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Патент USA US3046278

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aired rates Pater O?lice
1
3,ii46,268
Patented July 24, 1962
2
3,046,268
CATALYTIC PRQCESS FOR POLYMERIZING
ETHYLENHCALLY UNSATURATED HYDRO
CARBONS
Howard J. Cohen, Cincinnati, Ohio, assignor to National
Distillers and Chemical Corporation, New York, N.Y.,
a corporation of Virginia
strong reducing agents such as alkali metals (e.g., sodium),
alkaline earth metals (e.g., magnesium, calcium), organo
alkali compounds (e.g., alkylsodium), organometallic
compounds (e.g., trialkylaluminum), and the like with
further speci?c examples including tripropylaluminum,
triisobutylaluminum, tri-n-decylaluminum, butyl magne
sium chloride, dibutyl magnesium, metal hydrides such
No Drawing. Filed Sept. 22, 1959, Ser. No. 841,448
9 Claims. (Cl. 260-943)
as lithium hydride, magnesium hydride, etc.
Reaction conditions at which the polymerization may
be carried out with the novel catalyst system include the
The present invention relates to an improved polymer 10 following:
ization process and, particularly, to such a process utilizing
Temperature _______________ __ From —120° C. to 300° 0.,
a novel catalyst system for polymerizing ole?ns to high
preferably 50 to 250° C.
molecular weight polymers. Still more particularly, the
Pressure ___________________ __ Subatmospheric to 3000 at
invention relates to such a process using a catalyst system
that is advantageously soluble in conventional reaction
media employed for polymerizing ole?ns and is highly
stable against objectionable hydrolysis and thermal de
composition.
Ratio of catalyst components
(mol ratio of reducing agent:
mospheres, preferably at
mospheric to 200 atmos~
pheres.
M-contarning compound)_____ 0.1260 £50 : 1, preferably 1 to
Total
catalyst
concentration
(based on weight of monomer
In the process embodied herein, the catalyst system
to be polymerized) ________ __ 0.005 to 10%.
comprises (1) a suitable reducing agent and (2) a com 20
The compounds which may be polymerized according
pound of the formula
to the present invention consist generally of hydrocarbons,
such as the ole?ns containing 2 to 16 carbon atoms. Spe
ci?c examples of such hydrocarbons include ethylene,
wherein M’ is a metal from groups IVb, Vb and VII: of
the periodic table, such as Tit2 to +4, Zr+2 to +4, Hft2 to 25 propylene, butene-l, pentene~1, hexene-l, 4-methyl-pen
tene-l, butadiene, isoprene, styrene, methylstyrene, etc.
+4, V+2 to +5, Nb+2 to +5, and Ta+2 to +5, M is selected
Mixtures thereof, as for example mixtures of ethylene and
from the group consisting of Si, Ge, Sn and Pb, y is the
butene-l, may be used for copolymerization with the
valence of the metal M’, and R1, R2 and R3 is a hydro
catalyst system embodied herein.
carbon radical, e.g., alkyl, aralkyl, aryl, cycloalkyl, etc.,
The polymerization reaction is carried out in batch,
and preferably an alkyl radical such as one containing
semi-continuous or continuous operation. Most conveni
from one to eight carbon atoms and speci?cally, methyl,
ently, and in preferred embodiments, the process at lower
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl,
temperature operations is carried out in a diluent or liquid
t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, Z-ethylhexyl,
etc., and aryl radicals such as phenyl, p-tolyl, and the like.
Speci?c compounds falling within the scope of the afore~ “
said structural formula include tetrakis(trimethylsiloxy)
titanium, Ti[OSi(CH3)3]4, tetrakis(trimethylsiloxy)-zir
conium, tetrakis(triphenylsiloxy) vanadium, pentakis(tri
methylsiloxy) tantalum, tetrakis(triphenylstannoxy) tita
nium, Ti[OSn(C6I-I5)3]4, and others.
Compounds, other than the reducing agent, embodied
for use as a catalyst component may, for example, be pre
pared by the method of English and Sommer, J.A.C.S.
77, 170 (1955), and illustrated by preparation of tetrakis
(trimethylsiloxy)titanium by reacting trimethylsilanol
with titanium tetrachloride; by the method of Zeitler and
Brown, J.A.C.S. 79, 4616 (1957) showing preparation of
tetrakis (triphenylsiloxy) titanium by reacting triphenyl
reaction medium, the amount not being unduly critical
but it should be at least su?icient to permit eifective agita
tion and preferably to hold the major portion of the poly
mer in solution.
Suitable organic media include aliphatic alkanes or
cycloalkanes such as pentane, hexane, heptane, cyclohex
40 anes; hydrogenated aromatics such as tetrahydronaphtha
lene, high molecular weight liquid para?ins which are
liquid at‘ the reaction temperature; aromatics such as ben
zene, toluene, xylene, halogenated aromatics such as
chlorobenzene, chloronaphthalene, etc.
Other reaction
media include ethylbenzene, isopropylbenzene, ethyltolu
ene, n-propyl benzene, diethylbenzenes, mono- and di
alkyl naphthalene, n-pentane, n-octane, isooctane, methyl
cyclohexane, tetralin, decalin, and other inert liquid hydro—
carbons. In carrying out the polymerization reaction at
silanol with tetrabutoxytitanium; and still other com 50 relatively high pressures, such as at one thousand atmos
pounds, such as those in which M’ is vanadium may be
pheres and above, it may be carried out in the absence
prepared by reacting an appropriate alkali metal triorgano
or substantial absence of such reaction media and, in such
silanolate or stannolate with, for example, vanadium tetra
instance, the need for solvent recovery systems, etc., may
halide in accordance with the procedure of Tatlock and
be obviated.
Rochow, J. Am. Chem. Soc. 77, 170 (1955), and, forex 55 It is preferred that the reaction medium that is used
ample, the reaction of sodium triphenylsilanol or sodium
be essentially free of impurities which may react to de
trimethylsilanol with vanadium tetrachloride to prepare,
stroy catalyst activity or which copolymerize with the
respectively, tetrakis-(triphenylsiloxy) vanadium and tet
rakis~(trimethylsiloxy) vanadium.
ole?nic hydrocarbon; that is, appreciable quantities of
material such as carbon dioxide, oxygen and acetylenic
In reference to the ‘reducing agent that is one compo‘~
compounds should preferably be absent.
nent of the catalyst system embodied herein, particularly
For this process, the polymerizable hydrocarbons may
suitable and preferred are the alkylaluminum halides,
be used in substantially pure form or there may be used
such as dialkylaluminum halides, alkylaluminum dihalides,
a mixture containing major quantities thereof, provided
and mixtures thereof generally called “alkylaluminum sesj ' no impurities are present in substantial amounts to de
quihalides.” Thus, embodied for use herein are ethyl 65 stroy the catalyst and/or contaminate ‘the polymer
aluminum sesquibromide, ethylaluminum sesquichloride,
methylaluminum dibromide, dimethylaluminum bromide, .
methylaluminum vdichloride, dimethylaluminum chloride,
butylaluminum dibromide, dibutyl aluminum chloride,
hexylaluminum dibromide, dihexylaluminum bromide,
and similar alkylaluminum halides and mixtures thereof.
Still other reducing agents embodied for use herein are
product. For instance, ethylene obtained by the cracking
of hydrocarbon streams is satisfactory if acetylenic and
oxygenated materials are not present in more than trace
amounts.
In carrying out the herein described polymerization
process, it is preferable and highly desirable to maintain
the polymerization zone free of extraneous gases. This
3,046,268
4%
Example 2
can be done by keeping the reaction blanketed at all times
with an inert gas, for example, operating with an inert gas
such as nitrogen, argon or helium. Preferably, the reactor
and its contents are blanketed with the polymeriza-ble sub
In another run, the polymerization of ethylene was
carried out using V[OSi(C6H5)3]4 and diethylaluminum
chloride as the combination catalyst.
In such a run,
Stance’ e'g" ethYRM‘gaF’ to avc?d unnecessary dilution of 5 500 ml. of preheated decalin was charged to the reac
th? reactor contents with .the melt gasfs'
.
tor and the temperature adjusted to 125° C. The re
In order to further ‘describe the invention, the following
actor Contents, 2.1 m1. of a 0.133 M- decaun Solution of
examples set forth speci?c embodiments of catalyst sys(C H ) Alcl was added ‘followed b O 085 millimole of
terns embodied herein for polymerizing ethylene to high
molecular weight polymers.
5, 2C H
di
For the examples set forth, 1O V[OS,1( 6 5)3]4
1 d . 90 3'1 ‘f d
F80 W
m
“
m' o
1.
Aft
eca m‘, ' _ er
the reducing agent component of the catalyst System
was ethyl aluminum sesquichloride (a 1:1 mixture of
30 minutes of reaction at an ethylene pressure mamtained
at 60 mm- Hg gang?’ 2-57 grams of elhylene was ab_sorbefl
A1(C5H2)C12 and (A1(C2H5)2C1) o1- diethyl aluminum
The product was isolated and puri?ed as ‘described in
chloride and the other component was Ti[OSi(CH3)3] 4,
EXample 1 t0_Y1e1d Z61 _g1‘ ams of a tough: Yvnlte Polymer
V[OSi(C6H5)3]4 or Ti[OSi>(C6H5)3]4.
15 ‘The following tabulation sets forth additional data per
In each of the examples, the polymerization was carried
taming to the run of Example 2.
AW tide?
11
if use“
£3?‘ “ltii‘i?i? Agggggcilbigiiig.
egglggglagle ggllggggr poiylii?i’tca’???é’?d
grams
(CgHQzAlCl-i- grams’
V[OSi(CsH5)3]4
7 ____ __
0.28
3.3
2.57
260
2.61
tough, white solid.
out in a three-necked glass reaction ?ask equipped with
Example 3
a high speed stirrer7 thermometer, mercury manometer \for 30
In another run, ethylene was polymerized using a cam
reading reactor pressure, and feed lines supplying puri?ed
lyst combination of Ti[OSi(C6H5)3]4 and triethylalumi
ethylene and decahydronaphthalene. The ethylene was
Supplied through a Pressure reducmg valve on a demand
basis during the polymerization to maintain a constant
mum. In Such a mm, 300 ml_ of daca?n was introduced
into a one liter stirred pressure autoclave previously
?ushed with pure nitrogen The contents of the ?ask
ethylene Pressure in the reactor (60 mm Hg gauge)’ 35 were then heated to 180° C. under nitrogen and, after
The amount 0i ethylene absorbed was determmed fFOm
releasing the pressure in the autoclave, 5.72 grams (0.005
the pressure drop observed at constant temperature 111 a
mole) of THOSKCGHshh dispersed in 20 m1‘ of decalin
SUP-Ply tank of ‘known volume
.
was added, ‘followed by addition of 13 ml. of d 0.5 M
Example 1
.
4 sroklution 01f triethylaluminurg t(0.57610 gram, 0.0035 trlrliolle).
0
with 1.60 _m1' of decahydronaphthalene. (hell/[ed to
125. C‘) m a 250 m1‘ Team", a 0'1
solution (In ‘19”-
e au oc ave was r ressure
r o
.s.r1.g. w1
e
y ene
and the polymerizatrion carried out fit one hour and ten
minutes, the autoclave being repressured to 500 p.s.i.g.
hydronaphthalene) of the ethylaluminum sesqurchlo-ride
each time ‘it fell to 400 P Sig‘ The tsmperature of the
was added in amount su?icient to provide the concentraPolymerization reaction [ganged from 146434.. C At
tion shown for each run in the ‘following tabulation and, 45 the end of ‘the o1‘ merization reaction the viscol‘ls re_
after an elapse of 11/2 minutes, a 0.1 M solution of tetrakis(trimethylsiloxy) titanium was added to provide the
a t.
d t p 1 d1. h
d f
h’ ‘
1
.
cum pm 110 was Sc arge.
mm t e autoc ave mm
amount thereof shown for each run. After such addition
an excess of Water‘ The_s°hd Product: when cool’ was
of catalyst components, the polymerization was conducted
wnected ‘and treated Yvl‘th :hPptane 1“ ‘a mechamfial
at an ethylene pressure of 60 mm. Hg gauge, at 1250 Q 50 blender to remove decalin, agaln collected, treated twice
for 20 minutes, whereupon tha viscous Solution of the
with acetone in the blender, and ?nally collected‘ and dried
polymeric product was withdrawn from the reactor and
at 95° 0' “Pdar Vacuum- The dried Polym?nc Product
diluted with an equal volume of acetone. The solid polymer was collected by ?ltration, boiled 10 minutes in each
Obtalned Wglghad 8'2 grams, Corresponding to 3- yiald of
25 moles of Polyethylene P61‘ mole of iotal Catalyst
of three successive portions of a solution of one part by 55
While there are ‘above disclosed but a limited number
of embodiments of the process of the invention herein
volume of concentrated HCl and two parts by volume or‘
isopropyl alcohol, then boiled 10 minutes in each of three
portions of isopropyl alcohol, washed with acetone, and
dried in a vacuum oven at 120° C. to constant weight.
IEU‘JYL
Run
N0.
(mm?
(millimoles)
Al/Ti
a .er 20
Ratio
per gram Viscosity 1 grams/cc.2
Atomic grggnn?gies Relative Density, Softening
moles)
0. 193
0. 158
O. 123
0. 101
0. 16
O. 208
ments without departing from the inventive concept here
in disclosed, and it is desired therefore that only such
5135355541011 Properties of Isolated Polymer
a “111mm Tl.[OSl(CH3)3]l
cs?lsgilgg
presented, it is possible to produce still other embodi
mol of total
catalyst
O. 035
0. 017
0. 017
O. 017
0. 035
O. 035
110612;,
'
11. 0
18. 0
14.0
11'. 8
9. l
11. 9
1 Relative viscosity of a 0.1 weight percent solution in decahydronaphthalene at 130° 0.
B ASTM D-1238.
3 Under compression at 66 p.s.i.
3,046,268
limitations be imposed on the appended claims as are
stated therein.
What is claimed is:
reducing agent from the group consisting of tn'alkylalumi
num and alkylaluminum halides and (2) a compound of
the formula
'
1. A polymerization process which comprises contact
ing a lower molecular weight ethylenically unsaturated
hydrocarbon with a combination catalyst comprising (1)
a reducing agent from the group consisting of trialkyl
aluminum and alkylaluminum halides and (2) a com
pound of the formula
wherein M’ is a metal from groups IVb and Vb of the
periodic table, M is a member from the group consisting
of Si, Sn, y is the valence of M’ ‘and R1, R2 and R3 is
10
a hydrocarbon radical in which the mole ratio of .the
reducing agent to said compound is 0.1 to 50:1 to produce
wherein M’ is a metal from groups IVb and Vb of the
a normally solid polymer of said monoole?nic hydro
carbon.
periodic table, M is a member from the group consisting
of Si and Sn, y is the valence of M’, and R1, R2 and R3
ole?nic hydrocarbon is ethylene.
is a hydrocarbon radical to produce a normally solid
polymer of said unsaturated hydrocarbon.
2. A process, as de?ned in claim 1, wherein M’ is a
member from the group consisting of tetravalent vanadi
um and tetravalent titanium and M is silicon.
3. A process, as de?ned in claim 1, wherein the reduc
7. A process, as de?ned in claim 6, wherein the mono
15
8. A process, ‘as de?ned in claim 6, wherein the poly
merization reaction is canied out in presence of an inert
liquid reaction medium.
9. A process, as de?ned in claim 6, wherein the com—
pound is from the group consisting of Ti[OSi(CH3)3]4,
V[OSi(C6H5)3]4aI1d Ti(0Si(C6H5)3]4
ing agent is an alkyl aluminum halide.
References Cited in the ?le of this patent
4. A process, as de?ned in claim 1, wherein R1, R2
and R3 is methyl.
UNITED STATES PATENTS
5. A process, as de?ned in claim 1, wherein R1, R2
2,938,000
Wanless ______________._ May 24, 1960
and R3 is phenyl.
FOREIGN PATENTS
6. A polymerization process which comprises contact 25
ing a lower molecular weight monoole?nic hydrocarbon
534,792
Belgium ______________ __ Jan. 31, 1955
at from ~120° to 300° C. with from about 0.005 to
OTHER REFERENCES?
about 10%, based on the weight of the monoole?nic
et al.: J. Am. Chem. Soc. 77, January 5, 1955,
hydrocarbon, of a combination catalyst comprising (1) a 30 p. English
170.
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