U.S. patent number RE28,475 [Application Number 05/450,822] was granted by the patent office on 1975-07-08 for process for copolymerization of maleic anhydride with 1-olefins.
This patent grant is currently assigned to Gulf Research & Development Company. Invention is credited to Ronald G. Blecke, Robert W. Hill.
United States Patent |
RE28,475 |
Blecke , et al. |
July 8, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Process for copolymerization of maleic anhydride with 1-olefins
Abstract
Maleic anhydride and polymerizable liquid 1-olefins having from
4 to 14 carbon atoms are copolymerized employing a liquid-liquid
dispersion as the reaction mixture by use of excess liquid 1-olefin
as a diluent and a minor amount of a copolymer of maleic anhydride
with an aliphatic 1-olefin having from 14 to 18 carbon atoms as a
dispersing agent. Maleic anhydride and a polymerization initiator
becomes dispersed in the mixture of olefin and dispersing agent and
polymerization takes place when the temperature is raised to about
80.degree. C. with agitation.
Inventors: |
Blecke; Ronald G. (Lower
Salford Twp., Montgomery County, PA), Hill; Robert W.
(Gibsonia, PA) |
Assignee: |
Gulf Research & Development
Company (Pittsburgh, PA)
|
Family
ID: |
26954215 |
Appl.
No.: |
05/450,822 |
Filed: |
March 13, 1974 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
270331 |
Jul 10, 1972 |
03729451 |
Apr 24, 1973 |
|
|
Current U.S.
Class: |
526/203; 526/88;
526/272; 526/910 |
Current CPC
Class: |
C08F
267/04 (20130101); C08F 10/00 (20130101); C08F
22/04 (20130101); C08F 10/00 (20130101); C08F
4/28 (20130101) |
Current International
Class: |
C08F
10/00 (20060101); C08F 22/00 (20060101); C08F
22/04 (20060101); C08F 267/00 (20060101); C08F
267/04 (20060101); C08F 002/02 (); C08F 002/08 ();
C08F 222/06 () |
Field of
Search: |
;260/78.5R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Kight; John
Claims
We claim:
1. A dispersion process for manufacturing a copolymer of maleic
anhydride with an aliphatic 1-olefin comprising the steps:
a. forming a reaction mixture by mixing together at least one
polymerizable liquid 1-olefin having from 4 to 14 carbon atoms, a
minor amount of an equimolecular copolymer of maleic anhydride with
a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a
dispersing agent, a polymerization initiator and a quantity of
maleic anhydride which is less than a molar equivalent of the
amount of 1-olefin present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the polymerization
reaction is initiated,
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-olefin
is obtained as a polymerization product mixture, and
d. recovering the solid particles of product from the
polymerization product mixture by filtration or evaporation of the
liquid 1-olefin.
2. A dispersion process for manufacturing a copolymer of maleic
anhydride with 1-hexene consisting essentially of the steps:
a. forming a reaction mixture by mixing together 1-hexene, a minor
amount, between 1 and 2 weight percent concentration, of an
equimolar copolymer of maleic anhydride with a linear aliphatic
1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a
polymerization initiator and a quantity of maleic anhydride which
is less than a molar equivalent of the amount of 1-hexene
present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the polymerization
reaction is initiated,
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-hexene
is obtained as a polymerization product mixture, and
d. recovering the solid particles of product from the
polymerization product mixture by filtration or vaporization of the
liquid 1-hexene.
3. A dispersion process for manufacturing a copolymer of maleic
anhydride with 1-decene consisting essentially of the steps:
a. forming a reaction mixture by mixing together 1-decene, a minor
amount, between 1 and 2 weight percent concentration, of an
equimolecular copolymer of maleic anhydride with a linear aliphatic
1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a
polymerization initiator and a quantity of maleic anhydride which
is less than a molar equivalent of the amount of 1-decene
present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the polymerization
reaction is initiated,
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-decene
is obtained as a polymerization product mixture, and
d. recovering the solid particles of product from the
polymerization product mixture by filtration or vaporization of the
liquid 1-decene. .Iadd. 4. A dispersion process for manufacturing a
copolymer of maleic anhydride with an aliphatic 1-olefin comprising
the steps:
a. forming a reaction mixture by mixing together at least one
polymerizable liquid 1-olefin having from 4 to 14 carbon atoms, a
minor amount of an equimolecular copolymer of maleic anhydride with
a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a
dispersing agent, a polymerization initiator and a quantity of
maleic anhydride which is less than a molar equivalent of the
amount of 1-olefin present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the polymerization
reaction is initiated, and
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-olefin
is obtained as a polymerization product mixture. .Iaddend..Iadd. 5.
A dispersion process for manufacturing a copolymer of maleic
anhydride with 1-hexane consisting essentially of the steps:
a. forming a reaction mixture by mixing together 1-hexane, a minor
amount, between 1 and 2 weight percent concentration, of an
equimolecular copolymer of maleic anhydride with a linear aliphatic
1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a
polymerization initiator and a quantity of maleic anhydride which
is less than a molar equivalent of the amount of 1-hexane
present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the polymerization
reaction is initiated, and
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-hexane
is obtained as
a polymerization product mixture. .Iaddend..Iadd. 6. A dispersion
process for manufacturing a copolymer of maleic anhydride with
1-decane consisting essentially of the steps:
a. forming a reaction mixture by mixing together 1-decane, a minor
amount, between 1 and 2 weight percent concentration, of an
equimolecular copolymer of maleic anhydride with a linear aliphatic
1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a
polymerization initiator and a quantity of maleic anhydride which
is less than a molar equivalent of the amount of 1-decene
present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the polymerization
reaction is initiated, and
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-decene
is obtained as a polymerization product mixture. .Iaddend.
Description
DESCRIPTION OF THE INVENTION
The preparation of copolymers of maleic anhydride with various
unsaturated monomers, particularly ethylene and styrene is well
known in the art. More recently, copolymers of maleic anhydride
with various branched and linear aliphatic 1-olefins have been
prepared, some of which are finding uses in industry. It has been
found however, that in the preparation of a copolymer of maleic
anhydride and such 1-olefins that the recovery of the copolymers
presents some fairly difficult problems. The use of an excess of
olefin in solution polymerization processes so as to obtain more
complete reaction increases the difficulty of separating the
product.
A satisfactory practice which has been used as disclosed for
example, in U.S. Pat. 3,461,108, is to employ certain efficient
solvents for the polymerization step, keeping the monomers and in
some instances the polymers also in solution during the
polymerization, and then adding to the resulting solution another
liquid, which causes precipitation of the polymer products in
finely divided filterable solid form. The selection of the
combination of reaction solvent and precipitating solvent is
critical. A very limited choice of solvent combinations exists, no
completely satisfactory precipitating agent having been found for
some copolymers. Furthermore, the solvents are expensive and for
this reason must be separated and recovered. The solvent
separation, polymer filtration and washing steps require bulky
equipment and are time consuming.
It has been found in accordance with the present invention that
copolymers of maleic anhydride with a variety of polymerizable
1-olefins having from 4 to 14 carbon atoms can be produced in the
form of dispersions of solid particles in excess 1-olefin as a
diluent, provided there is employed as dispersing agent an
equimolecular copolymer of maleic anhydride with an aliphatic
1-olefin having from 14 to 18 carbon atoms and the reaction mixture
is heated to the vicinity of 80.degree. C. with agitation to
generate a liquid-liquid dispersion as a polymerization reaction
mixture.
Briefly, the present invention consists of a liquid dispersion
process for manufacturing a copolymer of maleic anhydride with an
aliphatic 1-olefin comprising the steps:
A. forming a reaction mixture by mixing together at least one
polymerizable liquid 1-olefin having from 4 to 14 carbon atoms, a
minor amount of an equimolecular copolymer of maleic anhydride with
an aliphatic 1-olefin having from 14 to 18 carbon atoms as a
dispersing agent, a polymerization initiator and a quantity of
maleic anhydride which is less than a molar equivalent of the
amount of 1-olefin present,
b. agitating the reaction mixture of step (a) and heating to
increase the temperature to the point at which the reaction mixture
becomes a liquid-liquid dispersion and the polymerization reaction
is initiated,
c. continuing agitation of the reaction mixture at a temperature
near the decomposition temperature of the polymerization initiator
until a dispersion of solid copolymer particles in liquid 1-olefin
is obtained as a polymerization product mixture, and
d. recovering the solid particles of product from the
polymerization product mixture by filtration or vaporization of the
liquid 1-olefin.
The procedure outlined above eliminates the usual precipitation
step in solution polymerization which requires costly separation of
solvent and precipitant when recycled, yields a liquid-liquid
dispersion type of reaction mixture which has a low viscosity and
is easily stirred, pumped and handled and permits operation at
higher solids content in the product mixture. This results in
greater throughput capacity and lower process costs for equipment
of a size comparable to that employed in solution polymerization.
The dispersion copolymerization process of this invention is
characterized by a combination of features which include the use of
a 1-olefin comonomer as the dispersing medium, a unique dispersing
agent and a temperature program which allows the dispersion to
develop. The process is discussed in greater detail below.
In carrying out the process there are some critical features which
must be taken into account. One of the most critical features is
selection of the polymeric dispersing agent. Only the copolymers of
the maleic anhydride with the higher 1-olefin appear to have good
dispersion efficiency. Equimolecular copolymers of maleic anhydride
with 14 to 18 carbon 1-olefins may be used for the purpose,
preferably at a concentration of 1 to 2 weight percent. The
copolymers, which may be made by published methods, for example the
method of U.S. Pat. 3,560,456, are characterized in the following
discussion.
The dispersing agents employed in the method of this invention are
linear, low molecular weight copolymers of straight chain 1-olefins
and maleic anhydride. The olefin and maleic anhydride are present
in a 1:1 molar ratio, as shown in the following structural formula.
R represents a linear alkyl substituent, the length of which is
determined by the choice of the olefin comonomer. In the
tetradecene copolymer, for example, the R substituent is dodecyl.
##EQU1##
The copolymer dispersing agents are white solids with melting
ranges which center from about 117.degree. C. (1-octadecene
copolymer) to about 129.degree. C. (1-tetradecene copolymer).
Typical physical properties are summarized below:
1-tetra- 1-octa- decene decene Property copolymer copolymer
______________________________________ Melting range, .degree.C
124-133 115-119 Equivalent acid value .sup.1 382 321 Specific
gravity .sup.2 1.036 0.973 Inherent viscosity .sup.3 0.147 0.144
______________________________________ .sup.1 Theoretical values,
ignoring end group effect. .sup.2 True density. .sup.3 5.0 g./dl.
in methyl isobutyl ketone at 77.degree. F.
The copolymer dispersing agents are soluble in a wide variety of
organic solvents, as shown below. The solubility of these
copolymers in hydrocarbon solvents is a unique characteristic, not
shared by copolymers of maleic anhydride with lower 1-olefins.
SOLUBILITY OF COPOLYMER DISPERSING AGENTS
______________________________________ 1-tetra- 1-Octa- decene
decene copolymer copolymer ______________________________________
Chlorinated solvents: Carbon tetrachloride S S 1,2-dichloroethane S
S Esters: Ethylacetate S S Hydrocarbons: Benzene S S Ligroin SlS S
Decalin SlS S Ketones: Acetone S S Methyl isobutyl ketone S S
Ethers: Bis(2-methoxyethyl)ether S S
______________________________________ Note.-S=soluble; >5
g./100 ml. SlS=slightly soluble; 1-5 g./100 ml.
In carrying on the heating program it is desirable to have the
solid maleic anhydride entirely mixed with liquid prior to raising
the temperature to the melting point of the maleic anhydride. The
temperature should be increased slowly enough so that the mixing or
stirring device employed in the reactor is able to maintain a
condition of efficient mixing during the rise in temperature. If
raising the temperature to the decomposition temperature of the
initiator is carried out too quickly, without efficient stirring,
polymer may adhere to the walls of the reactor. Although the
process will operate and a polymer dispersion does form, the solid
coating of polymer on the wall of the reactor will necessitate a
cleaning operation. The speed with which the temperature can be
raised to the decomposition temperature of the initiator depends to
a great extent upon the efficiency of the mixing apparatus in the
reactor. This is largely a matter of choice from among the many
types of mixing devices which are now available. A compromise will
have to be reached between mixing speed, power consumption,
residence time in the reactor and various cost factors.
Selection of the polymerization initiator is made mainly on the
basis of the decomposition temperature at which the compound
produces free radicals. This temperature should be above the
melting point of maleic anhydride but below the softening
temperature of the copolymer product. Peroxide initiators such as
ditert.butyl peroxide and benzoyl peroxide and
azobisisobutyronitrile are among those initiators which are
available commercially.
Unlike the dispersing agents, the choice of polymerizable 1-olefin
is not critical. Pure compounds or mixtures may be used in which
there is a polymerizable vinyl group. The balance of the molecule
may be straight chain, branched or cyclic in structure, including
vinyl aromatic monomers such as styrene.
The polymer products obtained by the present process may be used
for all the purposes to which corresponding products have been used
in the past and have no observable deficiencies in chemical or
physical properties. The solid particles of polymer obtained by
this technique appear to have a very desirable physical structure,
which render them easily handled in conventional processing
equipment. The operation of the process is illustrated by the
following specific examples.
EXAMPLE 1
To 2.5 moles of 1-hexene there is added 1.8 g. of tert.butyl
peroctoate as a polymerization initiator and 2.8 g. of an
1-octadecene-maleic anhydride copolymer as a dispersing agent and 1
mole of solid maleic anhydride. The mixture is then heated with
stirring. As the temperature rises above the melting point of the
maleic anhydride (53.degree. C.) the anhydride forms a second
liquid phase underneath the liquid hexane. There is little tendency
of the two liquid phases to intermix, even with vigorous agitation,
until the temperature reaches the vicinity of 80.degree. C. and
then only when the unique dispersing agent is present in the
mixture. When the two liquid phases begin to intermix and form a
liquid-liquid dispersion there is evidence that the
copolymerization reaction has begun. With continued stirring for a
sufficient time period at a temperature of about 80.degree. C. the
polymerization procedure yields a dispersion of solid copolymer
particles in the excess liquid 1-hexene employed as a diluent. When
the polymerization reaction is judged to be complete, the excess
olefin employed as a liquid reaction diluent is separated from the
polymer by evaporation or filtration, yielding finely divided
non-tacky, solid copolymer.
EXAMPLE 2
The procedure employed in this specific example is essentially the
same as described in Example 1. The reaction vessel is charged with
29.4 g. (0.3 mole) of maleic anhydride, 250 ml. of 1-hexene, 2.0 g.
of benzoyl peroxide, and 2 g. of maleic anhydride-1-octadecene
copolymer. The temperature profile from 60.degree. C. to 90.degree.
C. requires one hour. The dispersion develops normally and the
reaction is allowed to proceed at 90.degree. C. for an additional 5
hours. A powdery white solid, M.P. 136-140.degree. C. is isolated
in 96% yield after filtration and drying. The copolymer has a
solution viscosity of 0.10 dl./g.
EXAMPLE 3
The procedure and apparatus employed in this example was the same
as described in Example 1. The reaction vessel was charged with
29.4 g. (0.3 mole) of maleic anhydride, 250 ml. of 1-hexene, 2.0
ml. of tert.butyl peroctoate, and 2 g. of maleic
anhydride-1-tetradecene copolymer. The temperature profile from
60-80.degree. C. required one hour and the reaction was allowed to
proceed for 2 hours at 86.degree. C. Filtration and drying as
before gave a white solid, M.P. 142-160.degree. C., in 85% yield.
The copolymer had a solution viscosity of 0.13 dl./g.
EXAMPLE 4
The procedure and apparatus employed in this example were the same
as described in Example 1. The reaction vessel was charged with
29.4 g. (0.3 mole) of maleic anhydride, 250 ml. of 1-decene, 2.0
ml. of tert.butyl peroctoate, and 2 g. of maleic
anhydride-1-octadecene copolymer. The temperature profile from
60-90.degree. C. was slower as the dispersion developed slowly. The
resultant dispersion after filtration gave a white granular solid,
M.P. 105-113.degree. C.
EXAMPLES 5 and 6
Two batches of polymer were manufactured in a 50-gallon pilot plant
reactor using the dispersion copolymerization procedure. The
reaction charge for the two batches was:
1-hexene lbs 193 Maleic anhydride lbs 67 Tert.butyl peroctoate cc
520 Maleic anhydride - 1 - octadecene copolymer -dispersant lbs
2.3
Each batch was heated to 194.degree. F. (90.degree. C.), held two
hours and cooled. The excess hexene was evaporated from the product
using a Patterson-Kelly rotary vacuum dryer. Dried product was
passed through a 1/4 inch screen. The quantities of products of two
batches and their properties are tabulated below.
PILOT PLANT SYNTHESIS OF 1-HEXENE COPOLYMER
______________________________________ Example 5 6
______________________________________ Crude product, lbs 123 123
Reaction yield, percent 97.0 97.0 Dried product, lbs. 114 113
Overall yield, percent 89.9 89.1 Inherent viscosity, dl./g 0.161
0.169 Volatiles, percent 0.6 0.6
______________________________________
* * * * *