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Патент USA US3030443

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tea Patgm
1
2
3,030,433
silica gel, alumina, silica alumina, etc. the carrier and
salt hydrate are then exposed to BF3 until the desired
POLYMERIZATION 0F OLEFINS WITH METAL
SALT HYDRATE-BFs COMPLEX
amount of BF3 has reacted with the salt hydrate or
complete complex formation has been attained.
Harmon M. Knight, La Marque, and Joe T. Kelly, Dick
The amount of BB; which will be taken up by some salt
inson, Tex., assignors, by mesne assignments, to ‘Stand
ard Oil Company of Indiana, Chicago, 11]., a corpora
hydrates is also determined by the temperature at which
the BFs-salt hydrate complex is produced or is maintained.
At ordinary temperature of about 20° C. a particular
salt hydrate may complex with 1 mol of BF3 per mol
tion of Indiana
No Drawing. Filed Feb. 17,1958, Ser. No. 715,502
8 Claims. (Cl. 260-4580)
This invention relates to the polymerization of ole?ns
to polymeric materials and particularly of tertiary ole?ns.
An object of the invention is a solid polymerization
catalyst for certain ole?ns. Another object is a process
of polymerizing tertiary ole?ns and particularly removing
of hydrate water. On the other handat 50° C. the
complex may contain only about 0.7 mol of BF, per
‘mol of hydrate water. When the complex of the higher
temperature is brought to the lower temperature again
and exposed to BE, enough BF3 is taken up to return to
15 the 1:1 BF3 hydrate water ratio. Even though the solid
complex in some cases does lose some BF3 as .the com—
such ole?ns by polymerization from admixture with other
ole?ns.
' 3,030,433
Patented Apr. 17, 1962
plex ‘is brought to higher temperatures, the complex is
not completely dissociated until exposure to temperature
and time conditions such that the salt hydrate component
A further object is a process for polymerizing
conjugated diole?ns. A particular object is a process
‘employing a solid catalyst for polymerizing isobutylene.
itself dissociates by release of the water of hydration.
Other objects will become apparent in the course of the
‘detailed description-of the process.
In the process tertiary ole?ns and/or conjugated di
ole?ns are contacted with a catalyst consisting essentially
Thus the process may be carried out at temperatures
and pressures normally associated with polymerization of
ole?ns such as, isobutylene and diole?ns such as buta
diene. The upper temperature of operation is naturally
of a solid complex of a metal salt of an inorganic acid
containing water of hydration and boron tri?uoride. The 25 limited by the dissociation temperature of the particular
salt hydrate present in the solid complex catalyst. Par
polymeric product is then separated from the solid cata
ticularly suitable temperatures are between about 0° C.
1 st.
yThe catalyst -of the invention is a solid formed by the
and 50° C.
I
I
I
.
The hydrates of :the following metal salts of inorganic
organic acid containing water of hydration hereinafter 30 acids readily form solid complexes with boron tri?uoride:
aluminum arsenate, aluminum borate, aluminum ortho
spoken of .as a salt hydrate. The presence
’ of BF, _ in
phosphate. aluminum polyphosphate, aluminumpyrophos
‘the form of -a complex results in aitremendously active
phate, aluminum ‘sulfate, aluminum tungstate; barium
material with respect to polymerization of the de?ned
reaction of boron tr-i?uoride with a metal salt of an in
stannate; beryllium, pyrophosphate, beryllium silicate,
ole?ns. When a salt hydrate and BE, are contacted
for a prolonged period of time a solid material is pro 35 beryllium ‘stannate, beryllium sulfate; bismuth stannate,
bismuth tungstate; boron orthophosphate; calcium stan
duced which ‘contains the salt hydrate and about 1 mol
nate, calcium sulfate; cadmium pyroantimonate, cadmium
of BF3 per mol of water of-hydrationpresent in the salt
pyroarsenate, vcadmium borate, cadmium borotungstate,
hydrate. Although the ultimate complex contains this
cadmium orthophosphate, cadmium polyphosphate, cad
amount of BF3 different salt hydrates behave differently
:in their speed of, up-take of BF3 and some do not in a 40 mium pyrophosphate, cadmium stannate, cadmium sul
fate, cadmium tungstate_;ycerous sulfate, cerous tungstate;
-reasonable length of time reach this ultimate BF3 content
cobaltous arsenate, cobaltous pyroarsenate, cobaltous
of 1 mol per mol of hydrate water present. All salt
borate, cobaltous molybdate, cobaltous orthophosphate,
hydrate BF3 complexes ‘are not equally effective as cata
lysts, even with the same molar BF3 content. Some
cobaltous polyphosphate, cobaltous ,pyrophosphate, c0
.salt hydrates are extremely effective polymerization cata 45 baltous silicate, cobaltous stannate, cobaltous sulfate, co
baltous tungstate; chromic pyrophosphate, chromic sul
lysts when only tiny amounts of BF3 are reacted with
fate, chromic .tungstate; cupric arsenate, cupric borate,
‘the hydrate water. Other salt hydrates 'become only
‘cupric polyphosphate, cupric pyrophosphate, cupric sili
moderately effective catalysts even with the maximum
cate, cupric stannate, cupric sulfate; ferrous pyrophos
theoretical amount of BF3 reacted with ‘the hydrate water.
In general effective polymerization ability is present when
phate, ferrous silicate, ferrous stannate, ferrous sulfate;
ferric pyroantimonate, .ferric ‘pyroarsenate, ferric molyb
the particular salt hydrate contains from about 0.1 to
date, ferric ‘orthophosphate, ferric polyphosphate, ferric
‘about 1 mol of BF3 for each mol of water of‘hydration
pyrophosphate, ferric ‘silicate, ferric stannate, ferric sul~
‘present in vthe salt hydrate. It is to be understood that
fate; potassium dihydro-pyroantimonate; magnesium pyro
‘when the de?ned salt hydrate contains water in excess
of the theoretical amount of hydrate water in the form 55 antimonate, magnesium arsenate, magnesium pyroarse
nate, magnesium orthophosphate, magnesium pyro
of adsorbed water the adsorbed extraneous water will
phosp'hate, magnesium silicate, magnesium stannate,
take up BF3 and therefore it is apparently possible for
magnesium sulfate; manganous .pyroantimonate, man
'mol of the true hydrate water. It is preferred to operate
ganous pyroarsenate, manganous borate, manganous
“with salt hydrates which have been dried to remove ex 60 polyphosphate, manganous pyrophosphate, manganous
a salt hydrate to react with more than 1 mol of BFg-per
traneous water for example, by carefully heatingthe par
ticular salt hydrate below its decomposition temperature
until the adsorbed water has been evaporated.
_ The complex is very readily prepared by introducing
BF3 into a vessel containing the particular salt hydrate
and'permitting the two materials to'remain in the vessel
until a constant BF3 pressure is reached. Faster reaction
65
stannate, manganous sulfate; sodium orthophosphate,
sodium pyrophosphate; nickel pyroantimonate, nickel
pyroarsenate, nickel .borotungstate, nickel molybdate,
nickel orthophosphate, nickel pyrophosphate, nickel
silicate, .nickel silicomolybdate, nickel stannate, nickel
sulfate, nickeltungstate; lead borate,“lead stannate; anti
mony/arsenate, antimony sulfate; stannous pyrophosphate,
is obtained by using the salt hydrate-in a ?nely powdered
stannous sulfate; ‘stannic pyroarsenate, stannic pyrophos
form.
"It ~is'to be understood ‘that the solid ‘complex may be 70 phate; thorium 'pyrophosphate; titanium pyrophosphate;
vanadium silicate, ‘vanadium sulfate; zinc molybdate; zinc
T"used as a catalyst directly. Or the salt hydrate‘may ‘be
‘pyropho'sphate,'zinc' silicate, zinc sulfate; zirconium pyro
“depositedon a carrier such “as charcoal, Fuller’s earth,
3,030,433
.4
3
and the vacuum maintained for about one-half hour. By
weighing the vessel the amount of HE; complexed was
of rare earth sulfates; and ceric sulfate.
determined.
Particularly suitable are ferric stannate containing
The vessel containing the solid complex of ferric pyro
about 5 mols of hydrate water and 1 mol of BF3 per mol
of hydrate water; cobalt arsenate hydrate containing 3 5 phosphate hydrate and 0.3 mol of BF3 per mol of hydrate
water was placed in a shaker in an ice bath and cooled
mols of water of hydration and 0.5 mol of BF3 per mol
to about 20° C. Anhydrous n-hexane was added to the
of hydrate water; and ferric pyrophosphate hydrate con
vessel in an amount of about 500 ml. to serve as a solvent
taining about 7 mols of water of hydration and about
and also to improve heat transfer within the vessel.
0.3 mol of BF3 per mol of hydrate water.
The mono-ole?n feed to the process is a tertiary ole?n. 10 Technical grade isobutylene was added intermittently to
the vessel with shaking of the vessel; the additions were
Ole?ns which do not have a tertiary carbon atom are
adjusted to keep the temperature of the contents of
not appreciably affected by the catalyst _of the instant
the vessel below 40° C. After all the isobutylene had
process for example, a mixture of isobutylene, butene-l
phosphate, zirconium silicate, zirconium sulfate; mixture
been added the vessel was shaken for 15 more minutes.
and butene-2 contacted with one of the de?ned com
plexes results in a polymeric isobutylene product and es 15 The vessel was opened and the liquid material ?ltered
from the solid complex. The liquid product was distilled
sentially all the butene-l and butene-Z are recovered un
on an e?icient column to obtain a fraction of material
polymerized. The ole?n feed may be either essentially
boiling from 170—400° F. (gasoline range product) and
pure material or mixtures of ole?ns, reactive or reactive
and inert, or mixtures of reactive ole?ns with other inert
material boiling above 400° F.
material such as the corresponding saturated hydrocar 20 The operating conditions and the yield of product are
set out below:
bons. Examples of suitable ole?ns are isobutylene (2
methylpropene), 2-methylbutene-1, 2-methylbutene-2, 2
methylpentene-l, 3-methylpentene-2, 2,3-dimethylbutene
1, 2-ethylpentene-l, 3-ethylpentene-2, 2,3,4-trimethy1
pentene-Z, 2,6~dimethyloctene-1, and 2,4-dimethyloc
tene-4.
Fe4(P2Oq)3.61/2H2O
18
BF3/H2O (molar) ________________________ _..
25 Initial temp., ‘’ C. ________________________ __
0.3
13
Total reaction time (min.) _________________ _...
Reactive feed charged (gm.) _______________ __
25
411
Conjugated diole?ns are readily polymerized by the
solid complex catalyst of the instant process. A mixture
of the de?ned tertiary ole?ns and conjugated diole?ns may
be charged to the process. Examples of conjugated di
Product( recovered):
.
30
ole?ns suitable for use in the process are: butadiene-l,3,
The process may be carried out by adding solid com
170—400° F. (gm.) ___________________ __
266
Br number ______________________ __
160.0
Sp. gr. at 60° F ___________________ .. 0.7636
pentadiene-1,3, isoprene, hexadiene-1,3, Z-methylpenta
dime-1,3, 2-ethylbutadine-1,3, octadiene-2,4, Z-methyl
heptadiene-1,3, deeadiene-1,3, and 3,7-dimethyloctadiene
1,3.
----------------- -
BF3 absorbed (gm.) ______________________ __
Octane number (research) ________ __
I
35
plex to a batch reactor and introducing the ole?nic or
diole?nic feed therein and permitting the catalyst and
45
Br number ______________________ __
62.0
Sp. gr. at 60° F. _____________________ __ 0.8227
Kinematic vise. at 130° F. (cs/sec.) __
11.1
Total product recovered (gm.) _____________ __
311
the reactive material to sit for the desired time at the
particular temperature until reaction has been completed. 40
It is more effective to use a complex which has been put
into a ?nely powdered form and introducing ole?n under
conditions of temperature and pressure such that a sub
stantial amount of liquid phase is present at the start of
101.3
400° F.+ (gm.) _____ ___. ______________ __
EXAMPLE NO. 2
In this example the catalyst was a solid complex of
ferric pyrophosphate hydrate and BE, prepared as set
out in Example No. 1. The reactor was charged with
n-hexane diluent under conditions as in Example No. 1.
The reactive material in this run was pure grade buta
the polymerization. Stirring is used to provide better con
tacting of the powdered catalyst and the reactant mate 45 diene-1,3; this material contained 0.2 weight percent of
t-butyl catechol stabilizer. All of the butadiene was
rial. The process may be carried out in a continuous
charged without temperature rise in the reactor; when
manner by any of the procedures commonly used for
the material was completely charged the temperature in
polymerization for example, the feed material may be
the reactor abruptly ran away and reached a maximum
passed through a bed of solid complex, or it may be
passed through a ?xed-?uid bed of solid complex parti 50 of about 175° C. and the initial pressure rose to about
550 p.s.i.g. After about 60 minutes the temperature
cles, or it may be passed through a ?uid bed provided
started to drop in the reactor indicating completion of
with continuous draw-o?? of catalyst and continuous
the reaction, The liquid product was separated from the
introduction of fresh catalyst.
complex catalyst by ?ltration and the hexane removed
The process is illustrated by a number of examples car
ried out in a batch reactor. It is to be understood that 55 from the polymer product.
these examples are illustrative only and do not limit
the scope of the process.
EXAMPLE NO. 1
The material boiling above
170° F. weighted 888 grams for conversion of 83 weight
percent. This material was an extremely viscous liquid‘.
The conditions and results of this example are set out.
hereinafter.
The reactor was a 4 liter carbon steel vessel. The
vessel was oven dried before each test. Seventy-?ve 60 Fe4(P207)3.61/2H2O
BF3 absorbed (gm.) (gm.)
_____________________
________________ __
_..
grams of ferric pyrophosphate hydrate containing 6.5
BF3/H2O (molar) _______________________ __.
mols of water of hydration was added to the dried vessel
Initial temp., ° C _____________________ __ca__
which was closed and the air removed therefrom by a
vacuum pump. Technical grade isobutane in an amount 65 Total reaction time (min.) ____________ __ca__
Reactive feed charged (gm.) _______________ _..
of 500 grams was introduced into the evacuated vessel.
This isobutane had been treated with calcium hydride
to remove water.
The vessel was placed in an ice bath
and anhydrous boron tn'?uoride gas was added to the
vessel at a slow rate until the pressure inside the vessel 70
was 300 ‘p.s.i.g. The vessel was placed in a rocker and
‘rocked, vfor about 8 hours; then the vessel was allowed
181
0.3
175
60
1067
Product (recovered):
Br number _________________________ __
49.5
Sp. gr. at 60° F ______________________ __ 0.9226
Maleic anhydride value _______________ __
2.5
EXAMPLES NOS. 3-9
to stand about 24 more hours; then the vessel was de
Seven salts of differing composition were used as the
pressured and evacuated to remove excess BF3 and also
salt hydrate portion of the complex in separate examples
the isobutane. Then the vessel was heated to 80° C. 75 using isobutylene as the ole?n feed. All of these ex
3,030,433
5
6
amples were carried out following the procedure of Ex
3. The process of claim 1 wherein said ole?n is iso
ample No. 1. The results of these examples are set out
in Table I.
butylene.
It can be seen that solid complex contained BF3 in a
dime-1,3.
4. The process of claim 1 wherein said diole?n is ‘buta
5. The process of claim 1 wherein said hydrate is ferric
BFs/water of hydration mol ratio ranging from 0.1 to 1. 5
stannate hydrate.
The initial temperatures ranged from 11° C. to 30° C.;
6. The process of claim 1 wherein said hydrate is co
balt arsenate hydrate.
in all cases the individual temperature surges increased
to 40° C. The molar ratio of isobutylene charged to the
Table I
POLYMERIZATION OF ISOBU’I‘YLENE
Example N os
3
4
5
Salt (75 gm.)
CdSO4.H2O
A15(P3010)3.6H20
Fe2(SnOa)a.4.7H2O
BF; absorbed (gm.)
_._
BF3/H2O (molar) _____________________________________________________ ._
Temp., ° 0-.
--
Reaction time, min
Isobutylene charged (gm.) _
Isobutylene/salt hydrate (molar ratio) ................................. ._
Product (recovered):
170-400" F. (gnL)
Br number
_.
66
35
1
11
1
25-35
60
290
45
387
402
16
95
70
53
228
288
0. 7374
0.7612
0. 7636
103.0
102. 9
101. 8
128
Sp. gr. at 60° FOctane number (research) ____________________________________ __
400° F.+ (gm.)
16
0.3
20-30
_.
110
None
Br number
Sp. gr__
Viscosity (kinematic at 130° F., cs./sec.)
53
6
B311; (75 gm,)__
FGSDOEBHZO
Temp., ° C
Reaction time, min
__________________ __
_. _
Example Nos__
BFa/Hzo (molar) _______________________________________ --
84
75
0. 8160
3. 4
Viscosity index_
Product-Total recovered (gm.)
BFs absorbed (gm) .................................... ..
85
58
0. 8049
7 '
COSiO3.H2O
5
1
15-30
372
8
9
2C0BgO4.CO0zH2O ‘ COASgO7.3HzO
28
0.1
10-15
313
60
____________________ __
15-30
17
0.5
15-30
25
35
Isobutylene charged (gIIL) ______________________________ --
408
582
Isobutylene/salt hydrate (molar ratio) .................. ..
28
22
212
110
1 110
119
100
131
192
116
0. 7587
101. 6
146
61
0. 7669
100. 8
368
61
0. 7661
100. 3
285
53
0. 7686
101. 3
323
55
0. 8227
______________ _-
o. 8403
0. 8304
Product (recovered):
17 - 0°
(gm.) .................................. ._
Br number ____ __
Sp, gr-
V‘ cosity (kinematic at 130° F., cs./sec.) ________________________ -Viscosity index
_
Product-Total recovered (gm) ________________________ ._
358
22
30
443
545
____________________ -_
25. 1
29. 4
119
468
118
385
51
132
515
1 Variable composition—18% water content.
2 Some product lost in distillation.
7. The process of claim 1 wherein said hydrate is ferric
salt hydrate varied from 16 to 95. This ratio has been
pyrophosphate hydrate.
based on the salt hydrate charged in order to eliminate
8. A process comprising contacting isobutylene, at a
the variable of BF3 amount complexed.
Examination of the recovered product shows a varia 55 temperature between 0'’ C. and 50° C., with a catalytic
amount of a solid complex consisting of a metal salt
tion in polymerization eifectiveness of the diiferent solid
wherein said salt is selected from the class consisting of
complexes not only in the overall conversion but in the
arsenate, borate, phosphate, silicate, stannate and sulfate,
amount compared with gasoline range material produced.
Thus having described the invention, what is claimed
1s:
which salt contains water of hydration and between about
60 0.1 and 1 mol of boron tri?uoride per mol of water of
1. A polymerization process comprising contacting an
ole?n selected from the class consisting of tertiary ole?ns,
conjugated diole?ns and mixtures thereof, with a catalyst
consisting of a solid complex consisting of boron tri
?uoride and a metal salt wherein said salt is selected from 65
the class consisting of arsenate, borate, phosphate, silicate,
stannate and sulfate, which salt contains water of hydra
tion and wherein said contacting is carried out at a tem
perature between about 0° C. and 50° C.
2. The process of claim 1 wherein said complex con 70
tains between about 0.1 and 1 mol of BF;.; per mol of
water of hydration.
hydration and separating isobutylene polymer from said
complex.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,390,100
2,824,146
2,824,151
2,824,156
Hughes _____________ __ Dec.
Kelly et a1. __________ __ Feb.
Kelly et a1 ____________ __ Feb.
Kelly et al. __________ _._. Feb.
4,
18,
18,
18,
1945
1958
1958
1958
FOREIGN PATENTS
737,026
Great Britain _________ __ Sept. 21, 1955
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