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Патент USA US3069456

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3,069,446
Patented, Dec. 18, 1952
'5,
2
based on halogen analysis and are not intended to con
3,059,446
TKTANIUM HALIDE DEREVATIVES
Perry A. Argabright, Piseataway,
Edwin A. Sehmall,
note the actual molecular arrangement. In general, the
molecular ratio of titanium halide to organic electron
Roselle Park, N.J., assignors to Essa Research and En
donor is in the range of 1 to 1 to 4 to 1.
gineering (Ioinpany, a corporation of Delaware
The titanium complexes are prepared by mixing the two
No Drawing. Filed Dec. 3, 1958, Ser. No. 777,328
components in an inert hydrocarbon diluent. In indi
6 tCiaizns. ((12. 260-4295)
vidual preparations one or both of the reactants may be
This invention relates to novel derivatives of titanium
partly or completely soluble in the diluent, e.g., TiCl4,
halides. More particularly, it relates to the reaction prod
�Cl, (�I-I2)2S, �HCL TiBr4. In each case, the pro~
ucts of titanium halides with organic electron donors, these 10 cedure involves stirring the reaction mixture (at atmos
reaction products upon proper activation being active cata
phere pressure) in an inert atmosphere (N2) for one to
lysts for the low pressure polymerization of alpha ole
several hours and at a temperature between about 25� C.
?ns.
and the boiling point of the diluent. The resulting slurry
The low pressure polymerization and copolymerization
is then ?ltered and the solid product washed with several
of alpha ole?ns and diole?ns with catalyst systems made 15 portions of heptane. The complex is dried by vacuum at
up of a partially reduced, heavy, transition metal halide
room temperature. Typical reaction conditions are cited
and a reducing metal-containing compounchto high densi
in Table 1. All the products are colored (red to green)
ty, ?often isotactic, high molecular weight, solid, relatively
solids, decomposed by air or moisture, but stable in a nitro
gen atomsphere.
linear products has been assuming ever increasing im
portance and is now wellknown.
20
The alpha ole?nic feeds utilized in polymerization and
copolymerization include ethylene, propylene, ?butene-l,
heptene-l, dodecene-l, etc., with ethylene and propylene
preferred.
The resulting reaction? products are activated with a
metal alkyl compound, i.e. a trialkyl derivative of alumi
num, gallium, and indium, e.g. aluminum triethyl. The
two components in the proper proportions are admixed in
aninert solvent, e.g. a C3 to C18 paraflin such as isopentane
? Among the diole?ns that can be used in copolymeriza
25 or n-heptane, or an aromatic such as ?benzene or xylene,
tion are butadiene, isoprene, piperylene, vinylcyclohexene,
at temperatures vbetween 0� and 150� C. Slurries of dark
colored reduction products are obtained with some solu
cyclopentadiene, 1,4-pentadiene, etc. It is to be under
stood that wherever the term ?polymer? is used herein,
it connotes both homo- and copolymers.
The low pressure process is described in the literature,
e.g. see Belgian Patent 53 8,782 and ?Scienti?c American,?
September 1957, pages 98 et seq.
TiCl4.H2?S?CI-l2� complex reacts with AlEts to yield
products that are-nearly completely soluble in n~heptane.
In, general, the preferred ratio of alkyl compound to
' It has now been found that novel derivatives of titanium
the titanium halide reaction product is in the range of
halides are useful for this type of polymerization. These
novel derivatives are the reaction products of titanium
halides with organic electron donors as explained in further
detail below. The reaction products on proper activation
are useful in the low pressure polymerization of alpha ole
lto 1to 10to 1.
In the polymerization, the monomers are contacted with
the resulting catalyst in the presence of the same or dif
bility in the diluent. The solubility of the resulting prod
ucts depends on the nature of the titanium complex. The
fering inert hydrocarbon solvent such as isopentane, n
heptane, xylene, etc. The polymerization is conveniently
?ns. Alone or activated, they are possessed of catalytic
effected at temperatures of about 0� to 100� C. and
activity for isomerization, reduction, oxidation, etc.
The titanium halides utilized in the preparation of the
pressures ranging from about 0 to 500 p.s.i.g., usually 0
to 100 p.s.i.g. The catalyst concentration in the polym
reaction products can the titanium chlorides, bromides or
iodides with the ?rst two preferred, having a minimum of
erization zone is preferably in the range of about 0.03 to
0.5 wt. percent based on total liquid and the polymer prod
uct concentration in the polymerization zone is preferably
kept between about 5 to 15 Wt. percent based on total
two halogen atoms, e.g. TiCl2, TiCl3, TiBr2, TiBrz and
TiCl4. These materials are reacted with organic elec
45
tron donors.
contents so as to allow easy handling of the polymerized
Particularly preferred electron donors are triphenyl
mixture. The proper polymer concentration can be ob
chloromethane, diphenyl-chloromethane, benzyl sul?de,
tained by having enough of the inert diluent present or by
phenyl urethane, and tetraethyl-ammonium bromide.
stopping the polymerization short of 100% conversion of
An electron donor suitable for the needs of this inven
the monomers. When the desired degree of polymeriza
tion may be of two types.
tion has been reached, a C1 to C8 alkanol such as methyl
alcohol, isopropyl alcohol or n-butyl alcohol, desirably in
(1) A compound capable of donating a pair of elec
combination with a chelating agent for polymer deashing
trons to the titanium halide resulting in a complex
such as acetylacetone is normally added to the reaction
which contains a cation of marked stability.
mixture for the purpose of dissolving and deactivating,
55
the catalyst and for precipitating the polymer product
from solution. After ?ltration, the solid polymer may be
further washed with water, alcohol or acid such as hydro
chloric acid, dried, compacted and packaged.
(2) A compound capable of donating an anion to the
The polymers produced have molecular weights in the
titanium halide thereby producing a cation of high sta 60 range of about 50,000 to 300,000 or even as high as
bility.
3,000,000 as determined by the intrinsic viscosity meth
od using the I. Harris Correlation (I. Polymer Science,
8, 361, 1952). The polymers can have a high degree of
crystallinity and?a low solubility in n-heptane.
65
(2)
RiNeBXe + 'I?iX4 ??� minaret?
The exact structure of?the reaction product is very di?i
cult to postulatebecause of the complicated nature of
the molecule. Because of that, it should be understood
that where stoichiometric formulae are? shown, they are
It is to be understood that the term ?low pressure?
polymer as used herein connotes material prepared in
the indicated manner.
The advantages of this invention will be better under
stood by reference to the following examples:
EXAMPLE I.
Various derivatives of titanium chlorides and bromides
3,069,446
3
molar ratio of 2:1 based on the titanium.
These cat
alyst systems were then utilized in the polymerization of
ethylene. The details of conditions, yields, etc. for the
preparation of the titanium complexes are shown in Table
1 below.
Table 1
Metal halide
Organic component
A
as illustrations and that modifications may be made with
out departing from the spirit of the invention.
What is claimed is:
1. As a new composition of matter, the reaction prod
uct of a titanium halide consisting only of titanium and
halogen having a minimum of two halogen atoms and
an organic electron donor selected from the group con
were prepared with organic electron donors. The reac~
tion products were activated with aluminum triethyl in a
Conditions 1
Yield, g.
Stoichiometry 1
25 g.
0 g. @001 3 ___________ __
Room temp-40 hrs _______ ._
31.0
�C1-(TlCl4)2.
25 g.
25 g.
0 g. @0013?
0 g. �C1 3..-
75� C.?-40 hrs_____
75� O.?40 hrs_____
42. 0
28. 8
�Cl-(?I?iCla)2.
(b3CC1-(TiCl2)4.
25 g.
25 g.
25 g.
0 g. dagCHCl 4.
.5 g. (l?l'.g)gS _
. HC02Et a
Room temp.?90 h .
Room temp.?40 lien
Room temp.?45 hrs.
11.5
24. 0
19. 8
(dagCHCDg-TiCLg.
(I'I2)2S-T1Cl.1.
HC02Et-TiOl4.
Room temp.?90 hrs _______ __
19.0
Et4NBr-TiBr4.
25 g.
. EtiNBr 7 ________ __
5 Benzyl sul?de.
6 Phenyl urethane.
7 Tetraethyl-ammonium bromide.
1 Reactants diluted with 200 ml. normal heptane.
2 Indicated by halogen analysis.
' Triphenyl-chloromethane.
4 Diphenyl-chloromethane.
sisting of triphenyl chloromethane, diphenyl chloro
The relative activities of the catalyst system (based
methane, benzyl sul?de and phenyl urethane, the molar
ratio of titanium halide to organic electron donor being
on weight of said polymer) were:
Table 2
Relative activity 25 in the range of 1:1 to 4:1.
Catalyst:
�Cl?(TiCl3)-2
_____________________ __
(�HCl) 2?TiCl4
2. As a new composition of matter, the reaction prod
2.8
2. 8
___________________ _ _
�Cl--(TiCl4) 2
____________________ _._
2.3
�Cl--(TiCl2)4
____________________ __
1.9
HCO2Et--TiC14 ___________________ __
1.3
(H2)2S--TiC14 ____________________ __
1.0
E'QNBr-TiBL;
______________________ _... <1.0
uct of TiCl4 and triphenyl chloromethane, the molar ratio
of titanium compound to triphenyl chloromethane being
30
in the range of 1:1 to 4:1.
3. As a new composition of matter, the reaction prod'3
uct of TiC13 and triphenyl chloromethane, the molar ra
tio of titanium compound to triphenyl chloromethane
being in the range of 1:1 to 4:1.
4. As a new composition of matter, the reaction prod
It should be noted from this table that TiCl2-aluminum 35
uct of TiCl2 and triphenyl chloromethane, the molar ra
triethyl alone only gave traces of polymer. On the other
tio of titanium compound to triphenyl chloromethane
hand, the use of the trityl chloride reaction product of
being in the range of 1:1 to 4:1.
TiCl2 gave an active catalyst.
5. As a new composition of matter, the reaction prod
EXAMPLE II
40 not of TiCl4 and diphenyl chloromethane, the molar ratio
TiClg ___________________ __ (trace of polymer)
A similar example was run as in Example I except that
of titanium compound to diphenyl chloromethane being
propylene was polymerized. Again the complexed TiCl;
in the range of 1:1 to 4:1.
system activated with aluminum triethyl gave a much
6. As a new composition of matter, the reaction prod
more active catalyst than TiCl2 alone so activated. The
uct
of TiC14 and phenyl urethane, the molar ratio of ti
45
results and conditions are shown in Table 3 below. The
tanium compound to urethane being in the range of 1:1
compound designations are again the stoichiometric ones
to 4:1.
as explained previously.
Table 3
PROPYLENE POLYMERIZATION IN 300 ML. ROCKING BOMB AT 80� 0. FOR 2 HOURS
Complex _________________________ __
�C1?(TlC13)g
0.
0.
AlElia
0.5
e1
ercen
t
_-__
Diluent.g___l_3___ ______ __
-
_._-
Metal alkyl/Ti ratio ______________ __
Cat. concn., weight percent"
Solid polymer. 1;
Cat-e -. elem
Percent conv---
at
Xylene
4
4s3COl?(TiC1z)4
0. 59
GaEts
.
�
I
Xylene
0.
111E133
.
TiCla
0. 75
AbEta
..
1
.
0.
0. 57
.
a
Xylene
(CI-ICl)z?TiCli
.
a
Xylene n-Heptane n-Heptanc
HCO2Et?TiCl4
0v 57
0. 71
.
a
.
0. 3e
.
a
a
a
Xylene n-Heptane
Xylene
n-Heptane
?
2,
2,
1. 25
1. 25
10
3
3
5
5
0. 23
120
0. 5
29
0.5
2s
0. 64
49
0.69
53
0. 44
19
0. 48
20
0. 52
3e
0.60
1
0.33
4
91
80
21
39
14
31
38
G5
40
71
1s
25
1s
27
32
48
0.5
1
4
5
The advantages of this invention will be apparent to
those skilled in the art. Novel materials ?are made available which can have great importance in catalytic 65
opera'tlons'
Since the reaction between T101, and trityl cmoride is
References Cited in the file of this patent
UNITED STATES PATENTS
2 879 263
Anderson et a1
M at 24 1959
zjsssjseo
Weber ______________ __ May 12, 1959
2886.561
Reynolds et a1- -------- -- lg?lay 1;? i323
iggielig'閒gf ________ "Selig-22, 1959
nearly quantitative and gives an intensely colored prod
uct (yellow) it follows that trityl chloride can serve as 70
either a quantitative or qualitative analytical reagent for
2?912?424
2:925:392
cashers
566113251;
the detection of T1X4.
2,935,522
Samour ______________ _- May 3. 1960
533.362
Belgium _____________ __ May ?16, 1955
?FOREIGN PATENTS
It is to be understood that this invention is not limited
to the speci?c examples which have been offered merely 75
' ______ " Nov 16 1959
_____ _._ Feb. 16, 1960
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