylamino-) ethoxyphosphine oxide and hexamethylphosphoric triamide; ethers; esters such as methylmethacrylate; ketones; alcohols; the sulphur containing analogues of the ethers, esters, ketones and alcohols and organo-silicon compounds such as the silanes and siloxanes. It will be appreciated that the effect of, and the optimum conditions for using, a Lewis Base will depend on the particular Lewis Base selected. Catalyst systems including Lewis Base compounds or complexes including Lewis Base compounds are disclosed, inter alia, in British patent specifications Nos. 803,198; 809,717; 800,998; 896,509; 920,118; 921,954; 933,236; 940,125; 966,025; 969,074; 971,248; 1,013,363; 1,049,723; 1,122,010; 1,150,845 and 1,208,815; Dutch Patent Application 70 15555 and published German Patent Application 2,130,314. Of the Lewis Bases which can be used in the catalyst of the present invention the amines, particularly the diamines such as N,N,N',N'-tetramethylethylenediamine, and the cyclic amines such as pyridine, quinoline and isoquinoline are useful and the organo-phosphorus compound particularly the organo-phosphine oxide derivatives such as hexamethylphosphoric triamide are especially preferred.
Other Lewis Bases which may very conveniently be used are phosphorus compounds selected from materials of the formulae:
______________________________________(cl) T.sub.3-n P(Q).sub.a (EZG).sub.n ;(c2) ##STR1##(c3) T".sub.2 P(Q).sub.a X'P(Q).sub.a T".sub.2______________________________________
each T is independently halogen, a hydrocarbyl group, a group --NT"'2 or --OT"', or a heterocyclic group;
T' is T or a group (E--Z--G);
T" is T' or both the T" groups which are attached to the same P atom together form a group ##STR2## T'" is a hydrocarbyl group; X' is --O--, --NT""--,--E(CH2)m E-- or ##STR3## T"" is a hydrogen or T"", L is a bivalent hydrocarbyl radical and each L may be the same or different;
each E is --O--, --S-- or --NT""-- and may be the same or different;
G is --OT"", --ST"", --NT""2, --PT""2 or a heterocyclic ring system whereof the heteroatom is O, S, N or P;
Q is an oxygen or sulphur atom;
Z is a bivalent hydrocarbyl radical such that E and G or E and E are separated by not more than 3 carbon atoms;
each a is independently zero or 1;
m is a positive integer, and
n is 1, 2 or 3.
In the phosphorus compounds of the type (c1), (c2) and (c3), the groups T and T" attached to a given phosphorus atom are conveniently the same. In compound (c3) it is particularly convenient if all the groups T" are the same. The groups T, T' and T" can be alkylamino groups --NT2 '" or alkoxy groups --OT'" wherein T'" is an alkyl group such as methyl or ethyl. Alternatively, the groups T, T' and T" may be heterocyclic groups such as pyridyl, pyrrolyl, pyrrolidyl or piperidyl and may be attached to the phosphorus atom through a carbon or nitrogen atom. If T' or T" is a group (E--Z--G), this can be a group derived from, for example an hydroxy ether; an N,N-substituted alkanolamine, an N,N,N'-substituted diamine or an N,N-substituted aminothiol group. The group G can be derived from a heterocyclic compound such as pyridine, quinoline, isoquinoline, etc. If both of the groups T" attached to the same phosphorus atom together form a group ##STR4## this can be the divalent residue from a glycol, an N-substituted aminoalcohol, an N,N'-substituted diamine or an N-substituted aminothiol. In compounds (c1) and (c2) it is preferred that a is one and the group Q is oxygen. Conveniently, but not necessarily, in compounds (c3) the value of each a is the same, that is both are either zero or preferably one, and similarly it is preferred that both of the groups Q are the same and are oxygen.
In compound (c2), it is preferred that at least one of the groups E is --NT'"--. If a is zero, that is when the phosphorus is trivalent it is preferred that group T' is (E--Z--G).
In compund (c3), the group X' can be derived from a monoamine or an acyclic or cyclic diamine. If the group X' is of the type
--NT'" (CH.sub.2).sub.m NT'"--,
the group T'" is preferably a hydrocarbyl group such as methyl and m is preferably 2 or 3. If the group X' is of the type ##STR5## it is preferred that the groups L are both the same and are alkylene groups of the type
--(CH.sub.2).sub.m --,
particularly ethylene groups when X' is derived from piperazine. We have obtained satisfactory polymerisation systems using as the phosphorus compound (c3), materials in which the group X' is
--N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3)--; ##STR6## or particularly --O--
In compound (c3) when each a is zero it is preferred either that X' is derived from an acyclic or cyclic diamine or that at least one T" is a group (E--Z--G).
Phosphorus compounds of the type (c1), (c2) and (c3) which may be used as the third component of the catalyst include compounds of the formulae I to XXVIII.
______________________________________[(CH.sub.3).sub.2 N].sub.2 P(O)N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 I(CH.sub.3).sub.2 NP(O)[N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2].sub.2 II[(CH.sub.3).sub.2 N].sub.2 P(O)OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 III(CH.sub.3).sub.2 NP(O)[OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 ].sub.2 IV ##STR7## V ##STR8## VI ##STR9## VII ##STR10## VIII ##STR11## IX ##STR12## X[(CH.sub.3).sub.2 N].sub.2 P(O)N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3)P(O)[N(CH.sub.3).sub.2 ].sub.2 XI ##STR13## XII[(CH.sub.3).sub.2 N].sub.2 P(O)OP(O)[N(CH.sub.3).sub.2 ].sub.2 XIII ##STR14## XIV ##STR15## XV[(CH.sub.3).sub.2 N].sub.2 P(O)OP(O)(OC.sub.2 H.sub.5).sub.2 XVI[(C.sub.2 H.sub.5).sub.2 N].sub.2 P(O)OP(O)[N(CH.sub.3).sub.2 ].sub.2 XVII[(CH.sub.3).sub.2 N].sub.2 P(S)OP(O)[N(CH.sub.3).sub. 2 ].sub.2 XVIII ##STR16## XIX ##STR17## XXP[OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 ].sub.3 XXIP[N(CH.sub.3).sub.2 ][OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 ].sub.2 XXIIP[N(CH.sub.3).sub.2 ].sub.2 [OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 XXIII ##STR18## XXIV ##STR19## XXVP[OCH.sub.2 CH.sub.2 OCH.sub.3 ].sub.3 XXVIP[OC.sub.2 H.sub.5 ][OCH.sub.2 CH.sub.2 OCH.sub.3 ].sub.2 XXVIIP[N(CH.sub.3).sub.2 ].sub.2 [N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2] XXVIII______________________________________
it is preferred to use compounds of the formula I to XIX, for example those of formulae I, V and XIII.
Alternatively, the Lewis Base compound can be an organo-phosphine oxide derivative wherein at least one of the groups attached to the phosphorus atom is a heterocyclic group containing more than three, preferably five or six, atoms in the ring and attached to the phosphorus atom through either a ring carbon atom or ring heteroatom, catalysts containing such phosphorus compounds being described in our copending British Patent Application No. 7989/73. A further Lewis Base compound which may be used is a phosphine oxide wherein the phosphorus atom is included in an endocyclic ring system, which also includes three other heteroatoms, catalysts containing such phosphorus compounds being described in our copending British Patent Application No. 7988/73.
Catalysts in accordance with the present invention are of high polymerisation activity and stereospecificity. In addition to the three components a), b) and c), the catalyst preferably also includes a substituted or unsubstituted polyene, the presence of which gives a further improvement in the polymerisation characteristics of the catalyst system. The polyene may be an acyclic polyene such as 3-methylheptatriene-(1,4,6) or a cyclic polyene such as cyclooctatriene, cyclooctatetraene or particularly cycloheptatriene or may be a derivative of such polyenes. Such derivatives can be substituted with alkyl or alkoxy groups as in methylcycloheptatriene, dimethylcycloctatetraene and methoxycycloheptatriene or may be tropylium salts, tropylium complexes, compounds of the type ##STR20## tropolone and its derivatives of the type ##STR21## or tropones of the formula ##STR22## where M' is hydrogen, halogen, or a hydrocarbyl group, particularly an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl or alkaryl group wherein the alkyl group has 1 to 20 carbon atoms or a condensed benzene ring having two carbon atoms in common with the cycloheptatriene ring;
M" is a monovalent group containing at least one of the elements N, S or O;
M'" is a hydrocarbyl group of 1 to 20 carbon atoms, halogen or M";
M1v is the same as M' and/or M";
Rv1 is a hydrocarbyl group having 1 to 20 carbon atoms, which may be substituted with an alkoxy- or a hydrocarbylamino-group
c and d are integers wherein c + d ≦ 7 and usually 2 or less, particularly one;
e and f are integers wherein e + f ≦ 6; and g is an integer wherein g ≦ 6.
Tropylium salts and tropylium complexes are salts of cycloheptatriene which may be prepared by the process described in Dokl. akad. Nauk, USSR, 113, page 339 (1957). It will be appreciated that there are many derivatives of the type described including, for example methoxyethyltropylether ##STR23##
The proportions of the various catalyst components can be varied widely depending both on the materials used and the absolute concentrations of the components. However, in general for each molecular proportion of the TiCl3 which is component a) of the catalyst, there may be present from 0.1 up to 20 molecular proportions of component b) and from 0.01 up to 10 molecular proportions of component c), with the amount, in moles, of component c) not being greater than the amount, in moles, of component b). It is particularly preferred to use from 0.5 up to 15, and especially 1.0 up to 8 molecular proportions of component b) and from 0.05 up to 5.0 and especially 0.2 up to 2.0 molecular proportions of component c).
If the catalyst also includes a polyene, the molecular proportions of the polyene plus the Lewis Base should preferably, in total, be less than the molecular proportion of component b) (the organo-metallic compound) which is present in the catalyst. For each molecular proportion of component b), the molecular proportion of the polyene is conveniently in the range from 0.01 up to 1.0, especially from 0.05 up to 0.5, for example 0.2.
A preferred catalyst within the present invention comprises a) one molecular proportion of a solid TiCl3 containing component which is the product of mixing together TiCl4 and an organo-aluminium compound of formula
AlR'.sub.x.sbsb.1 X".sub.3-x.sbsb.1
at a temperature not exceeding 20░ C, heating the reaction mixture to a temperature of from 20 up to 80░ C, separating the reduced solid from the reaction medium, treating the reduced solid with an ether of formula
R.sup.IV --O--R.sup.V,
separating off any excess ether, contacting the treated solid with TiCl4 and isolating the resulting TiCl3 component, all stages being effected in the presence of an inert hydrocarbon diluent; b) from 0.1 up to 20 molecular proportions of a trihydrocarbyl aluminium compound; c) from 0.1 up to molecular proportions of a Lewis Base compound which is a diamine, a cyclic amine or an organo-phosphorus compound including compounds of the type (c1), (c2) and (c3) and d) from 0.01 up to 1.0 molecular proportions for each mole of component b) of a substituted or unsubstituted polyene which is cyclooctatriene, cyclooctatetrene or cycloheptatriene or alkyl or alkoxyl derivatives thereof; wherein the total amount in moles of components c) and d) does not exceed the amount in moles of component b) and wherein
R' is an alkyl group having 1 to 18 carbon atoms;
X" is a halogen atom;
Riv and RV can be the same or different and are alkyl groups containing 4 to 6 carbon atoms; and
x1 is from 1.5 up to 2.0.
The catalysts of the present invention are particularly suitable for the polymerisation and copolymerisation of mono-α-olefines.
Thus, according to a further aspect of the present invention at least one mono-α-olefine, or a mixture of at least one mono-α-olefine and ethylene, is contacted with a polymerisation catalyst comprising a) a solid TiCl3 -containing component having a specific surface area of at least 50 meters2 /gm; b) at least one organo-aluminium compound of the formula AlR2 X; c) at least one Lewis Base compound; and optionally d) a substituted or unsubstituted cyclic polyene; wherein
R is a hydrocarbyl group; and
X is a hydrocarbyl group, hydrogen or halogen.
Any mono-α-olefine monomer which is capable of being polymerised using a Ziegler catalyst may be polymerised by the process of the present invention. Thus, monomers which can be polymerised by the present process include butene-1, and 4-methylpentene-1 and particularly propylene. The olefines may be copolymerised either together or with ethylene, and such a copolymerisation is conveniently effected using a sequential polymerisation process such as described in British Patents 970, 478; 970, 479 and 1,014,944.
We have found that the process of the present invention can be used for the polymerisation of propylene to give a high yield of polymer relative to the amount of catalyst used and also a relatively low proportion of the undesirable soluble polymer.
As noted, catalysts in accordance with the present invention can be used to prepare a large proportion of polymer for the use of a small quantity of catalyst. It is well known that catalysts of the "Ziegler" type are susceptible to the effects of impurities and the activity and stereospecificity of such catalysts can be affected in a detrimental manner by the presence of small quantities of impurities, particularly oxygen and polar compounds such as water and alcohol in the monomer and/or diluent when used. Thus, for the polymerisation of olefine monomers using Ziegler catalysts, it is known to use pure monomers and diluents. However, when using catalysts in accordance with the present invention, these can be used in smaller proportions than the conventional Ziegler type catalyst and accordingly are more susceptible to any impurities present in the system. Thus, for use with the catalyst of the present invention, we prefer that the monomers, and any diluents, which are of normal commercial purity, are subjected to a further purification procedure.
Any suitable purification treatment can be used and the treatment can be effected in more than one stage if desired. The particular purification treatment used will be dependent on the purity of the starting materials.
Satisfactory purity can be achieved in most cases by passing the monomer (and diluent, if used) through a bed of a material which is capable of absorbing the impurities contained in the monomer of diluent, for example as described in British patent specifications Nos. 1,111,493 and 1,226,659.
Using catalysts in accordance with the present invention, polymerisation can be carried out in the presence or absence of an inert diluent such as a suitably purified paraffinic hydrocarbon. If a diluent is not used, polymerisation can be effected in the liquid phase using excess liquid monomer as the suspension medium for catalyst and polymer product. If the monomer is used in the gaseous phase, polymerisation can be effected using any technique suitable for effecting a gas/solid reaction such as a fluidised bed reactor system.
Polymerisation may be effected either in a batch manner or on a continuous basis. The catalyst components may be introduced into the polymerisation vessel separately but it may be preferred, particularly if polymerisation is being effected on a continuous basis, to mix all the catalyst components together before they are introduced into the polymerisation reactor. Alternatively, not all of the catalyst is added at the beginning of the polymerisation. Thus, a proportion of the catalyst may be added to initiate polymerisation and further quantities of one or more of the catalyst components are added at one or more times during the polymerisation. Conveniently at least 25% of each catalyst component is added to initiate polymerisation, the remaining catalyst components being added during the polymerisation. Since feeding a slurry of TiCl3 may be inconvenient, it may be preferred that all of the TiCl3 is added, together with some of each of the other catalyst components, to initiate polymerisation and the rest of the other catalyst components are added during the polymerisation. It is desirable that in any mixing of the catalyst components the TiCl3 component is not allowed to come into contact with the Lewis Base compound which is component c) in the absence of the organo-metallic compound which is component b) of the catalyst.
The polymerisation can be effected in the presence of a chain transfer agent such as hydrogen or a zinc dialkyl, in order to control the molecular weight of the product formed.
Using catalysts in accordance with the present invention, particularly catalysts wherein the Lewis Base is a phosphorus compound and which also include a cyclic polyene, we have been able to polymerise propylene to obtain a high yield, relative to the amount of catalyst used, of a polymer having a high flexural modulus which in some cases may be as high as that of commercially available propylene polymers which have been obtained in a lower yield and from which a catalyst removal step is necessary.
Thus, as a further aspect of the present invention there is provided a propylene polymer wherein the titanium and halogen contents of the polymer derived from the residual catalyst in the polymer, are respectively not more than 60 parts per million (ppm) by weight and not more than 250 ppm by weight, and the flexural modulus of the polymer is at least one GN/m2, said polymer being the direct product of polymerisation.
The flexural modulus of the polymer is the modulus as measured by the apparatus described in Polymer Age, March 1970, pages 57 and 58 at 1% skin strain after 60 seconds at 23░ C and 50% relative humidity using a test strip as described in Examples 1 to 15. The halogen contained in the polymer will be predominantly, or solely, combined chlorine and the chlorine content is preferably less than 200 ppm, particularly less than 150 ppm, typically from 100 up to 200 ppm.
The titanium content is preferably less than 55 ppm and is typically in the range from 20 up to 55 ppm.
the titanium and chlorine content of the polymer may be determined by any suitable analytical technique and we have found X-ray fluorescence spectrometry to be a particularly convenient technique of analysis.
In general, polymers in accordance with the present invention, particularly propylene homopolymers, when formed into test strips, have a flexural modulus in excess of 1.10 GN/m2, usually at least 1.15 GN/m2. Preferred polymers have a flexural modulus of at least 1.20 GN/m2 and particularly preferred polymers have a modulus of at least 1.30 GN/m2 and especially of at least 1.40 GN/m2, for example as high as 1.45 GN/m2. Thus propylene homopolymers in accordance with the present invention have a flexural modulus in the range from 1.00 up to 1.50, or higher, GN/m2.
Propylene polymers in accordance with the present invention are the direct product of polymerisation and are obtained without subjecting the polymer to any treatment to remove either catalyst residues or undesirable polymeric materials such as stactic polymers, polymers of low crystallinity or crystalline polymers of low molecular weight, from the polymerisation product. Whilst the polymers of the present invention are obtained without an extraction process, the flexural modulus can be increased by extraction with a suitable solvent. Whilst it is possible to use a high boiling aliphatic hydrocarbon such as heptane for such an extraction, we have found that extraction with low boiling solvents which extract only a small proportion, typically between 2 and 4% by weight of the polymer, can produce a significant increase in the modulus of the polymer. Thus, by extraction of 3.7% by weight of a polymer using diethyl ether, the flexural modulus increased from 1.22 GN/m2 up to 1.44 GN/m2.
Polymers in accordance with the present invention have a high molecular weight as indicated by the melt flow index measured according to ASTM Test Method D 1238-70, using Condition N (that is a temperature of 190░ C and a weight of 10 kgm). Polymers in accordance with the present invention have a melt flow index of less than 200. Preferred polymers have a melt flow indes of less than 100, particularly less than 50, for example between 5 and 50.
Propylene polymers in accordance with the invention are in the form of powder and this typically has particles which are essentially all in the size range from 400 up to 1200 microns, and the major proportion of the particles, that is at least 50%, and in some cases 90% or more, by weight, are in the range from 500 up to 850 microns. The powder may be used directly or can be subjected to an extrusion process to form laces which are cut into granules. The polymer, either in the form of powder or granules, can be used in the known manner for the production of injection moulded articles or extruded articles, or other products.
Various aspects of the present invention will now be described with reference to the following Examples which are illustrative of the invention. In all the Examples, the surface area of the titanium trichloride-containing component, was at least 50 meters2 /gm.
(1) Reaction of TiCl4 with organo-aluminium compound
770 ml of a hydrocarbon diluent comprising a mixture of C12 isomers (mainly pentamethylheptane) and 385 ml of TiCl4 were introduced, under an atmosphere of nitrogen into a 5 liter reaction vessel and stirred at 250 rpm. The solution of TiCl4 in the diluent was cooled down to 0░ C. Over a period of 8 hours, a 25% by weight solution of aluminium ethyl sesquichloride (which contained equal molar proportions of ethyl aluminium dichloride and diethyl aluminium monochloride) in the same diluent, was added to the reactor whilst stirring and maintaining the temperature at 0░ C. Sufficient of the sesquichloride solution was added to provide 0.9 moles of diethyl aluminium monochloride for each mole of TiCl4.
After the addition of the aluminium ethyl sesquichloride solution had been completed, the reaction medium, which consists of a suspension of fine particles at 0░ C, was stirred for 2 hours. The solid reaction product, a brown coloured material, was separated from the liquid phase by filtration.
(2) Treatment of the solid reaction product with a complexing agent.
A quantity of the solid product obtained in the first stage and containing 1.68 moles of TiCl3 was stirred at 35░ for 1 hour, with a solution consisting of 2230 ml hexane and 336 ml diisoamyl ether.
The resulting solid material was separated from the liquid phase without washing.
(3) Reaction of the solid obtained from stage 2) with TiCl4
The solid from stage 2) was suspended in a solution of 662 ml hexane and 442 ml of TiCl4 and stirred for 2 hours at 65░. The liquid phase was then separated and the resulting solid product, the "solid catalyst complex," was washed 4 times with a liter of hexane at 25░ C and then once with a liter of hexane at 65░ C. The solid catalyst complex was separated from the hexane and dried with pure dry nitrogen.
(4) Properties of the solid catalyst complex
The specific surface area of the material obtained in the manner described was found to be 109 m2 /gm. The solid catalyst complex was then used to polymerise propylene as set out in detail hereafter.
Polaymerisation was effected using propylene which had been purified by passing gaseous propylene in turn through a column (3 inches diameter, 3 feet length) containing 1/16 inch granules of Alcoa F1 alumina at 50-60░ C, and then through a similar column containing BTS catalyst (Cupric oxide reduced to finely divided metallic copper on a magnesium oxide support) at 40-50░ C, condensing the issuing gas and passing the liquid propylene through four columns (all 3 inches diameter; two of 3 feet in length, two of 6 feet in length) at 25░ C, each containing 1/16 inch pellets of Union Carbide 3A molecular sieves.
This treatment reduced the water content of the monomer from 5-10 ppm by volume to <1 ppm by volume and the oxygen content from 1-2 ppm by volume to <0.5 ppm by volume. The level of inert compounds (nitrogen, ethane, etc.) was unchanged at 0.3% and the level of unsaturated hydrocarbons (allene, methyacetylene, etc.) was unchanged at <1 ppm.
Polymerisation was carried out in a stainless steel autoclave, of total capacity 8 liters, which was fitted with a vertical anchor stirrer. The autoclave was heated to 70░ C, evacuated, and the vacuum was released with propylene. The autoclave was then evacuated again and the procedure repeated 5 times. A solution of aluminium triethyl (8 gm millimoles) in n-heptane (6.5 ml) was mixed with a Lewis Base and a cyclic polyene (when used). When the Lewis Base was octamethylpyrophosphoramide benzene (0.84 ml) was also added to dissolve the Lewis Base. This mixture was injected into the above-described autoclave containing propylene gas at 35░ C and 2 p.s.i. gauge. A suspension in 1.8 ml of an inert high-boiling hydrocarbon of 1 gram millimole of the titanium trichloride prepared as described above, was injected into the autoclave and then, within 5-10 seconds, 5 liters of liquid propylene were added, the stirrer being operated at 150 rpm. This propylene addition was effected by allowing 5.5 liters of liquid propylene to transfer from a burette at 50░ C to the autoclave. Hydrogen (200 gram millimoles) was added and the temperature of the autoclave contents was raised to 65░ C over 10 minutes. The hydrogen was commercially available hydrogen (99.99% pure) wich had been further purified by passing through a column (8 inches by 4 feet in length) containing a molecular sieve material (Union Carbide 3A) at 20░ C. The hydrogen was stored in the sieve column and drawn off as required. Polymerisation was allowed to proceed at a temperature of 65░ C and a pressure of 435 p.s.i. gauge. More hydrogen (20 gram millimoles on each occasion) was added after 10, 25, 45, 80 and 120 minutes from the time of the first hydrogen addition. After polymerisation for 21/2 hours, (in some cases polymerisation was terminated after μ hour, and only the first two additions of hydrogen were made), the autoclave was vented over a period of 10 minutes to remove unpolymerised propylene, and free-flowing, grey powder was obtained. The polymerisation conditions are set out in Table 1. In all examples the catalyst contained 1 gm millimole of TiCl3 and 8 gm millimoles of aluminium triethyl.
TABLE 1__________________________________________________________________________Example or ConversionComparative Lewis Base Polyene (mM) Time gm/mMol TiCl.sub.3Example Type (a) mMol Type (b) mMol (hours) (c)__________________________________________________________________________1 HMPT 0.8 CHT 0.8 21/2 19752 HMPT 0.8 -- NIL 21/2 950A -- NIL -- NIL 3/4 14003 HMPT 1.6 CHT 1.6 21/2 14804 PDEPT 0.8 -- NIL 21/2 13055 PDEPT 0.8 CHT 0.8 21/2 13256 OMPA 0.8 -- NIL 21/2 13907 OMPA 0.8 CHT 0.8 21/2 12008 DDDPO 0.8 -- NIL 21/2 14009 DDDPO 0.8 CHT 0.8 21/2 105010 Pic 0.8 -- NIL 3/4 130011 Pic 0.8 CHT 0.8 21/2 141012 TPPO 0.8 -- NIL 3/4 170013 TPPO 0.8 CHT 0.8 21/2 134514 TOTPO 0.8 CHT 0.8 21/2 150015 OMPA 0.8 COT 0.8 21/2 520__________________________________________________________________________ Notes to Table 1 a) HMPT is hexamethylphosphoric triamide pDEPT is N,N,N', N',N"-pentamethyl-N"-β-dimethylamino-ethylphosphoro triamide (Formula I) OMPA is octamethylpyrophosphoramide (Formula XIII) DDDPO is 2-dimethylamino-1,3-dimethyl-1,3,2-diaza-phospholidine-2-oxide (Formula V) Pic is γ-picoline TTPO triphenylphosphine oxide TOTPO is ##STR24## b) CHT is 1,3,5-cycloheptatriene COT is cyclooctatetraene c) Calculated on amount of polymer obtained and quantity of TiCl.sub.3 nominally used.
The properties of the polymers obtained were then determined. The flexural modulus was measured using a cantilever beam apparatus as described in Polymer Age, March 1970, pages 57 and 58. The deformation of a test strip at 1% skin strain after 60 seconds at 23░ C and 50% relative humidity was measured. The test strip which had dimensions of approximately 150 ū 19 ū 1.6 mm was prepared by mixing 23 g of the polymer, which had been dried for 3 hours at 90-100░ C in a stream of hot nitrogen, with 0.1% by weight of an antitoxidant (`Topanol` CA), and adding the mixture to a Brabender Plasticiser, at 190░ C, 30 rpm and under a load of 10 kg to convert it to a crepe. The crepe was placed within a template, between aluminum foil and pressed by means of an electric Tangye Press at a temperature of 250░ C. The pressing was pre-heated for a period of six minutes, under just enough pressure to make the polymer flow across the template, that is with an applied force of about 1 ton. After the pre-heat period, the applied force was raised to 15 tons in 5 ton increments, de-gassing (that is releasing pressure) every 5 tons. After 2 minutes at 15 tons, the press was cooled by means of air and water for 10 minutes or until room temperature was reached.
The plaque was then cut into strips of dimensions 150 ū 19 ū 1.6 mm. Duplicate strips of each polymer were placed into an annealing oven at 130░ C, and after 2 hours at this temperature the heat was switched off and the oven cooled to ambient temperature at 15░ C. per hour.
The melt flow index was measured by ASTM Test Method D 1238-70, Condition N (190░ C and 10 kgm). The fraction of polymer soluble in boiling heptane was determined by Soxhlet extraction for 16 hours using about 150 mls of heptane and 5 gms of polymer. The Ti contents of the polymers were calculated from the yield of polymer relative to catalyst and the Ti and Cl contents were determined experimentally by X-ray fluorescence spectrometry. The incident X-rays were obtained from a chrome anode. The net intensity ratios of the Tikα and ClKα lines were compared with those obtained from samples which had also been chemically analysed. The precision of analysis is ▒ 1 ppm for Ti and ▒5 ppm for Cl.
The results obtained are set out in Table 2.
TABLE 2__________________________________________________________________________ % wt Hot Heptane FlexExample or Cl (ppm) (g) Soluble ModComparative Ti (ppm) Calc. Polymer (GN/m.sup.2) MFI Example Calc. Found (h) Found (d) (e) (f)__________________________________________________________________________1 24 35 87.5 ND 13.4 1.05 82 50 37 92.5 ND 18.2 0.75 143 32 44 110 150 9.2 1.28 144 37 40 100 ND 19.4 0.96 375 36 48 120 ND 9.4 1.18 126 35 42 105 ND 20.6 0.88 367 40 54 135 170 7.8 1.35 228 34 37 92.5 ND 19.8 0.80 99 46 46 115 160 10.2 1.28 2210 37 42 105 ND 34.5 0.48 3111 34 40 100 ND 15.5 1.15 2612 28 35 87.5 ND 29.8 0.61 3013 36 42 105 120 11.3 1.25 2414 32 41 102.5 ND 10.1 1.07 5.615 92 105 263 ND 6.9 1.22 29.5A 34 26 65 ND 41.5 0.39 92__________________________________________________________________________ (d) measured by Soxhlet extraction with boiling heptane for 16 hours. (e) Measured as indicated using the apparatus described in Polymer Age, March 1970, Page 57 ff. (f) Measured according to ASTM Method D 1238-70, Condition N. (g) N.D. means not determined. (h) 2.5 times the amount of Ti found.
It will be observed that in all cases in which the catalyst also included cycloheptatriene (that is Example 1, 3, 5, 7, 9, 11, 13 and 14), the polymer obtained had a flexural modulus in excess of 1.00 GN/m2 and most case the flexural modulus was 1.15 GN/m2 or greater.
The general procedure of Example 1 to 15 was repeated using a different TiCl3 component.
The TiCl3 component was prepared as generally described in Examples 1 to 14 but with the following modifications:
To a solution of 600 ml of TiCl4 in 2400 ml of hexane maintained at 1░ C was added, over a period of 4 hours, 1800 ml of a solution of diethyl aluminum monochloride, in hexane, the solution containing 692 ml of the dietyl aluminium monochloride. The mixture was stirred and maintained at 1░ C during the addition. When the addition had been completed, the reaction medium was stirred for 15 minutes and then raised to 65░ C within about one hour and maintained for one hour at 65░ C whilst stirring. The procedure was then as described except that the amount of solid used was sufficient to provide 3.05 moles of TiCl3 and this was treated with a solution of 440 ml of hexane and 690 ml of diisoamyl ether and the solid product was suspended in a solution of 1300 ml of hexane and 442 ml of TiCl4. The catalyst complex had a specific surface area of 149.6 m2 /gm, and the pororosity (pores less than 300 A diameter) was found to be 0.16 cm3 /gm. The mean pore diameter was 40-45 A.
The polymerisation conditions and the properties of the polymers obtained are set out in Table 3. The polyene used in both cases was 1,3,5-cycloheptatriene. Duplicate samples of the polymers obtained were subjected to an extraction treatment by Soxhlet extraction with boiling diethyl ether (about 200 mls of the ether for 15 gms of polymer) for 16 hours, and test pieces were formed from the combined extracted polymers. Using the polymer of Example 16, a total of 3.7% by weight of polymer was extracted and the flexural modulus increased to 1.44 GN/m2. Using the polymer of Example 17, a total of 2.1% by weight of polymer was extracted and the flexural modulus of the extracted polymer was 1.46 GN/m2.
TABLE 3__________________________________________________________________________ Hot Conv. Heptane Flex (gm/Mal) Cl(ppm) (g) Solubles ModExampleLewis Base Polyene Time TiCl.sub.3 Ti(ppm) (g) Calc. % w/w GN/m.sup.2 MFINo. (a) (mMol) (mMol) hours (c) Calc. Found (h) Found (d) (e) (f)__________________________________________________________________________16 HMPT 0.8 0.8 21/2 1300 37 47 117.5 ND 9.3 1.22 1917 HMPT 1.6 1.6 21/2 1050 46 53 133.5 230 5.3 1.45 22__________________________________________________________________________(a) See Table 1(c)(d)(e)(f) See Table 2(g)(h)
The polymers of Examples 7, 9 and 17 were subjected to particle size analysis by sieving. The results obtained are set out in Table 4.
TABLE 4______________________________________Particlesize Eg 7 Eg 9 Eg 17(microns) (% wt) (% wt) (% wt)______________________________________<210 0.55 0.25 0.90210-300 1.3 2.15 0.80300-422 6.85 1.25 0.45422-500 32.1 15.95 1.85500-850 58.65 74.75 91.90 850-1180 0.95 4.30 2.251180-1400 0.15 0.40 0.051400-2000 0.40 1.05 1.80______________________________________
A polymerisation flask equipped with efficient stirrer and a water jacket was dried carefully and 1 liter of an inert hydrocarbon diluent having a boiling range of about 170-175░ C was introduced. The diluent was evacuated at 60░ C purged with nitrogen and evacuated which treatment effectively reduced the water and oxygen contents of the diluent to below 10 ppm by weight. The diluent was then saturated with propylene to one atmosphere pressure. The propylene used was purified as described in Examples 1 to 15. Four millimoles of triethyl-aluminium were introduced followed by the Lewis Base to be tested. After half hour 2 millimoles of TiCl3 were introduced. The pressure in the reaction vessel was maintained at one atmosphere by supply of propylene from a burette. After a period of 2.5 hours from the introduction of the TiCl3 the run was terminated with 10 ml of isopropanol and a sample of supernatant liquid extracted for determining the conventration of soluble polymer. The solid was filtered and washed three times with petrol ether and dried in a vacuum oven at 120░ C for an hour. The yield of solid plus calculated soluble polymer equalled within experimental error the propylene lost from the burette.
The results obtained are set out in Table 5.
Comparative examples, indicated by letters, were carried out in a similar manner by omitting the Lewis Base.
TABLE 5______________________________________ %Ex. or Yield of Weight ofCompara- Lewis Base Polymer (gm/ Solubletive Ex. Type mMol TiCI.sub.3) Polymer(i) (a) (mMol/1) (j) (k)______________________________________18 DDDPO 0.25 77 6.219 OMPA 0.5 91 5.020 OMPA 1 47 3.421 PDEPT 0.5 71 3.722 HMPT 0.25 65 8.9 23* HMPT 2 43 2.5 B* -- NIL 96 20.7C -- NIL 127 25.5______________________________________ (a) See Table 1 (i) In all the examples and comparative examples except those marked with an asterisk (*) the TiCl.sub.3 used was as described in Examples 16 and 17. In the examples marked * the TiCl.sub.3 was prepared as described in Examples 1 to 15 with the following exceptions: -The first stage was carried out on a smaller scale using a solution of 640 mls hexane and 150 ml TiCl.sub.4 in a 2 litre flask with stirring at about 150 r.p.m. and adding a solution, consisting of 320 ml of hexane, and 175 ml of diethyl aluminium monochloride, the addition being for a period of 8 hours. After separating the solid reaction product from the first stage, this was washed 5 times with 500 ml of dry hexane, the solid being resuspended for each wash. The product was then freed from adsorbed hexane by flushing with nitrogen. The treatment with complexing agent was effected using 172 ml of hexane and 256 ml of diisoamyl ether. The resulting solid was separated from the liquid phase, washed 5 times with 500 ml of hexane at 25░ C and dried with nitrogen. The treatment with TiCl.sub.4 was effected using 850 ml of a 40% by volume solution of TiCl.sub.4 in hexane The surface area of material prepared in this manner was 159 m.sup.2 /gm. (j) Based on solid polymer only. (k) % based on total polymer (solid + soluble) formed.
Polymerisations were carried out as in Examples 18 to 23 but using 10 millimoles of diethyl aluminum chloride in place of triethyl aluminum with 5 millimols of TiCl3. The propylene feed contained approximately 0.15 volume percent of hydrogen in order to modify the molecular weight. The results obtained are as set out in Table 6. The TiCl3 used was as described for Examples 16 and 17.
It was found that if the amounts of Lewis Base used were higher than those used in the Examples, there was a reduction in the yield of polymer together with an increase in the proportion of soluble polymer formed.
The procedure of Examples 1 to 15 was repeated using the same form of titanium trichloride except that the quantities and method of addition of the aluminium triethyl, cycloheptatriene and hexamethylphosphorictriamide were varied. In all the experiments a solution of aluminium triethyl, 1,3,5-cycloheptatriene and hexamethylphosphoric triamide in n-heptane was prepared, in the molar ratios of 5:1:1, the concentration of the aluminium triethyl being 0.88 moles/liter of solution.
TABLE 6______________________________________ % WeightExample Yield of ofor Com- Lewis Base MFI Polymer Solubleparative Type mMol (190/10) (gm/mMol) PolymerExample (a) l (f) (g) (j) (k)______________________________________23 OMPA 0.5 ND 53 0.324 DDDPO 0.5 47 38 0.325 HMPT 0.5 54 38 0.326 HMPT 1 ND 55 0.3D -- NIL 37 40 1.1______________________________________(a) See Table 1(f)See Table 2(g)(j)See Table 5.(k)
In Examples 28 and 31, all of the solution containing aluminium triethyl and the other components was added at the start of the polymerisation. In Examples 29 and 32, only part of the aluminium triethyl and the other components was added at the start of the polymerisation, further additions being made 30 minutes, 1 hour, 1.5 hours and 2 hours after the start of the polymerisation. In Example 30, only part of the aluminium triethyl and the other components was added at the start of the polymerisation, further additions being made 1.5 hours and 3 hours after the start of the polymerisation. In Examples 29, 30 and 32, the solution added during the polymerisation had been diluted by the addition of a sufficient quantity of n-heptane to give an aluminium triethyl concentration of 0.117 moles/liter of solution.
The details of the polymerisation process are set out in Table 7, and some characteristics of the polypropylene product are given in Table 8.
TABLE 7______________________________________Addition ofAlEt.sub.3 solution Before During Total Conversion Polyn. Polyn. Reaction (gm/mMol)Example (mMol) (mMol) Time TiCl.sub.3)No. (1) (1) (hours) (c)______________________________________28 12 NIL 21/2 62529 4 4 ū 2 21/2 168030 8 2 ū 2 61/2 177031 8 NIL 21/2 117532 4 4 ū 1 21/2 1825______________________________________ (c) As in Table 1 (1) Amounts quoted in respect of quantities of aluminium triethyl, quantities of 1,3,5-cyclo-heptatriene and hexamethylphosphoric triamide both 0.2 of the amount of aluminium triethyl.
TABLE 8______________________________________ % Weight Hot Heptane Flex Cl (ppm) Soluble ModExample Ti (ppm) Calc. Polymer (GN/m.sup.2) MFINo. Calc. Found (h) (d) (e) (f)______________________________________28 77 65 162.5 9.2 1.25 18.529 28 36 90 10.9 1.16 16.530 27 35 87.5 8.9 1.25 1131 41 49 122.5 9.7 1.26 1732 26 27 67.5 15.8 0.92 25______________________________________(d)(e)As in Table 2(f)(h)
The procedure of Examples 1 to 15 was repeated with the following differences. The catalyst system consisted of one gm millimole of the TiCl3 component of Examples 16 and 17, 12 gm millimoles of diethylaluminium chloride and hexamethylphosphoric triamide in the quantities given in Table 9. 5.1 liters of liquid propylene were transferred from a burette at 42░ C and 250 gm millimoles of hydrogen were also added. Ten further additions of hydrogen (20 gm millimoles on each occasion) were made 7, 15, 22, 30, 40, 55, 75, 95, 115 and 135 minutes after the start of the polymerisation. Further details of the polymerisation conditions and the results obtained are given in Table 9.
TABLE 9__________________________________________________________________________ % Weight Hot Conversion Heptane FlexExample or HMPT to Solid Soluble ModComparative (mMol) (gm/mMol TiCl.sub.3) Ti (ppm) Polymer (GN/m.sup.2) MFIExample (a) (c) Calc. Found (d) (e) (f)__________________________________________________________________________E O 1160 40 50 4.6 1.24 2333 0.5 1280 37 40 1.8 1.43 1234 1.0 1410 34 42 2.4 1.50 1735 1.5 1300 37 40 3.0 1.53 2236 2.0 1130 42 50 4.9 1.42 35__________________________________________________________________________(a) HMPT is as defined in Table 1(c) As in Table 1(d)(e) As in Table 2.(f)
Polymerisation was carried out in a steel autoclave of capacity 8 liters fitted with an anchor stirrer/scraper. 400 grammes of dry polypropylene was added while stirring the autoclave at 70░ C. The stirrer speed was 150 rpm. The autoclave was evacuated, after half an hour the vacuum was released with propylene, and then the autoclave was re-evacuated. This procedure was repeated a further five times over an hour and a half to leave an atmosphere of propylene. The stirrer was stopped and a solution, in heptane, of aluminium triethyl, Lewis Base and 1,3,5-cycloheptatriene was injected into the autoclave by means of a syringe. The autoclave contents were stirred for 10 minutes, the stirrer was stopped and 2 millimoles of the titanium trichloride material were added. The stirrer was restarted and propylene gas was then admitted to the top of the autoclave from a heated stock vessel containing liquid propylene,. A pressure of 400 psi gauge was established over a period of about 30 minutes. The temperature was maintained at 70░ C throughout. Hydrogen was added evenly during the pressurisation stage. Polymerisation was effected at 400 psig and 70░ C, and hydrogen was added throughout the polymerisation. After the desired polymerisation time, the propylene supply was switched off, and the autoclave vented to atmospheric pressure. The gas cap was purged with nitrogen and the polymer emptied out. The polymer obtained was a free flowing, greyish powder. The polymerisation conditions are set out in Table 10 and the characteristics of the products obtained are summarised in Table 11.
TABLE 10__________________________________________________________________________ Other Catalyst Components Lewis Hydrogen CarrierType of Base CHT Polymerisation mole % on PolymerExampleTiCl.sub.3 AlEt.sub.3 (mMol) (mMol) Time propylene TypeNo. (m) (mMol) (n) (b) (hours) (p) (q)__________________________________________________________________________37 I 12 1.2 1.2 5.0 α A38 I 12 2.4 2.4 5.0 α A39 I 12 1.2 1.2 5.0 0.5 A40 I 12 1.2 1.2 4.5 1.5 A41 II 12 2.4 2.4 5.0 0.5 A42 II 12 1.2* 1.2 5.0 1.0 A43 III 12 1.2 1.2 2.5 0.32 B44 III 12 1.2 1.2 5.0 β B45 III 12 1.2 1.2 2.5 NIL B__________________________________________________________________________(b) See Table 1(m) I - The TiCl.sub.3 -containing material was prepared using the procedure of Examples 16 and 17 with the exception that the TiCl.sub.4 solution was reacted with 3722 ml of a solution, in hexane, of diethyl aluminium monochloride. The solution contained 692 ml of diethyl aluminium chloride. The TiCl.sub.4 treated material was washed five times with hexane, but was not dried. II- The TiCl.sub.3 -containing material was obtained by a repeat of the preparation described for Example 23. The surface area was found to be 225.3 m.sup.2 /gm, and the porosity was found to be 0.22 cm.sup.3 /gm (pores less than 300 A diameter). III - The TiCl.sub.3 -containing material was obtained by a repeat of the preparation described for Examples 16 and 17.(n) The Lewis Base was hexamethylphosphoric triadmide in all the examples except that marked * in which the Lewis Base was tetramethylethylenediamine.(p)30 millimoles of hydrogen were introduced during pressurisation, and during the polymerisation, 25 millimoles of hydrogen were added for every 250 ml of liquid propylene evaporated into the autoclave from the stock vessel.60 millimoles of hydrogen were introduced during pressurisation and, during the polymerisation, 10 millimoles of hydrogen were added for each 200 ml of liquid propylene evaporated into the autoclave from the stock vessel. In the other examples, hydrogen was monitored into the system to maintain the indicated level of hydrogen.(q) Polymer A had the following characteristics:Titanium content 28 ppm (by weight)MFI 23Flexural Modulus 1.39 GN/m.sup.2Residual Soluble 4.0% (by weight)polymerPolymer B had the following characteristics:Titanium content 75 ppm (by weight)MFI 26Flexural Modulus 1.36 GN/m.sup.2Residual Soluble 3.9% (by weight)polymer
TABLE 11__________________________________________________________________________ Total Net Cl (ppm) FlexuralTi found (ppm) (r) (g) Residual Solubles MFI ModulusExample(r) Calc (% wt) (r) (s) (f) (r) (GN/m.sup.2)No. Total Net Found (h) Total Net Total Net (e)__________________________________________________________________________37 59 66 178 165 5.7 6.1 5.8 4.1 1.4438 75 90 ND 225 4.1 4.1 3.9 2.2 1.6139 64 75 ND 188 5.3 5.7 4.9 3.1 1.4340 75 93 ND 233 6.2 7.0 25 28 1.4141 76 96 286 240 6.6 7.6 11 7.6 1.5242 90 113 ND 283 6.7 7.6 18 16 1.3443 85 93 315 233 2.9 2.2 15 9.5 1.4244 87 94 ND 235 6.1 7.2 11.2 7.2 1.4245 68 66 ND 165 7.0 7.8 ˜0.1 ˜0.1 1.32__________________________________________________________________________(e)(f) See Table 2(g)(h)(r) "Total" is the quantity as measured on the total product, that is the product including the carrier polymer, "Net" is a calculated value deduced from the known properties of the carrier polymer and the measured value for the total product and represents the value for the polymer formed in the polymerisation.(s) The proportion of residual soluble polymer was determined by adding 1 gramme of solid polymer to 50 ml of the inert hydrocarbon diluent used in the TiCl.sub.4 reduction stage of the catalyst used in Examples 1 to 15, and heating to 185░ C, with stirring, until the polymer had fully dissolved (this took about 10 minutes). The solution was cooled to 60░ C and maintained at this temperature, with stirring, for 18 hours. The precipitated polymer was separated by filtration at 60░ C, and the proportion of polymer which remained dissolved in the diluent determined by evaporating the solution to dryness.
Polymerisation of propylene was effected in a fluidised bed reactor of volume of 0.13 meter. The reactor was provided with a gas distributor plate at its base.
5 kgm of carrier polymer B (as defined in Table 10) for each run, was heated to 40 -50░ C in an evacuated chamber (at about 5 mm pressure) for 1.5 hours, the chamber being intermittently purged with hot propylene vapour, to remove volatile impurities from the polymer.
The carrier polymer was then introduced into the reactor through which propylene was being circulated at 80░ C and a pressure of about 200 psig. The pressure was raised to 400 psig and hydrogen was introduced in the amount indicated in Table 12.
A solution, in heptane, of aluminium triethyl, 1,3,5-cycloheptatriene and hexamethylphosphoric triamide in the molecular proportions of 5:1:1, was introduced into the reactor in a quantity as indicated in Table 12. A slurry containing 8 millimoles of TiCl3 (Type III as defined in Table 10) was introduced to initiate polymerisation which was effected for four hours at 80░ C.
The propylene used was purified as described in Examples 1 to 15. The propylene was cooled in a heat exchanger and passed through the gas distributor plate to fluidise the polymer particles.
From the reactor, the propylene was passed to a cyclone, to remove fine polymer particles which were returned to the reactor, and the propylene was then recycled in the manner described, fresh feed propylene being added to the recycle propylene. The propylene vapour was passed through the reactor at a sufficient rate to fluidise the bed of polymer particles.
At the end of four hours, the polymer was discharged from the reactor through an intermediate pressure vessel into a low pressure separation vessel which was stirred and purged with nitrogen to remove unreacted propylene. The results obtained are set out in Table 12.
TABLE 12__________________________________________________________________________ Residual TotalHydrogen Net Cl (ppm) Solubles Flex(mole % on Ti found (r) (g) (% wt) (r) Mod A1Et.sub.3Examplepropylene (ppm) (r) Calc (s) MFI (r) (GN/m.sup.2) (mMol)No. (p) Total Net Found (h) Total Net Total Net (e) (t)__________________________________________________________________________46 0.85 43 34 91 85 11.3 13.4 44.0 50.0 1.20 13047 0.75 41 31 53 78 10.5 12.4 35.5 39.0 1.19 12048 0.64 38 27 ND 68 9.6 11.2 29.0 29.5 1.16 120__________________________________________________________________________(e)(f) See Table 2(g)(h)(p) See Table 10(r) See Table 11(s)(t) The aluminium triethyl also included 1,3,5-cycloheptatriene and hexamethyl-phosphoric triamide in the relative proportions indicted in the description.
The polymerisation procedure of Examples 1 to 15 was repeated, using, as the TiCl3 -containing components TiCl3 of Types II and III (as defined in Table 10). The other catalyst components were, aluminium triethyl (8 millimoles), tetramethylethylenediamine (0.8 millimoles) and 1,3,5-cycloheptatriene (0.8 millimoles). The results obtained are set out in Table 13.
TABLE 13______________________________________Example No. 49 50______________________________________Type of TiCl.sub.3 (m) III IIConversion(gm/mMol TiCl.sub.3) (c) 1300 1150(Calc 38 42Ti (ppm)(Found 54 61Cl (ppm) Calc (h) 135 183MFI (f) 9.4 8.6Residual Solublepolymer (wt %) (s) 8.3 7.4Flexural Modulus (e) 1.34 1.17(GN/m.sup.2)______________________________________(c) See Table 1(e)(f) See Table 2(h)(m) See Table 10(s) See Table 11
The procedure of Examples 37 to 45 was repeated using, as the catalyst 2 millimoles of a titanium trichloride component, 16 millimoles of aluminium triethyl, 1.6 millimoles of 1,3,5-cycloheptatriene and 1.6 millimoles of 2-dimethylamino-1,3-dimethyl-1,3,2-diazaphospholidine-2-oxide. The titanium trichloride compound used was obtained using the procedure described in Examples 16 and 17 except that the product was not dried.
The carrier polymer used had a titanium content of 27 ppm (by weight), a melt flow index of 29 and a flexural modulus of 1.40 GN/m2.
84 millimoles of hydrogen were added during the pressurisation of the reactor, and, during the polymerisation, hydrogen was added at intervals in amounts of 10 millimoles of hydrogen for each 200 ml of liquid propylene vaporised from the stock tank.
Polymerisation was effected for 5 hours and the product obtained had the following characteristics:
______________________________________Conversion 450 gm/millimole of TiCl.sub.3Total Flexural Modulus 1.44 GN/m.sup.2MFI 17.5Calculated Net Ti 107 ppm (by weight)______________________________________
|Brevet citķ
|Date de dķp¶t
|Date de publication
|29 juil. 1958
|14 fķvr. 1961
|Montedison Spa
|Production of isotactic poly (alpha-olefins) having regulated molecular weight
|8 janv. 1964
|23 nov. 1965
|Gulf Oil Corp
|Polyolefin catalysts and processes
|21 sept. 1966
|24 mars 1970
|Phillips Petroleum Co
|Process and catalyst for polymerization of alpha-monoolefins having three or more carbon atoms per molecule
|5 dķc. 1966
|22 dķc. 1970
|Eastman Kodak Co
|Stereosymmetric polypropylene
|30 dķc. 1966
|16 fķvr. 1971
|Montedison Spa
|Olefin polymers having a controlled granulometry and process for their preparation
|18 dķc. 1967
|17 ao¹t 1971
|Eastman Kodak Co
|Process for producing substantially ash-free polyolefin polymers
|27 mars 1969
|18 janv. 1972
|Phillips Petroleum Co
|Carbon disulfide with trialkyl phosphine as adjuvant for polymerization catalyst and polymerization process
|5 nov. 1971
|14 ao¹t 1973
|Hoechst Ag
|Mixed catalyst for the polymerization of alpha olefins
|31 mars 1975
|5 oct. 1976
|Standard Oil Company (Indiana)
|Catalyst component comprising brown titanium trichloride
|Brevet citant
|Date de dķp¶t
|Date de publication
|25 janv. 1979
|8 juil. 1980
|Hercules Incorporated
|Titanium trichloride catalyst component for propylene polymerization
|3 avr. 1978
|16 sept. 1980
|Standard Oil Company (Indiana)
|Process for forming high performance titanium trichloride olefin polymerization catalyst components
|19 juin 1979
|17 fķvr. 1981
|Toyo Stauffer Chemical Co., Ltd.
|Titanium trichloride catalytic component and method for homo- or co-polymerization of α-olefin
|22 janv. 1979
|24 mars 1981
|Mitsubishi Chemical Industries Ltd.
|Process for polymerizing propylene
|12 fķvr. 1979
|14 avr. 1981
|Exxon Research & Engineering Co.
|Titanium trichloride catalyst complex and process for the production thereof
|8 janv. 1979
|16 juin 1981
|Sumitomo Chemical Co., Ltd.
|Process for producing propylene polymer or copolymer
|14 mai 1980
|5 janv. 1982
|Chisso Corporation
|Process for producing α-olefin polymers
|12 oct. 1979
|9 fķvr. 1982
|Toyo Stauffer Chemical Co., Ltd.
|Titanium trichloride catalytic component and method for homo- or co-polymerization of α-olefin
|25 avr. 1980
|11 mai 1982
|Shell Oil Company
|Olefin polymerization catalyst component and composition and method of preparation
|16 juil. 1980
|2 nov. 1982
|Mitsubishi Chemical Industries Limited
|Process for polymerizing propylene
|5 nov. 1981
|12 juil. 1983
|Shell Oil Company
|Olefin polymerization process with novel supported titanium catalyst compositions
|19 nov. 1980
|26 juil. 1983
|Exxon Research & Engineering Co.
|Titanium trichloride catalyst complex and process for the production thereof
|5 sept. 1978
|23 ao¹t 1983
|Imperial Chemical Industries Plc
|Transition metal compound
|1 mai 1980
|23 ao¹t 1983
|Shell Oil Company
|Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions
|30 oct. 1981
|8 nov. 1983
|Shell Oil Company
|Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions
|28 sept. 1981
|13 dķc. 1983
|Chisso Corporation
|Process for producing α-olefin polymers
|21 juil. 1983
|6 ao¹t 1985
|Chisso Corporation
|Process for producing α-olefin polymers
|12 mai 1982
|24 sept. 1985
|Exxon Research & Engineering Co.
|Titanium trichloride catalyst component and the process for the production thereof
|19 mars 1985
|14 oct. 1986
|Montedison S.P.A.
|Catalyst components and catalysts for the polymerization of olefins
|13 fķvr. 1987
|1 mars 1988
|Shell Oil Company
|Preparation of spherical magnesium alkoxide particles
|13 nov. 1987
|4 avr. 1989
|Shell Oil Company
|Process for the in-reactor stabilization of polyolefins
|8 ao¹t 1988
|3 avr. 1990
|Shell Oil Company
|Preparation of olefin polymerization catalyst component
|8 ao¹t 1988
|14 ao¹t 1990
|Shell Oil Company
|Method for crystallizing magnesium chloride and method for using in a catalyst composition
|10 juil. 1989
|20 nov. 1990
|Shell Oil Company
|Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene
|21 dķc. 1988
|25 juin 1991
|Sumitomo Chemical Company, Limited
|Catalyst system for olefin polymerization and method for production of olefin polymers by using the same
|26 fķvr. 1990
|18 fķvr. 1992
|Shell Oil Company
|Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process
|7 oct. 1991
|2 juin 1992
|Shell Oil Company
|Process for the production of elastomeric primarily isotactic polyolefins and catalysts for use in said process
|26 fķvr. 1990
|2 juin 1992
|Shell Oil Company
|Process for producing mildly elastomeric primarily isotatic polypropylene and poly-1-butene
|11 mai 1990
|2 juin 1992
|Shell Oil Company
|Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process
|25 fķvr. 1992
|17 nov. 1992
|Shell Oil Company
|Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process
|10 avr. 1989
|27 avr. 1993
|Phillips Petroleum Company
|Process for polymerizing 1-olefins and catalyst therefor
|25 avr. 1989
|14 dķc. 1993
|Shell Oil Company
|Process for the production of elastomeric, primarily syndiotactic polypropylene and catalysts for use in said process
|15 oct. 1990
|14 dķc. 1993
|Shell Oil Company
|Process for the production of elastomeric, primarily syndiotactic polypropylene and catalysts for use in said process
|19 fķvr. 1992
|15 mars 1994
|Shell Oil Company
|Process and catalyst for producing mildly elastomeric primarily isotactic polymers
|30 mars 1993
|9 mai 1995
|Huntsman Polypropylene Corporation
|Process for the production of polypropylene
|13 mai 1997
|14 juil. 1998
|Solvay Polyolefins Europe-Belgium (Societe Anonyme)
|Process for the stereospecific polymerization of alpha-olefins and catalyst system which can be employed for this polymerization
|6 juin 1995
|20 oct. 1998
|Nippon Oil Co., Ltd.
|Catalyst components for polymerization of olefins
|9 dķc. 2004
|18 juil. 2006
|Equistar Chemicals, Lp
|Carbene donor-modified Ziegler-Natta catalysts
|2 oct. 2009
|18 janv. 2011
|Equistar Chemicals, Lp
|2-hydroxypyridine N-oxide-modified ziegler-natta catalyst system
|2 oct. 2009
|13 sept. 2011
|Equistar Chemicals, Lp
|Nitroso-modified Ziegler-Natta catalyst system
|9 dķc. 2004
|15 juin 2006
|Sandor Nagy
|Carbene donor-modified Ziegler-Natta catalysts
|2 oct. 2009
|7 avr. 2011
|Sandor Nagy
|Indazole-modified ziegler-natta catalyst system
|2 oct. 2009
|7 avr. 2011
|Sandor Nagy
|Pyridazine-modified ziegler-natta catalyst system
|29 sept. 2010
|7 avr. 2011
|Equistar Chemicals, Lp
|Pyridazine-modified ziegler-natta catalyst system
|29 sept. 2010
|7 avr. 2011
|Equistar Chemicals, Lp
|Nitroso-modified ziegler-natta catalyst system
|29 sept. 2010
|7 avr. 2011
|Equistar Chemicals, Lp
|Indazole-modified ziegler-natta catalyst system
|29 sept. 2010
|7 avr. 2011
|Equistar Chemicals, Lp
|2-hydroxypyridine n-oxide-modified ziegler-natta catalyst system
|Classification aux ╔tats-Unis
|526/139, 502/118, 502/123, 526/351, 526/142, 526/128, 526/141, 502/127, 502/121, 502/122, 526/140, 502/125, 502/124, 502/126
|Classification internationale
|Classification coopķrative
|Classification europķenne


text:
Senate Bill 1797 by Senator Clark Jolley would combine many of the functions of the Commission for Teacher Preparation and the Office of Accountability into a new agency known as the Commission for Educational Quality and Accountability. The State Department of Education would take responsibility for Professional Development programs currently provided by the Commission for Teacher Preparation. In addition, the SDE would also become responsible for National Board of Professional Teaching Standards program.
The responsibility for setting "cuts scores and performance levels" would move from the State Department of Education to the new Commission.
Read the bill.


text:
Lamu German Post Office
German nationals Clement Denhardt and G. A. Fisher first made contact with the Lamu hinterland in the late 1870s. They soon struck a friendship with Ahmed Abdullah Simba, the Sultan of Witu, who at the time was having problems with the rulers of Lamu and Zanzibar and so welcomed a new ally. Shortly afterwards, Witu became a German protectorate.
This building was the first German Post Office ever established along the East African coast. The Post office was established on November 22nd 1888 by the Germans, led by Clement Denhardt. The communications and trade contacts for the German Protectorate in Witu could at the time be served through Lamu, a well-established town with links to the outside world.
The Post office operated for more than two years before its closure on March 3rd 1891 after the withdrawal of the German settlement in Witu.


text:
My Content
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Sam Wilson weaves delicate guitar strains into the pattern on six of the cuts to provide a softened balance between the flurries oozing from Borgo's horns. Wilson makes a solid contribution with his advanced concepts as he dances over the strings adding an intimate touch to the tunes. On four of the selections with Wilson also on board, trumpeter John D'Earth puts sparkle into play. He and Borgo take off on a dual mission while Wilson smoothes the path as the rhythm guitarist; then Wilson joins the improvising fun with rounds of his own.
Drummer Mark Ferber keeps the solid time on all selections. He and either bassist Pete Spar or Roberto Miranda underpin the program that stays mainly inside but does occasional flirting with the liberated side.
Two jazz standards are featured. Mingus's "Duke Ellington's Sound of Love" gets a romantic reading from a typical Mingus-style three-horn front line, which includes trombonist Alan Ferber. Borgo and Ferber then jump into the quartet mode doing Dave Holland's classic "Conference of the Birds." Borgo switches to soprano saxophone, which neatly blends with the frictionless tones from Ferber's trombone. One other configuration is offered. Borgo joins with alto saxophonist David Pope on the swinging Pope original "Pomodori," which opens up to a wild, merry chase as both reed players blow with enthusiasm.
Borgo offers a varied palette on this recording. He touches on the past, teases with the future, but mainly speaks in the present tense. The assorted groupings yield diversified but consistently appealing music having tangibility without sacrificing challenge.
Track Listing: Massanetta Springs (7:18) / Only in My Dreams (6:21) / Heron Pool (8:59) / Scomotion (5:14) / Duke Ellington
Personnel: David Borgo-tenor & soprano saxophones; John D
Title: Massanetta Springs | Year Released: 2003 | Record Label: Circumvention Music
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text:
by Alan Schwarz
March 8, 2006
PHOENIX–Make no mistake, Chase Utley posed. When the Team USA second baseman launched a shot deep into the Phoenix evening, he joined the rest of Chase Field in assuming that his imminent three-run home run would complete a stunning comeback and save Team USA from one of the most shocking upsets in international baseball history. Utley flipped his bat and began his trot, figuring that the world had regained its order.
It didn't. Canadian center fielder Adam Stern, punctuating the best single-game performance in this young World Baseball Classic, jumped against the fence to snare Utley's drive and the hopes of Team USA along with it. The eighth inning ended, Canada held on to its 8-6 lead, and won a game that will determine the outcome of Pool B less than bruise 50 states worth of egos.
"It's a very quiet locker room right now," U.S. manager Buck Martinez said. "Everyone feels like they got kicked in the stomach."
Canada scored in each of the first five innings, mounting an 8-0 lead behind lefty starter Adam Loewen. Team USA erupted for six runs off two relievers in the bottom of the fifth–capped by a 448-foot grand slam by Jason Varitek–but never scored again, stunning the crowd of 16,993 at Chase Field.
"I just didn't do anything right today," said U.S. starter Dontrelle Willis, who gave up five runs in 2 2/3 innings. "Just one of those games where you just tip your hat to the other opposing team."
Despite the outcome, both Canada (2-0) and the United States (1-1) can either advance to the second round or still be eliminated, depending on the outcome of other games. But Canada can determine its own fate: A win against Mexico in Thursday's game (8 p.m. ET) behind starter Jeff Francis will make it the Pool B winner.
If Canada loses, given Mexico's 10-4 win over South Africa Wednesday night–and assuming a probable Team USA win over South Africa Friday behind ace Roger Clemens–Canada, Mexico and Team USA would all finish 2-1 and face a complicated tie-breaking system, one that will separate teams first by fewest runs allowed in games among each other.
Mexico beating Canada while scoring three runs or more would send Mexico and the United States advancing to the second round in Anaheim this Sunday. Mexico beating Canada while scoring two runs or less would advance Mexico and Canada, with the United States eliminated.
Assuming that win over South Africa isn't exactly what Team USA is doing at the moment, though, Clemens or not. Wednesday's loss to Canada showed what everyone in baseball knows: That single games can be as dangerous as licking lawnmower blades.
"I think one thing we have learned quickly in this international play is anything can happen," Martinez said. "You put your flag on your chest and you go out there and play, and people get fueled by that. You see exceptional things being done by very competitive people."
No one was more exceptional Wednesday than Stern, who is expected to stick with the Red Sox as a fifth outfielder this spring. The former Nebraska star hit an RBI triple, two-run single and solo, inside-the-park home run in the first five innings. He sparkled defensively as well, nabbing a sinking line drive to end the sixth inning and adding his against-the-wall grab against Utley to end the eighth.
"Any win in this tournament is huge, and coming against the USA, they have the most talent out there. I won't lie," Stern said. "But that's why you play these games, and it's a time of year where one game, you don't know what's going to happen. Over 162, I don't know if we'd fare so hot. One game you've got to go out there and bust it. That's what we did."
Stern, who was so proud to have played for Canada in the 2004 Olympics that he tattooed a maple leaf and the Olympic rings above his heart, said that his American Red Sox teammates had teased him last week about how Canada would lose so fast in the WBC that he would barely miss any spring-training games. "I'll have something to say about that," he recalled telling them with a vengeful smile.
Even though he and his teammates said it loudly, and Canada came away with what instantly was called the country's biggest win ever in international competition, the celebration would have to wait.
"I think we're going to let this marinate for a few hours, but after that we have to get ready for Mexico," Stern said. "Nothing's guaranteed right now. Talk to us after tomorrow and we'll have something to say."


text:
Florida lawmakers approved a bill that relaxes a measure to clean up the Everglades and sent it to Gov. Jeb Bush over the objections of environmentalists.
By a 96-18 vote, the Florida House passed a measure that scraps a 2006 deadline that was set in 1994.
The 1994 bill required farmers to use filtering ponds or other methods to ensure that less phosphorus and other pollutants entered the fragile Everglades. While the original set explicit limits and deadlines, the 2003 revision requires the runoff to be cleaned up only "to the maximum extent practicable."
The Florida Senate voted 38-0 to approve the measure.
Backed by the sugar industry and supported by the governor, the bill has come under fire from those who say the delay could jeopardize federal funds critical to the $8 billion federal and state effort to restore water flow the Everglades during the next several years.
On Wednesday, U.S. Sen. John Kerry, a Massachusetts Democrat, added his name to the list of federal lawmakers urging Florida legislators to defeat the measure.
On Tuesday, U.S. House Appropriations Chairman Bill Young, a Florida Republican, called on the governor to veto it.
A federal judge has ordered state officials to a hearing in Miami to discuss the impact of the legislation and whether it conflicts with current requirements. U.S. District Judge William Hoeveler has overseen the Everglades restoration effort for more than a decade.
A sugar industry spokesman hailed the legislation as a practical modification to a 10-year-old program. Robert Coker, vice president for U.S. Sugar Corp., also accused critics of conducting a scare campaign to thwart passage of the measure.
"I'm tired of the extreme environmentalists hiding behind Everglades restoration because they don't like the sugar industry," said Coker.
Opponents of the plan said slowing implementation of higher water quality standards could erode congressional support for what will be one of the most expensive public works projects in U.S. history.
"What I do know is that if we lose federal funding for this important restoration, it could be many more decades before we can fully restore the Everglades," said House Democratic Leader Doug Wiles. "And members, that is not a risk I am prepared to take."


text:
Artist: Eric Church
Album: Chief
Genre: Country
Label: EMI Records Nashville
Released: 2011
Quality: FLAC (tracks+.cue)
- Creepin' (3:53)
- Drink In My Hand (3:11)
- Keep On (2:39)
- Like Jesus Does (3:19)
- Hungover & Hard Up (2:53)
- Homeboy (3:47)
- Country Music Jesus (3:53)
- Jack Daniels (5:04)
- Springsteen (4:23)
- I'm Gettin' Stoned (4:03)
- Over When It's Over (2:40)
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Contemporary country singer and songwriter Eric Church has been on a roll since 2006. He's had a slew of charting singles and albums, won Top New Solo Vocalist at the Academy of Country Music Awards for 2010, and in early 2011, both the Caldwell County EP and "Homeboy" -- the pre-release single for Chief -- hit number 13 on the chart. That said, he hasn't reached the commercial heights -- yet -- that peers such as Jason Aldean and Justin Moore have. That isn't necessarily a bad thing, because Church is having it both ways: he scores consistently enough to keep his label interested, but also maintains his independence to a degree, which turns on his fans. Church co-wrote 10 of the 11 songs on Chief. Once more teamed with producer/guitarist/bandleader Jay Joyce, he delivers a collection that, on the one hand, stays close to his outlaw pose -- in the new contemporary country sense of the term -- while being firmly entrenched in the music's mainstream. "Homeboy" offers a taste of the kinds of streetwise characters Church seems to prefer to write and sing about (even if they are him at times), though the production is atypical of the rest of the set. "I'm Gettin' Stoned" commences with a National Steel guitar and a thumping tom-tom before winding its way into neo-blues-rock before pulling in the reins; his lyrics bemoan the fact that an ex is getting married while he's left to get wasted alone. It's a new kind of "cryin' in your beer" song. "Drink in My Hand," with its ringing, open '70s rock guitars (why does everyone these days ape the opening of Little Feat's "Easy to Slip?"), and sharp crackling snare, defiantly state that no matter how oppressive his boss is, he cannot ruin the experience of his own cold beer once the work day is done. "Springsteen" isn't so much about the Boss as it is a nostalgic ode to an early love and the memory of the legendary songwriter's music as an accompanying soundtrack to it. It's a clever, if somewhat cloying, tune, but it gets the feeling across in spades. "Country Music Jesus" is a paean and a prayer, a rockist wish for a "long haired hippie prophet who preaches from the book of Johnny Cash" to save what's left of the tradition, and then evokes the spirit of Charlie Daniels to underscore it. Chief is defiant, well-conceived, and more carefully executed than it sounds, with some excellent songs. While it doesn't break any new ground and remains firmly entrenched in contemporary country's geography, it evokes the riled-up, bluesy hard country rock sound of Hank Jr. enough that it separates Church from the genre's other practitioners who are attempting the same thing.


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By Nick Worth
A reassignment of water department supervisor Armando Aguilera to concentrate on training other city employees has resulted in City Manager Ray Alley taking over as head of the Holbrook City Water Department.
"I will be the immediate supervisor of the water department in order to facilitate some changes," Alley said. "I want the department to be more accountable, and to carry out some facility repairs that have been lacking."
Alley said he wanted to reassign Aguilera to a training role because his 32 years of experience in the water department make him a "valuable asset" to the city. He said Aguilera would see no reduction in pay in the new job, even though he has been moved from a supervisory position to an hourly employee.
"He demoted me after 33 years of service to the city," Aguilera said Tuesday. "I'm not in agreement, but he's the big boss, so I'll do what he says."
Aguilera said he is not yet sure of what his new duties will be.
"Yesterday Ray told me I would not be supervising anymore," said Aguilera. "I asked him what I would be doing and he said, 'The same thing.'"
"I've known Armando for 32 years," Alley said. "He's a hard worker and has 32 years of valuable experience the city can draw on.
"Armando is doing us a big favor by taking this position," Alley said. He said Aguilera's experience will come in handy in several areas, such as training the younger water department employees, writing policies, taking care of the water monitoring reports and cross training employees from other city departments to do water department work.
"Armando is also one of the top two backhoe operators in the city, so we may ask him to help out in the streets department, if needed," said Alley. "His biggest goal will be to cross train department employees.
"We're not going to be here forever," said Alley. "A lot of the older people in the city need to pass their knowledge down to the younger workers."
Asked how he could assume the duties of water department supervisor in addition to his roles as city manager, public works director and head of the streets department, Alley admitted he is busy.
"I have a lot of help," Alley said. "Armando is still here and I have good people all around me. Plus, I enjoy working."
Alley said making the change was the right thing to do. "I don't do much in the street department anymore," he added.
"When I first got here four years ago, I was hired to get the city in shape financially and facility-wise, and that's what I've tried to do," Alley said. "I started with the street department. I was not popular at first, but I made changes and our streets are now in great shape.
"I'd put our street crews up against any in the state, public or private," said Alley.
He added that he also changed the city parks department with "significant personnel and operations changes.
"In my opinion, it's in better shape with more parks than it's ever been," he said.
As for his plans for the water department, Alley said water facilities improvements would be high on the list.
He said several of the department's pump houses and lift stations are in need of work, ranging from simple painting to full-scale construction. Two lift stations located near the Hopi Travel Plaza are in need of new block buildings to replace the existing frame and siding structures, which are succumbing to the weather. Five other lift and booster pump stations are in need of cleaning and other work on the structures, Alley said.
"I think there's room for improvement in our water department facilities," said Alley. "There's always something to be done, even in winter."
By Nick Worth


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Astros working around injuries in rotation
Astros working around injuries in rotation
Astros interim manager Tony DeFrancesco said Fernando Abad, who strained his right oblique in Monday's game, probably won't make his next start.
Edgar Gonzalez strained his hamstring in Friday's game and threw a bullpen session on Tuesday. DeFrancesco said Gonzalez's availability for his next start -- scheduled to come on Friday in Milwaukee -- is up in the air.
Lucas Harrell, who has pitched a career-high 182 2/3 innings entering Tuesday's start, may not get another outing. Bud Norris, managing a blister problem and a skin irritation on his scalp, will start on Wednesday, but his availability for the final series in Chicago could be a question mark.
That leaves Jordan Lyles and Dallas Keuchel as the only totally healthy starters in the Astros' six-man rotation. The club will probably revert to a five-man rotation until the end of the season.
"We're kind of banged up right now, but we're just trying to piece together our starting rotation for the next five days," DeFrancesco said.
Fernando Rodriguez is the most likely candidate for a spot start. Rodriguez threw a career-high 72 pitches in 4 1/3 innings of emergency relief on Monday.
"He won't be available for a few days, but in five days, he could be one of the starters in Chicago," DeFrancesco said. "It's going to be day to day with the rotation. It's unfortunate, but September baseball just seems to get harder and harder right now."
The injuries aren't limited to the rotation. Third baseman Matt Dominguez has flu-like symptoms and wasn't at the ballpark on Tuesday. Infielder Marwin Gonzalez is day to day with a sprained left ankle.


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Sidetracked (Paperback)
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From the dean of Scandinavian noir, the fourth riveting installment in the internationally bestselling and universally acclaimed Kurt Wallander series, the basis for the PBS series staring Kenneth Branagh. In the award-winning Sidetracked, Kurt Wallander is called to a nearby rapeseed field where a teenage girl has been loitering all day long. He arrives just in time to watch her douse herself in gasoline and set herself aflame. The next day he is called to a beach where Sweden's former Minister of Justice has been axed to death and scalped. The murder has the obvious markings of a demented serial killer, and Wallander is frantic to find him before he strikes again. But his investigation is beset with a handful of obstacles--a department distracted by the threat of impending cutbacks and the frivolity of World Cup soccer, a tenuous long-distance relationship with a murdered policeman's widow, and the unshakably haunting preoccupation with the young girl who set herself on fire. Fascinating and astute, Sidetracked is a compelling mystery enhanced by keen social awareness.
About the Author
Henning Mankell is the internatinally acclaimed, bestselling author of the Kurt Wallander novels. Mankell's novels have been translated into forty-five languages and have sold more than forty million copies worldwide. He was the first winner of the Ripper Award and also received the Glass Key and the Crime Writers' Association Golden Dagger, among other awards. His Kurt Wallander mysteries have been adapted into a PBS television series starring Kenneth Branagh. During his life, Mankell divided his time between Sweden and Mozambique, where he was artistic director of the Teatro Avenida in Maputo. He died in 2015.
Praise For…
"Presents Mankell at his best…if you haven't bought Sidetracked, do so ASAP" --Los Angeles Times Book Review
"[I]t is Wallander's voice . . . that captures us." --New York Times Book Review
"Mankell joins the worthy ranks of such past masters as Georges Simenon [and] Nicholas Freeling." --The Wall Street Journal
"Full of emotion yet cleanly written, apparently straightforward yet fraught with intriguing revelations, Mankell's latest mystery is strongly recommended." --Library Journal


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My doctor told me I needed to let my muscles repair themselves as they get tears in them. He suggest I exercise 4 times a week but try to do more using different machines. - by DIDMIS
For various reasons during the past year I have taken breaks from exercise. I find that after taking some time off, I come back feeling stronger and more motivated.
If you are feeling tired all the time, you aren't progressing in your workouts, you aren't having good workouts, or you just feel blah about working out, take some time off. You are probably suffering from burnout and your body needs time to recover.


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In Reply to: Re: Slightly Woozy, Ears Ringing, Lightheaded -- Anybody ? posted by Cut-Throat on July 03, 2000 at 10:32:37:
: Hi,
: I just finished an Allergen-free diet. This means I ate very little of anything. No processed foods etc. No bread, dairy. Lots of white fish, rice. a few fruits and vegetables. Ny symptoms did not change at all. My allergist has now ruled out a food allergy.
: I believe it is a common substance that I am breathing, because my symptoms do not change at all from day to day. They are very constant.Thanks for your comments.
Hmmm you just reminded me of something. Recently we re-caulked the tub in our master bathroom. When I got into bed to go to sleep I immediately began to feel lightheaded and woozy, and my stomach began churning. I laid there for a few minutes and the feelings got worse... then I sat up in bed and the dizziness subsided a bit. I laid back down and it all came back. I got up and went to sleep in the extra bedroom... and felt absolutely fine. I believe that as I was inhaling the fumes from the caulking substance in my bed, it was causing me to feel that way... especially since when I went into the other bedroom where I wasn't close to the fumes, I felt fine. There definitely can be a substance that's continually present around you that is making you feel this way. Best wishes to you in finding out what's bothering you.
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