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Патент USA US3091619

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United States Patent 0 "ice
3,091,601
Patented May 28, 1963
2
1
3,091,601
OLEFINIC COPOLYMERS
Frederick P. Rediug, Charleston, and Charles W. Mc
Gary, Jr., Siouth Charleston, W. Va., assignors to Union
Carbide Corporation, a corporation of New York
No Drawing. Filed Sept. 20, 1957, Ser. No. 685,086
36 Claims. (Cl. 260-805)
plest singly branched aliphatic alpha-ole?n is 3-methyl-1
butene; illustrative plurally branched aliphatic alpha-ole
?ns are 4,4-dimethyl-1-pentene and 5,5-dimethyl-l-hex
cue; the simplest cycloaliphatic alpha-ole?n is vinylcyclo
propane; and the simplest aromatic alpha-ole?n is styrene.
Further it is intended to encompass within this term those
alpha-ole?ns containing a mono- or dihalogen (i.e., F, Cl,
Br, I) substituted aromatic group. Where the branch
chain alpha-ole?n monomer contains a halogen substituted
The present invention relates to novel copolymers and
methods of making the same. More particularly, it re 10 aromatic group, determination of the preferred comono
lates to crystalline and crystallizable copolymers of
branch-chain alphaole?ns and methods employed in their
preparation.
'
This application is a continuation-in-part of the noW
mer(s) for polymerization therewith according to the
number of carbon atoms in the branch chain or in the
monomer molecule to form cocrystalline copolymers in
accordance with our invention and as described above can
abandoned application Serial Number 660,996, ?led in the 15 be most desirably accomplished by treating each halogen
substituent as a methyl radical; the spatial displacement
United States Patent O?ice May 23, 1957, by Frederick
of each halogen ‘atom in this instance being approximately
P. Reding and Charles W. \McGary, Ir.
that of a methyl radical. It should be noted that regard
According to heretofore customary procedures it was
for halogen substituents in these determinations while de
known to polymerize certain ole?nic compounds such as
ethylene, propylene and the like to high molecular weight 20 sirable and even preferred is not considered to be critical.
Also introduced to form the desired mixture is a cata
solid homopolymers. But insofar as is presently known,
lyst composition composed of a halide or mixture thereof
no methods have been found for preparing crystalline
of a transition metal of groups IV-B, V-B and VI-B of
copolymers including terpolymers and the like from two
the periodic table, such as, for example, vanadium, tita
or more branch-chain alpha-ole?ns and particularly, solid,
high molecular weight substantially crystalline and crys
tallizable copolymers thereof.
25 nium or tungsten and an organo metallic compound or
metal hydride selected from the following group:
Accordingly, the present invention comprises forming
a mixture of two or more branch-chain alpha-ole?n mono
mers, the mixture of said monomers being selected from
cyclic (i.e., aromatic and cycloaliphatic) or acyclic alpha
ole?ns and which are members of a singly or plurally
branches homologous series, each of said monomers con
taining at least 5 and usually up to 20 carbon atoms and
preferably 5 to 12 carbon atoms, and the range in varia
tion of the total number of carbon atoms of each of said
monomers contained in said mixture being from 0 to 2
(that is, each monomer having the same number of car
bon atoms or differing by not more than 2 atoms thereof
from the comonomer(s) in the reaction mix) and wherein
wherein Al is aluminum; Zn is zinc, Be is beryllium; Mg
is magnesium; and Li is lithium; R is hydrogen or a
monovalent hydrocarbon radical, that is a saturated ali
phatic hydrocarbon radical containing at least two and
preferably two to twelve carbon atoms; a saturated cyclo—
35 aliphatic hydrocarbon radical containing at least three and
preferably three to twelve carbon atoms; or an aromatic
hydrocarbon radical containing six to twelve or more
carbon atoms; and each of R1 and R2 is hydrogen or a
monovalent hydrocarbon radical, i.e., a saturated aliphatic
said mixture, the branch-chains of the reactant monomers 40 hydrocarbon radical containing at least two and preferably
two to twelve carbon atoms, a saturated cycloaliphatic
are monovalent hydrocarbon radicals and those halogen
hydrocarbon radical containing at least three and prefer
substituted monovalent aromatic radicals wherein the
ably three to twelve carbon atoms; an aromatic hydrocar
halogen substituentts) are attached to an aromatic nu
bon radical containing six to twelve or more carbon atoms;
cleus, i.e., saturated hydrocarbon radicals containing at
least 1 to 18 carbon atoms and preferably 1 to 10 car 45 or a halogen when no hydrogen is linked directly to the
metallic nucleus, i.e., when each of ‘R, R1 and R2 is other
bon atoms, saturated aliphatic hydrocarbon radicals con
than hydrogen; together optionally with an inert diluent
taining 1 and preferably 2 to 18 carbon atoms, saturated
and heating said mixture to a temperature ranging from
and unsaturated cycloaliphatic hydrocarbon radicals con
0° C. to 150° C. and above, to cause the formation of
taining from 3 to 18 and preferably 3 to 10 carbon atoms
and aromatic hydrocarbon radicals containing from 6 to 50 crystalline or crystallizable copolymers of said monomers.
Illustratively, the following ole?n monomers can be
18 carbon atoms and preferably 6 to 10 carbon atoms,
copolymerized in accordance with the practice described
and including halogen substituted aromatic derivatives
herein to yield the corresponding copolymers: 3-methyl-l
thereof; the range in variation of the total number of
butene
and 4-methyl-l-pentene; 3-methyl-l-pentene and 4
carbon atoms in each of the branch-chains of the mono
methyl-l-pentene; S-methyl-l-hexene ‘and 4-methyl-1-pen
mers in said mixture being from O to 2 and preferably
tene; allylcy-clopentane with allylcyclohexane; allylcyclo
from 0 to 1; and wherein also each of said branch-chains
hexane with 4-cyclohexyl-l-butene; allylcyclohexane with
of the reactant ole?n monomers in said mixture is posi
styrene; l-allylnaphthalene with 2-vinylnaphthalene; al
tioned at least 1 and preferably 2 carbon atoms removed
lylbenzene with 4-phenyl-1-butene; styrene with allylben
from the nearest ethylenically (i.e., ole?nically) unsatu
rated carbon atom
zene; styrene with para-chlorolstyrene or with an isomeric
mixture of ortho, meta and para-styrene; 4-(2-nap-hthyl)
l-butene with l-allylnaphthalene; l-allylnaphthalene with
4-(1-naphthyl)-1-butene; 4-(1-naphthyl)-l~butene with 4
While it is essential that the branch-chains be at least one
(2 - naphthyl) - 1 -'butene; 9-allyl?uorene with 2-allyl
carbon atom removed from the ethylenically unsaturated 65 fluorene; 4-allyl-l-cyclohexene with 4-vinyl-l-cyclohexene;
group, their position relative thereto is not otherwise crit
4-allyl-1—cyclohexene with allylcyclohexane; 4-allyl-1
cyclohexene with vinylcyclohexane; l-allyl-4-chloroben—
ical.
zene with styrene; 1-allyl-4-chlorobenzene with allylben
A “branch-chain ‘alpha-ole?n” as further de?ned for
zene; and 4,4-dimethyl-1-pentene with 5,5-dimethyl-1
the purposes of this disclosure is an alpha-ole?n which
contains at least one carbon atom chemically bonded to 70 hexene.
The product copolymers prepared in accordance with
at least three other carbon atoms. For example, in this
the practice of our invention, for example and most par
category and within the purview of this invention the sim
3,091,601
ticularly, the copolymers of 3-methyl-l-butene and 4
num hydride, didodecylaluminum hydride, aluminum hy
methyl-l-pentene are much tougher than the homo
dride, diethylberyllium, diisobutylberyllium, dioctylberyl
lium, didodecylberyllium, diphenylberyllium, ethylberyl
lium chloride, isobutylberyllium chloride, oc-tylberyllium
chloride, beryllium hydride, dodecylberylliurn chloride,
polymer-s, poly-3-methyl-l-butene and poly-4-methyl-l
pentene having similar molecular weights (melt indices),
as well as possessing superior clarities, melting points,
oxidation resistance and equal or greater stiffness values
than corresponding polyethylenes or polypropylenes.
These high stiffness values and melting points are due
to the high degree of crystallinity over the entire composi
tion range of the copolymers of our invention.
This 10
crystallinity is shown by X~ray di?raction patterns. Nor
mally, the incorporation of a comonomer into a polymer
lithium hydride, phenyl lithium, naphthyl lithium, iso
butyl lithium, cyclohexyl lithium, dodecyl lithium, di
ethylzinc, diisobutylzinc, dioctylzinc, didodecylzinc, di
phenylzinc, ethylzinc chloride, isobutylzinc chloride, octyl
zinc chloride, zinc hydride, decylzinc chloride, cyclo
propylzinc chloride, diisobutylmagnesium, dioctylmag
nesium, didodccylmagnesium, diphenylrnagnesium, iso
butylmagnesium chloride, octylmagnesiurn chloride, mag
chain disrupts the crystallinity, and even at relatively low
combined comonomer concentration, the ability to crys~
nesium hydride and dodecylmagnesium chloride. The
tallize is destroyed.
15 preferred organo metallic cocatalyst is a trialkylalurninum,
The copolymers of 3-methyl-l-butene and 4-methyl-1
i.e., triisobutylaluminum. The second component is a
pentene of our invention are characterized by stiffnesses in
metallic halide such as vanadium tetrachloride, vanadium
the range of 110,000 p.s.i. to 275,000 p.s.i. at 25° C.
trichloride, vanadium dichloride, vanadyl trichloride,
with melting points from 210° C. to 300° C. as the
vanadyl dichloride, titanium tetrachloride, titanium tri
proportion of 3-methyl-l-butene constituent is varied 20 chloride, titanium dichloride, zirconium tetrachloride,
from 0 to 100 percent, respectively. The proportion-s of
chromium trichloride, chromyl dichloride, titanium tetra
3-methyl-1-butene and 4-methyl-l-pentene can be varied
?uoride, titanium tri?uoride, titanium tetrabromide, ti
over this entire range to yield desirable copolymers.
tanium tribromide, tungsten tetrachloride and tungsten
The cocrystalline copolymers of this invention are use
hexachloride. Vanadium trichloride and titanium tri
ful in the production by extrusion or molding of shaped 25 chloride are most advantageously employed in this re
articles, i.e., gear boxes, self~lubricating bearings, and
gard. Halides or oxyhalides of other metals in groups
particularly those articles requiring high use temperatures
IV-B, V-B or VI—B of the periodic system of the ele
as Well as solvent resistant funnels, beakers, bottles, sinks
ments, for example, zirconium, hafnium, niobium, tan
and the like, which articles are prepared by standard
talum, chromium or molybdenum, can- be used in place
procedures. Certain of these cocrystalline copolymers, 30 of the titanium trichloride or other metallic halide.
i.e., the copolymers of 3-methyl-1-butene and 4-methy1-1~
The molecular ratio of the trialkylalurninum to vana
pentene, are especially useful in the formation of textile
dium or titanium trichloride can vary from 0.1 to 10 or
?bers for employment in those applications requiring
more. The ratio employed is not narrowly critical and
high strength characteristics and resistance to the e?ects
may be varied considerably. Thus, the polymerization
of high temperature.
35 works as well at higher ratios while a preferred ratio for
The polymerization reaction can occur in the absence
e?‘ioient and economic operation is from 0.5 to 5.0. The
of a diluent but the presence of a suitable organic diluent
function of these metallic halides being that of catalysts
is preferred.
or initiators, any catalytic amount can be used.
Sui-table inert organic diluents are those
which serve as the solvent for the monomer, but need
The techniques used in combining the catalyst, diluent
not necessarily function as such ‘for either the product co 40 and monomer are well known procedures designed to
polymers or the catalyst.
Appropriate inert organic
diluents are saturated ‘aliphatic, saturated cycloaliphatic
and aromatic hydrocarbons. The amount of diluent pres
exclude moisture. The alkylaluminum cocatalyst can be
added to the diluent, where diluent is employed, in the
reaction vessel prior to the addition of the metal halide
cocatalyst; however, these various components can be
ent to obtain a suspension polymerization is not critical.
In general, it is, of course, desirable to have at least one 45 added in reverse order also. The monomer is introduced
percent by weight of monomer in the diluent although
as a liquid and the vessel is then sealed with subsequent
this restriction is an economical one. Nor are metal
halide to diluent ratios critical. Thus ratios of at least
0.05 millimol of metal halide per 100 grams of diluent
are thoroughly operative. The diluent, however, must
not contain certain highly polar substituents, (i.e., nitriles
and the like), oxygen, sulfur, active hydrogen (i.e., al
cohols, water, certain amines) or ole?nic unsaturation
‘which react with the catalyst and consequently inactivate
it. Usually it is considered desirable economically to
stirring of the reaction mix at the desired temperature.
The reaction then takes place under autogeneous pressure.
If desired, polymerization can be conducted at atmos
pheric, superatmospheric or subatmospheric pressures in
agitator equipped vessels. In such case, air and moisture
can be excluded by maintaining an inert atmosphere -(e.g.,
nitrogen), and a grinding medium may optionally be
included in the reaction mix (e.g., glass beads), for the
55 purpose of decimating the metal halide and continuously
have 10 grams or more of monomer per gram of metal
renewing exposed surfaces of the decimated particulate
halide present in the reaction mixture although these
proportions are likewise lacking in criticality. Suitable
hydrocarbon solvents are, for example, toluene, benzene,
metal halide to the monomer.
This latter procedure results uniformly in an increased
yield of polymer especially when solid metal halides are
xylene, methylcyclohexane, cyclohexane, hexane, heptane, 60 employed. However, where vanadium trichloride is
and highly purified kerosene. Aromatic diluents such
utilized, as the cocatalyst with or without agitation and
as benzene and toluene are preferred diluents due to
grinding in situ as described immediately hereinabove, a
their greater efficiency as wetting agents for the co
marked and unexpectedly larger yield of product polymer
polymer.
~
results.
The catalyst employed herein is composed of two com 65
The temperature of polymerization has a marked
effect on the molecular weight of the polymer obtained.
ponents as described hereinabove, which may or may
In general, the higher the temperature, the lower is the
not react chemically with each other in the reaction mix.
molecular weight. Temperatures ranging from 25° C. to
The ?rst component is an organometallic compound or
about 85° C. are most advantageously employed. Polym
metal hydride such as, for example, triisobutylaluminum,
trioctylaluminum, tributylaluminum, triethylaluminum, 70 erization is very rapid and concomitantly the molecular
weight of the product polymer is very low at temperatures
triisopropyl-aluminum, tridodecylaluminum, triphenyl
in excess of 150° C. At temperatures below 0° C., the
aluminum, diethylaluminum chloride, diisobutylaluminum
polymerization rate falls to very low values.
chloride, dioctylaluminum chloride, didodecylaluminum
chloride, monoisobutylaluminum hydride, diethylalumi
The period of time during which the polymerization
num hydride, diisobutylaluminum hydride, dioctylalumi 75 reaction is permitted to proceed is not critical. Thus,
3,091,601
5
periods of as little as a few minutes (e.g., 5 minutes)
to 4 hours or 7 days can be employed. The longer the
reaction period the more complete the conversion. Fac~
tors such as, for example, the reaction temperature and
the position of the side chain will in?uence the rate of
reaction. Thus, lower polymerization temperatures an
100,000 and 260,000 p.s.i. at 279°, 168°, 41° and 25 ° C.,
respectively. A molded plaque was tough and clear.
Example 3
Example 2 was repeated except that 30 grams of 3
methyl-l-butene and 10 grams of 4-methyl-1-pentene were
relative closeness of the side chains from the ethylenically
used. A 27 gram yield of copolymer was obtained and
modulus which is calculated by multiplying by one hun
dred, the force necessary to stretch a sample of polymer
and clear.
the copolymer had a density of 0.864 g./cc. at 25° C., a
unsaturated group of the reaction monomers will slow
melt index (325° C.) of 0.56, and stiifnesses of 100;
the reaction.
The term “stillness” as used herein refers to the tensional 10 1,000; 10,000; 100,000 and 235,000 p.s.i. at 240°, 206°,
110°, 35°, 25° C. respectively. The copolymer was tough
Example 4
one percent of its original length. These values are meas
ured by an Instron tester made by the lnstron Engineer
‘Example 2 was repeated except that 20 grams of 3~
ing Company of Quincy, Massachusetts (Model 37).
15 methyl-l-butene and 20 grams of 4-methyl-1-pentene were
The term “melt index” as is employed throughout this
used. The copolymer weighed 34 grams, had a density of
speci?cation refers to the melt index test which is de
0.854 g./cc. at 25° C., a melt index (325° C.) of 1.4,
scribed in detail in ASTM Test Procedure D1228-52T,
Procedure A, modi?ed in the temperature employed is
and stiifnesses of 100; 1,000; 10,000; 100,000 and 202,000,
p.s.i. at 208°, 192°, 105°, 36°, and 25° C., respectively.
325° C. A ten gram sample placed in 1a % inch diameter 20 The copolymer was tough and clear.
tube at 325° C. and a load of 2610 grams is applied to a
Example 5
plunger which forces the melted polymer through a die
having a diameter of 0.0825 inch. The “melt index” of
The following materials were placed in a bottle under
the polymer is the rate in decigrams per minute, at which
an atmosphere of nitrogen.
the polymer is extruded under these conditions. Illustra 25
150 ml. of benzene
tively, polymers of such high molecular weights as those
10 grams of 3-methyl-1-butene
disclosed herein extrude more slowly and therefore have
30 grams of 4-methyl-1-pentene
a lower melt index.
5.4 grams of triisobutylalurninum
It should also be noted that the term “copolymer” as
employed herein refers to polymers containing two or 30 1.0 gram of vanadium trichloride
more polymerized branched alpha-ole?n monomers and
thus includes terpolymers and the like as well.
The following examples are further illustrative of the
invention.
The bottle was rotated in a 50° C. bath for 65 hours after
which time the mixture was thick with suspended
copolymer. The copolymer Was washed as previously to
remove the catalyst residue and weighed 38 grams after
Example 1
35 drying. The copolymer had a density of 0.841 g./cc., at
25 ° C., a melt index (325° C.) of 1.4, and stiifnesses of
The following materials were placed in a bottle under
an atmosphere of nitrogen.
1,000; 10,000; 100,000 and 152,000 p.s.i. at 151°, 69°,
31°, and 25° C., respectively.
150 ml. of benzene
Example 6
35 grams of S-methyl-l-butene
40
5 grams of 4-methyl-1-pentene
Example 5 was repeated except that 5 grams of 3
5.2 grams of triisobutylahuninum
methyl-l-butene and 35 grams of 4-methyl-1-pentene were
1.0 gram of vanadium trichloride
used. The dried copolymer Weighed 36 grams and had
The bottle was then rotated in a 50° C. bath for 70 hours
a density of 0.836 g./cc. at 25° C., a melt index (325° C.)
after which time the mixture was thick with suspended
of 0.69, and stiffnesses of 1,000; 10,000; 100,000 and
copolymer of 3-methyl~1-butene and 4-methyl-1-pentene.
The catalyst residue was removed by washing the polymer
with isopropanol and water containing hydrochloric acid.
The copolymer was then washed with isopropanol and
water until it was acid free and was dried. The copolymer
weighed 18 grams, and had a density of 0.875 g./=cc. at
25° C., a melt index (325° C.) of 0.99 and stiifnesses of
1,000; 10,000, 100,000 and 220,000 p.s.i. at 244°, 154°,
39° and 25° C., respectively. The metallic halide em
ployed in this and the following examples was ground
before use by shaking a mixture of the halide, glass beads
and diluent in a bottle before use.
A Red-Devil paint
mixer was employed for shaking the mixture.
Example 2
153,000 p.s.i. at 179°, 52°, 31.5", and 25° C., respec
tively.
Example 7
The following materials were placed in a bottle under
an atmosphere of nitrogen.
150 ml. of benzene
20 grams of 3-methyl-1-butene
20 grams of 4-methyl-1-pentene
5.2 grams of triisobutylaluminum
1.0 gram of titanium trichloride
The bottle was then rotated in a 50° C. bath for 232 hours
after which time the mixture was thick with suspended
copolymer. The copolymer was Washed as previously
The following materials were placed in a bottle under 00 and after drying, weighed 32 grams. The copolymer
had a melt index (325° C.) of 12, and sti?lnesses of 1,000;
an atmosphere of nitrogen.
10,000; 100,000 and 178,000 p.s.i. at 165°, 75°, 36°, and
150 ml. of benzene
25°
C., respectively.
35 grams of 3-methyl-l-butene
Example 8
5 grams of 4-methyl-1-pentene
65
The following materials were placed in a bottle under
5.2 grams of triisobutylaluminum
1.0 gram of vanadium trichloride
an atmosphere of nitrogen.
The bottles were then rotated in a 50° C. bath for 42
200 ml. of toluene
hours after which the polymerization mixture was thick
36 grams of 3-methyl-1-butene 4 grams of 4-methyl-1-pen
with suspended copolymer. The catalyst residue was re 70
tene
moved by washing the copolymer of 3-methyl-1-butene
5.0 grams of triisobutylaluminum
and 4-methyl~1-pentene with isopropanol and water con
1.0 gram of vanadium trichloride
taining hydrochloric acid. The dried copolymer weighed
The bottle was rotated in a 50° C. bath for 112 hours
27 grams, had a density of 0.880 g./cc. at 25° C., a melt
index (325° C.) of 0.31, and stiifnesses of 1,000; 10,000‘, 75 after which time the mixture was solid with suspended
3,091,601
7
8
polymer. After working up the copolymer as previously,
Example 11
a 31 gram yield of dried copolymer was obtained.
The
The following materials were placed in a bottle under
an atmosphere of nitrogen.
100 ml. of toluene
10 grams of 3-methy1-1-heXene
10 grams of 4-methyl-1-pentene
3.0 grams of triisobutylaluminum
copolymer had a melt index (325° C.) of 5.7 and stiff
nesses of 1,000; 10,000; and 100,000 p.s.i. at 225°, 151°,
and 58°, respectively.
It should be noted that the infrared spectra of the
products obtained in Examples 1 through 8 showed that
units of both monomers were incorporated in the polymer.
0.6 gram of vanadium trichloride
The X-ray di?raction pattern of the products indicated the
polymers were crystalline with a crystalline di?raction 10 The bottle was capped and rotated in a 50° C. bath for
pattern different from those of the homopolymers of the
six days. The catalyst residues were removed as described
two monomers.
This latter fact indicates that the two
in the other examples. The dried copolymer weighed
monomer units in the copolymer chain had cocrystallized.
nine grams and had a density of 0.842 g./cc.
Molded plaques of the products were clear indicating
The infrared spectrum of the product showed the poly
true homogeneous copolymers rather than mixtures of 15 mer contained both monomer units. The X-ray di?frac~
homopolymers.
tion pattern was crystalline and similar to that of homo
Example 9
polymeric 4-methyl-1-pentene.
an atmosphere of nitrogen.
However, small di?er
ences in the pattern demonstrate that the product is a
The following materials were placed in a bottle under
cocrystalline ‘copolymer rather than poly-4-methyl-1
20 pentene. The melting point of the product was 220° C.
compared to 240° C. and 280° C. for homopolymer-ic
4-methyl-1-pentene and 3-methyl-1-hexene. A molded
plaque of the product was clear indicating a homogeneous
150 ml. of toluene
15 grams of allylcyclopentane
15 grams of allylcyclohexane
5.0 grams of triisobutylaluminum
2.0 grams of vanadium trichloride
25
copolymer rather than a mixture.
Example 12
The following materials were placed in a bottle under
an atmosphere of nitrogen.
formed polymer with isopropanol containing hydrochloric 30 150 ml. of toluene
acid. The copolymer was then washed with isopropanol
15 grams of allylcyclohexane
and water until it was acid free and it was then dried.
15 grams of 4-cyclohexyl-l-butene
The product weighed 14.5 grams and had a density of
5.0 grams of triisobutylaluminum
0.942 g./cc.
1.5 grams of titanium .trichloride
The infrared spectrum of the product showed that 35
The bottle was capped and rotated in a 50° C. bath for
units of both monomers were incorporated in the polymer.
90 hours. The catalyst residue was removed from the
The X-ray diffraction pattern of the product indicated the
formed polymer with isopropanol containing hydrchloric
polymer was crystalline with a crystalline diffraction pat
acid. The copolymer was then washed with isopropanol
tern somewhat diiferent from those of the homopolymers
The bottle was capped and rotated in a 50° C. bath for
90 hours. The catalyst residues were removed from the
of the two monomers. This latter fact indicates that the 40 and water until it was acid free and it was then dried.
The copolymer weighed 12 grams and had a density of
two monomer units in the copolymer chain had cocrystal
lized. The crystal melting point of the copolymer was
0.951 g./cc.
Example 13
205° C. compared to 230° C. and 210° C. for homo
polymeric allylcyclohexane and allylcyclopentane, respec
The following materials were placed in a bottle under
tively. A molded plaque of the product was clear indicat 45 an atmosphere of nitrogen.
ing a true homogeneous copolymer rather than a mixture
15 0‘ ml. of toluene
of polymers.
15 grams of styrene
Example 10
15 grams of allylcyclohexane
5.0 grams triisobutylaluminum
The following materials were placed in a bottle under 50 2.0 grams of titanium trichloride
an atmosphere of nitrogen.
The bottle was capped and rotated in a 50° C. bath for
6 days.
100 ml. of toluene
10 grams of 3-methyl-1-pentene
10 grams of 4-methyl-1-pentene
3.0 grams of triisobutylaluminum
0.6 gram of vanadium trichloride
The catalyst residue was removed from the
formed polymer with isopropanol containing hydro
55 chloric acid. The copolymer was then washed with iso
propanol and water until it was acid free and it was then
dried.
The copolymer Weighed 20 grams and had a
density of 1.003 g./cc.
The infrared spectrum of the product showed that both
The bottle was capped and rotated in a 50° C. bath for
16 hours. The catalyst residues were removed as de— 60 monomer units were included in the polymer. The
scribed in the other examples.
The dried copolymer
The infrared spectrum of the product showed that units
of both monomers were present in the polymer.
X-ray diffraction pattern showed the product to ‘be crys
talline.
weighed 17 grams and had a density of 0.857 g./ cc.
The
The product melted at 220° C. compared to
230° C. for each of the respective homopolymers.
Example 14
X-ray ditffraction pattern showed the product to be 65
The following materials were placed in a bottle under
crystalline with a crystal diifraction pattern different from
an atmosphere of nitrogen.
those of the homopolymers of the two monomers. This
latter fact indicates that the two monomer units in the
100 ml. of toluene
15 grams of para-allyl toluene
of the copolymer was 235° C. compared to 240° C. and 70 15 grams of styrene
4.0 grams of triisobutylaluminum
200° C. for homopolymeric 4-methyl-1-pentene and
1.0 gram of vanadium trichloride
3- methyl-l-pentene respectively. A molded plaque of
the product was clear indicating a homogeneous co
The bottle was rotated in 1a 50° C. bath for 94 hours
polymer.
75 after which time the mixture was thick with suspended
copolymer chain had cocrystallized. The melting point
3,091,601
10
carried on for a period of 42 hours. The product ob
tained was 13 grams of dried copolymer of allylcyclo
copolymer of para-allyl toluene ‘and styrene. The cat
alyst residue was removed by washing the polymer with
isopropanol and water containing hydrochloric acid.
The dried, crystalline copolymer weighed 22 grams and
hexane and 4-phenyl-1-butene having a density of 1.0240
and a melting point of 130° C. to 133° C. Infrared an
alysis further indicated the presence of both monomers
had a density of 1.046 grams per cc. at 25° C. and a
in the copolymer.
melting point of 192° C. to 198° C. Infrared analysis
further indicated the presence of both monomers in the
Example19
copolymer.
The following materials were placed in a bottle under
Example 15
an
atmosphere of nitrogen.
The following materials were placed in a bottle under 10
150
ml. of toluene
an atmosphere of nitrogen.
15 grams of styrene
75 ml. of toluene
15 grams of 1-allyl-4-chlorobenzene
10 grams of allylbenzene
510 grams of triisobutylaluminum
15 ‘2.0 grams of vanadium trichloride
10 grams of 1-allyl-4-chlorobenzene
2.0 grams of triisobutylaluminum
The reaction mix was treated in a manner similar to that
0.8 gram of vanadium trichloride
described in Example 14 except that the reaction was
This reaction mix was treated in a manner similar to
carried on for a period of 7.2 hours. Twelve grams of
that described in Example 14 except that the reaction
dried, crystalline copolymer of styrene and 1-allyl-4
20
was carried on for a total of 34 hours while being vi
chlorobenzene wherein the crystallinity was determined
brated in a Red-Devil paint mixer and resulted in the
by X-ray diffraction was obtained and was further char
acterized by having a density of 1.1525 and a melting
isolation of 15 grams of a dried copolymer of allylben
point of 212° C. to 215° C. Infrared analysis further
zene and 1-allyl-4-chlorobenzene of high crystallinity as
determined by X-ray diffraction having a melting point 25 indicated the presence of both monomers in the copoly
of about 223° C. Infrared ‘analysis further indicated
mer.
[the presence of both monomers in the copolymer.
Example 20
Example 1 6
The following materials were placed in a bottle under
The following materials were placed in a bottle under 30 an atmosphere of nitrogen.
an atmosphere of nitrogen.
5 0 grams of toluene
100 ml. of hexane
10 grams of l-allylnaphthalene
10 grams of 4-cyclohexyl-l-butene
10 grams of 4-(2-naphthyl)-l-butene
10 grams of 4-phenyl-l-butene
4.0 grams of triisobutylaluminum
35 2.0 grams of vanadium trichloride
3.0 grams of triisobutylaluminum
1.0 gram of titanium trichloride
The reaction mix was treated in a manner similar to that
The reaction mix was treated in a manner similar to that
described in Example 14 except that the reaction was
carried on for a period of '96 hours. 10.5 grams of dried,
described in Example 14 except that the reaction was
carried on for a total of 18 hours and resulted in the
crystalline copolymer of l-allylnaphthalene and 4-(2
isolation of 16 grams of dried, crystalline copolymer
naphthyl)-1-butene wherein the crystallinity was deter
mined by X-ray diffraction was obtained. This copoly
of 4-cyclohexyl-1-butene and 4-phenyl-1-but-ene having a
density of 1.0645 and a melting point of 118° C. to 123°
mer was further characterized by a density of 1.1200‘
C. Infrared analysis further indicated the presence of
grams per cubic centimeter and a melting point of 151°
both monomers in the copolymer.
45 C. to 160° ‘C. Infrared analysis further indicated the
presence of both monomers in the copolymer.
Example 17
What is claimed is:
The following materials were placed in a bottle under
1. The method for producing a solid cocrystalline co
an atmosphere of nitrogen.
polymer of 3-methyl-1-pentene and 4-methyl-1-pentene
100 ml. of toluene
50 having a high degree of crystallinity over the entire com
position range as determined by its X-ray diffraction pat
10 grams of styrene
tern which comprises forming a mixture of 3~methyl-1
10 grams of 4-phenyl-.1-butene
pentene and 4-methyl-1-pentene, together with a catalyst
3.0 grams of triisobutylaluminum
consisting essentially of a halide of a transition metal
1.0 gram of vanadium trichloride
55 selected from the group consisting of group I-V-B, group
The reaction mix was treated in a manner similar to that
V~B and group Vl-B of the periodic table and a com
described in Example 14 except that the reaction was
carried on for a total of 18 hours and resulted in the
isolation of '16 grams of dried copolymer of styrene and
pound selected from the group consisting of:
4-phenyl-1~butene having a high crystallinity as deter
mined by X-ray diffraction, a density of 1.0645 and a 60
melting point of 152° C. to ;156° C. Infrared analysis
further indicated the presence of both monomers in the
copolymer.
Example 18
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, an aromatic hy
drocarbon radical containing from 6 to ‘12 carbon atoms,
65 a saturated aliphatic hydrocarbon radical containing 2
The following materials were placed in a bottle under
to 12 carbon atoms and a saturated cycloaliphatic hydro
an atmosphere of nitrogen.
carbon radical containing 3 to 12 carbon atoms, each of
R1 and R2 is a member selected from the group consist
100 ml. of heptane
ing of hydrogen, a saturated aliphatic hydrocarbon radical
10 grams of allylcyclohexane
containing '2 to ’12 carbon atoms, a saturated cycloali
70
10 grams of ‘4-phenyl-1-butene
phatic hydrocarbon radical containing 3 to 10 carbon
3.0 grams of triisobutylaluminum
atoms and an aromatic hydrocarbon radical containing
1.0 gram of titanium trichloride
6 to 12 carbon atoms, md halogen when no hydrogen
is linked directly to the metallic nucleus, and heating said
The reaction mix was treated in a manner similar to that
described in Example 14 except that the reaction was 75 mixture at a temperature of from 0° C. to 150° C. to
3,091,601
11
12
cause the formation of a substantially crystalline co
polymer of 3-methyl-1-pentene and 4-methyla1-pentene.
2. The method for producing a solid cocrystalline co
polymer of 3-methyl-‘1-hexene and 4-methyl-1-pentene
having a high degree of crystallinity over the entire com
position range as determined by its X-ray di?raction pat
tern which comprises forming a mixture of 3-methyl-l
hexene and 4-methyl-l-pentene, together with a catalyst
consisting essentially of a halide of a transition metal
selected from the group consisting of group IV-B, group
V~B and group VI-B of the periodic table and a com
pound selected from the group consisting of:
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, an aromatic hy
drocarbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2
to 12 carbon atoms and a saturated cycloaliphatic hydro
carbon radical containing 3 to 12 carbon atoms, each of
R1 and R2 is a member selected form the group consist
ing of hydrogen, a saturated aliphatic hydrocarbon radi
10 cal containing 2 to 12 carbon atoms, a saturated cyclo
aliphatic hydrocarbon radical containing 3 to 10 carbon
atoms and an aromatic hydrocarbon radical containing
6 to -12 carbon atoms, and halogen when no hydrogen is
linked directly to the metallic nucleus, and heating said
15 mixture at a temperature of from 0° C. to 150° C. to
cause the formation of a substantially crystalline copoly
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
mer of 3-methyl-1-butene and 4-methyl-l-pentene.
Be is beryllium, Li is lithium, R is a member selected
5. The method for producing a solid cocrystalline co
from the group consisting of hydrogen, an aromatic hy
polyrner of allylcyclohexane and 4-cyclohexyl-l-butene
drocarbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2 20 having a high degree of crystallinity over the entire com~
position range as determined by its X-ray di?raction pat
to 12 carbon atoms and a saturated cycloaliphatic hydro
tern which comprises forming a mixture of allylcyclo
carbon radical containing 3 to 12 carbon atoms, each of
hexane and 4-cycloheXyl-1-butene, together with a catalyst
R1 and R2 is a member selected from the group consist
consisting essentially of a halide of a transition metal se
ing of hydrogen, a saturated aliphatic hydrocarbon radi
cal containing 2 to 12 carbon atoms, a saturated cyclo 25 lected from the group consisting of group IV-B, group
VB and group VI-B of the periodic table and a com
aliphatic hydrocarbon radical containing 3 to 10 carbon
pound selected from the group consisting of:
atoms and an aromatic hydrocarbon radical containing
6 to 12 carbon atoms, and halogen when no hydrogen is
linked directly to the metallic nucleus, and heating said
mixture at a temperature of from 0° C. to 150° C. to
cause the formation of a substantially crystalline co
30'
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, an aromatic hy
drocarbon radical containing from 6 to 12 carbon atoms,
polymer of allylcyclopentane and allylcyclohexane hav
ing a high degree of crystallinity over the entire composi 35 a saturated aliphatic hydrocarbon radical containing 2 to
12 carbon atoms and a saturated cycloaliphatic hydro
tion range as determined by its X-ray di?raction pattern
carbon radical containing 3 to 12 carbon atoms, each of
which comprises forming a mixture of allylcyclopentane
R1 and R2 is a member selected from the group consist
and allylcyclohexane, together with a catalyst consisting
ing of hydrogen, a saturated aliphatic hydrocarbon radi
essentially of a halide of a transition metal selected from
the group consisting of group ‘IV-B, group V-B and group 40 cal containing 2 to '12 carbon atoms, a saturated cyclo
aliphatic hydrocarbon radical containing 3 to 10 carbon
VI-B of the periodic table and a compound selected from
atoms and an aromatic hydrocarbon radical containing
the group consisting of:
16 to v12 carbon atoms, and halogen when no hydrogen is
polymer of '3-methyl-l-hexene and 4-methyl-1-pentene.
3. The method for producing a solid cocrystalline co
and R-Li
linked directly to the metallic nucleus, and heating said
45
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, an aromatic hy
drocarbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2
to 12 carbon atoms and a saturated cycloaliphatic hydro
carbon radical containing 3 to 12 carbon atoms, each of
R1 and R2 is a member selected from the group consist
ing of hydrogen, a saturated aliphatic hydrocarbon radi
cal containing 2 to 12 carbon atoms, a saturated cyclo
aliphatic hydrocarbon radical containing 3 to 10 carbon
atoms and an aromatic hydrocarbon radical containing
‘6 to 12 carbon atoms, and halogen when no hydrogen is
mixture at a temperature of from 0° C. to 150° C. to
cause the formation of a substantially crystalline copoly
mer of allylcyclohexane and 4-cyclohexyl-1-butene.
6. The method for producing a solid cocrystalline co
polymer of allylcyclohexane and a styrene having a high
degree of crystallinity over the entire composition range
50
as determined by its X-ray diffraction pattern which com
prises forming a mixture of allylcyclohexane and styrene,
together with a catalyst consisting essentially of a halide
of a transition metal selected from the group consisting
of group IV-B, group V-B and group VI—B of the per
iodic table and a compound selected from the group con
sisting of:
linked directly to the metallic nucleus, and heating said
mixture at a temperature of from 0° C. to 150° C. to 60 wherein Al is aluminum, Mg is magnesium, Zn is zinc,
cause the formation of a substantially crystalline copoly
mer of allylcyclopentane and allylcyclohexane.
4. The method for producing a solid crystalline co
polymer of 3-methyl-1-butene and 4-methyl-l-pentene
having a high degree of crystallinity over the entire com
position range as determined by its X-ray diifraction
pattern which comprises forming a mixture of 3-methyl
l-butene and 4-methyl-1-pentene, together with a catalyst
consisting essentially of a halide of a transition metal se
lected from the group consisting of group IV-B, group
V-B and group VI—B of the periodic table and a com
pound selected from the group consisting of:
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, an aromatic hy
drocarbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2
to 12 carbon atoms and a saturated cycloaliphatic hy
drocarbon radical containing 3 to 12 carbon atoms, each
of R1 and R2 is a member selected from the group con
sisting of hydrogen, a Saturated aliphatic hydrocarbon
radical containing 2 to 12 carbon atoms, a saturated cyclo
aliphatic hydrocarbon radical containing 3 to 10 carbon
atoms and an aromatic hydrocarbon radical containing
6 to .12 carbon atoms, and halogen when no hydrogen is
linked directly to the metallic nucleus, and heating said
75 mixture at a temperature of from ‘0° C. to 150° C. to
3,091,601
13
Be is beryllium, Li is lithium, R is a member selected from
the group consisting of hydrogen, an aromatic hydro
carbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2
to 12 carbon atoms and a saturated cycloaliphatic hydro
carbon radical containing 3 to 12 carbon atoms, each of
R1 and R2 is a member selected from the group consist
ing of hydrogen, a saturated ‘aliphatic hydrocarbon radi
cal containing 2 to 12 carbon atoms, a ‘saturated cyclo
aliphatic hydrocarbon radical containing 3 to 10 carbon
atoms and an aromatic hydrocarbon radical containing 6
to 12 ‘carbon atoms, and halogen when no hydrogen is
linked directly to the metallic nucleus, and heating said
polymer of styrene, ortho-chlorostyrene, meta-chloro
styrene and para-chlorostyrene having a high degree of
crystallinity over the entire composition range as deter
mined by its X-ray diifraction pattern which comprises
admixing styrene with a mixture of orthochlorostyrene,
meta-chlorostyrene and para-chlorostyrene, together with
a catalyst consisting essentially of a halide of a transition
metal selected from the group consisting of group IV—B,
group V-B and group VI-B of the periodic table and a
compound selected from the group consisting of:
1111
14
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
cause the formation of a substantially crystalline copoly
mer of allylcyclohexane and styrene.
7. The method for producing a solid cocrystalline co
15 mixture at a temperature of from 0° C. to 150° C. to
cause the formation of a substantially crystalline co
wherein Al is aluminum, Mg is magesium, Zn is zinc, Be
is berryllium, Li is lithium, R is a member selected from
polymer of styrene and allylbenzene.
10. The method for producing a solid cocrystalline co
the group consisting of hydrogen, an aromatic hydro
polymer of 4-(2-naphthy1)-l-butene and l-allylnaphthal
carbon radical containing from 6 to 12 carbon atoms, a
ene having a high degree of crystallinity over the entire
composition range as determined by its X-ray diffraction
pattern which comprises forming a mixture of 4-(2
saturated aliphatic hydrocarbon radical containing 2 to
12 carbon atoms and a saturated cycloaliphatic hydro
carbon radical containing 3 to 12 carbon atoms, each of
R1 and R2 is a member selected from the group consisting
naphthyl)-1-butene and l-iallylnaphthalene, together with
a catalyst consisting essentially ‘of a halide of a transition
of hydrogen, a saturated aliphatic hydrocarbon radical 25 metal selected from the group consisting of group IV—B,
group V-B and group VI-B of the periodic table and
containing 2 to 12 carbon atoms, a saturated cycloaliphatic
a compound selected from the group consisting of:
hydrocarbon radical containing 3 to 10 carbon atoms and
an aromatic hydrocarbon radical containing 6 to 12
carbon atoms, and halogen when no hydrogen is linked
directly to the metallic nucleus, and heating the resulting 30
mixture at a temperature of from 0° C. to 150° C. to
in
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, @an aromatic hy
drocarbon radical containing from ‘6 to 12 carbon atoms,
‘and para-chlorostyrene.
8. The method for producing a solid cocrystalline co 35 a saturated aliphatic hydrocarbon radical containing 2
to 12 carbon atoms and a saturated cycloaliphatic hy
polyrner of allylbenzene and 4-phenyl-1-butene having a
drocarbon radical containing 3 to 12 carbon atoms, each
high degree of crystallinity ‘over the entire composition
of R1 and R2 is a member selected from the group con
range as determined by its X-ray diffraction pattern which
sisting of hydrogen, a saturated aliphatic hydrocarbon
comprises forming a mixture of iallylbenzene and 4-phenyl
l-butene, together with a catalyst consisting essentially 40 radical containing 2 to 12 carbon atoms, a saturated cyclo
raliphatic hydrocarbon radical containing 3 to 10 carbon
of a halide of a transition metal selected from the group
atoms and an aromatic hydrocarbon radical containing
consisting of group IV—B, group V—B and group VI-B of
6 to 12 carbon atoms, and halogen when no hydrogen is
the periodic table and a compound selected from the
linked directly to the metallic nucleus, and heating said
group consisting:
cause the formation of a substantially ‘crystalline oopoly
mer of styrene, ortho-chlorostyrene, meta-chlorostyrene
mixture at a temperature of from 01° C. to 150° C. to
cause the formation of a substantially crystalline co
polymer of 4-(2-naphthyl)-1-butene and l-allylnaphthal
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
ene.
11. The method for producing a solid cocrystalline co
Be is beryllium, Li is lithium, R is a member selected from
the group consisting of hydrogen, an ‘aromatic hydro 50 polymer of l~allylnaphthalene and 4-(l-naphthyl)-1
butene having a high degree of crystallinity over the en
carbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2
tire composition range as determined by its X-ray diifrac
to 12 carbon atoms and a saturated cycloaliphatic hy
tion pattern which comprises forming a mixture of l-allyl
naphthalene and 4-(1-naphthyl)-1-butene, together with
drocarbon radical containing 3 to 12 carbon atoms, each
a catalyst consisting essentially ‘of a halide of a transition
of R1 and R2 is a member selected from the group con
sisting of hydrogen, a saturated aliphatic hydrocarbon
metal selected from the group consisting of group IV-B,
radical containing 2 to 12 carbon atoms, a saturated cyclo
group V-B, and group VI-B of the periodic table and a
aliphatic hydrocarbon radical containing 3 to 10 carbon
compound selected from the group consisting of:
atoms and an aromatic hydrocarbon radical containing 6
R-Al-Rz, R-—Zn-—R1, R—Be—R1, R—Mg—-Rr, and R-Ll
to 12 carbon ‘atoms, and halogen When no hydrogen is 60
linked directly to the metallic nucleus, and heating said
l,
mixture at a temperature ‘of from 0° C. to 150° C to
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium; R is a member selected
from the group consisting \of hydrogen, an aromatic hy
9. The method for producing a solid cocrystalline c0 65 drocarbon radical containing from ‘6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2
polymer of styrene and allylbenzene having a high degree
to 12 carbon atoms, and a saturated cycloliphatic hydro
of crystallinity over the entire composition range as deter
carbon radical containing 3 to 12 carbon atoms, each
mined by its X-ray diffraction pattern which comprises
of R1 and R2 is a member selected from the group con
forming a mixture of styrene and allylbenzene, together
with a catalyst consisting essentially of a halide of a transi 70 sisting of hydrogen, a saturated aliphatic hydrocarbon
radical containing 2 to 12 carbon atoms, a saturated cyclo
tion metal selected from the group consisting of group
aliphatic hydrocarbon radical containing 3 to 10 carbon
IV—B, group V-B and group VI~B of the periodic table
atoms, and an aromatic hydrocarbon radical containing 6
and a compound selected from the group consisting of:
to 12 carbon atoms, and halogen when no hydrogen is
75 linked directly to the metallic nucleus, and heating said
cause the formation of a substantially crystalline copoly
mer of allylbenzene and 4-phenyl-1-butene.
3,091,601
15
16
mixture at a temperature of from 0° C. to 150° C. to
IV-B, group V—B and group VI-B of the periodic table
and a compound selected from the group consisting of:
cause the formation of a substantially crystalline copoly
mer iof leallylnaphthalene and 4-(1-rnaphthyl)-l-butene.
12. The method for producing a solid cocrystalline co
polymer of 4-(1-naphthyl)-1-butene and 4-(2-naphthyl)
wherein Al is duminum, Mg is magnesium, Zn is zinc, Be
l-butene having a high degree of crystallinity over the en
is beryllium, Li is lithium, R is a member selected from
the group consisting of hydrogen, an aromatic hydrocar
bon containing from 6 to 12 carbon atoms, a saturated
4-(l-naphthyl)-1-butene and 4-(2-naphthyl)-1-butene, to
gether with a catalyst consisting essentially of a halide of 10 aliphatic hydrocarbon radical containing 2 to 12 carbon
atoms and a saturated cycloaliphatic hydrocarbon radical
a transition metal selected from the group consisting of
containing 3 to 12 carbon atoms, each of R1 and R2 is a
group IV-B, group V—B and group Vii-B of the periodic
member selected from the group consisting of hydrogen,
table and a compound selected from the group consisting
a saturated aliphatic hydrocarbon radical containing 2 to
of:
12 carbon atoms, a saturated cycloaliphatic hydrocarbon
tire composition range as determined by its X-ray dif
fraction pattern which comprises forming a mixture of
radical containing 3 to 10 carbon atoms and an aromatic
hydrocarbon radical containing 6 to 12 carbon atoms,
and halogen when no hydrogen is linked directly to the
metallic nucleus, and heating said mixture at a tempera
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected
from the group consisting of hydrogen, an aromatic hy
drocarbon radical containing from 6 to 12 carbon atoms,
a saturated aliphatic hydrocarbon radical containing 2 to
ture of from 0° C. to 150° C. to cause the formation of
a substantially crystalline copolymer of 4-allyl-1-cyclo
hexene with 4-vinyl-1-cyclohexene.
15. The method for producing a solid cocrystalline co
12 carbon atoms and a saturated cycloaliphatic hydro
polymer of 4-allyl-1-cyclohexene and allylcyclohexane
carbon radical containing 3 to 12 ‘carbon atoms, each of R1 25 having a high degree of crystallinity over the entire com
and R2 is a member selected from the group consisting
position range as determined by its X-ray diffraction pat
of hydrogen, a saturated aliphatic hydrocarbon radical
tern which comprises forming a mixture of 4-allyl-1
containing 2 to 12 carbon atoms, a saturated cycloali
cyclohexene and allylcyclohexane, together with a cat
phatic hydrocarbon radical containing 3 to 10 carbon
alyst consisting essentially of a halide of a transition
atoms and an aromatic hydrocarbon radical containing 6
metal selected from the group consisting of group IV-B,
to 12 carbon atoms, and halogen when no hydrogen is
group V-B and group VI—B of the periodic table and a
linked directly to the metallic nucleus, and heating said
compound selected from the group consisting of:
mixture at a temperature of from 0° C. to 150‘0 C. to
cause the formation of a substantially crystalline copoly
mer of 4-(1-napththyl)-1-butene and 4-(2-naphthyl)-1 35
butene.
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
13. The method for producing a solid cocrystalline co
Be is beryllium, Li is lithium, R is a member selected
polymer of 9-allyl?uorene and 2-allyl?uorene having a
from the group consisting of hydrogen, an aromatic hy
high degree of crystallinity over the entire composition
drocarbon radical containing from 6 to 12 carbon atoms,
range as determined by its X-ray di?raction pattern which
a saturated aliphatic hydrocarbon radical containing 2 to
comprises forming a mixture of 9-allyl?uorene and 2-a1lyl
12 carbon atoms and a saturated cycloaliphatic hydro
?uorene, together with a catalyst consisting essentially
carbon radical containing 3 to 12 carbon atoms, each of
of a halide of a transition metal selected from the group
R1 and R2 is a member selected from the group consisting
consisting of group IV-B, group V-B and group VI-B of
of hydrogen, a saturated aliphatic hydrocarbon radical
the periodic table and a compound selected from the group 45 containing 2 to 12 carbon atoms, a saturated cycloali
consisting of:
phatic hydrocarbon radical containing 3 to 10 carbon
atoms and an aromatic hydrocarbon radical containing 6
to 12 carbon atoms, and halogen when no hydrogen is
linked directly to the metallic nucleus, and heating said
wherein Al isaluminum, Mg is magnesium, Zn is zinc, Be
50 mixture at a temperature of from 0° C. to 150° C. to
is beryllium, Li is lithium, R is a member selected from
the group consisting of hydrogen, an aromatic hydro
carbon radical containing from 6 to 12 carbon atoms, a
cause the formation of a substantially crystalline copoly
mer of 4-al1yl-1-cyclohexene and allylcyclohexane.
16. The method for producing a solid cocrystalline co
saturated aliphatic hydrocarbon radical containing 2 to 55 polymer of allylcyclohexane and vinylcyclohexane having
a high degree of crystallinity over the entire composition
12 carbon atoms and a saturated cycloaliphatic hydrocar
bon radical containing 3 to 1-2 carbon atoms, each of R1
and R2 is a member selected from the group consisting of
hydrogen, a saturated aliphatic hydrocarbon radical con
taining 2 to 12 carbon atoms, a saturated cycloaliphatic
hydrocarbon radical containing 3 to 10 carbon atoms and
an aromatic hydrocarbon radical containing 6 to 12 car
bon atoms, and halogen when no hydrogen is linked di—
range as determined by its X-ray diffraction pattern which
comprises forming a mixture ‘of allylcyclohexane and vinyl
rcyclohexane, together with a catalyst consisting essentially
of a halide of a transition metal selected from the ‘group
consisting of group IV-B', group V-B and group VI-B of
the periodic table and a compound selected from the group
consisting of:
rectly to the metallic nucleus, and heating said mixture at
a temperature of from 0° C. to 150° C. to cause the for 65
mation of a substantially crystalline copolymer of 9
allyl?uorene and 2-allyl?uorene.
14. The method for producing a solid cocrystalline co
polymer of 4-allyl-1-cyclohexene with 4-vinyl-1-cyclo—
hexene having a high degree of crystallinity over the en
tire composition range as determined by its X-ray dif
fraction pattern which comprises forming a mixture of
wherein Al is aluminum, Mg is magnesium, Zn is zinc,
Be is beryllium, Li is lithium, R is a member selected from
the group consisting of hydrogen, an aromatic hydrocar
lbon radical containing from 6 to 12 carbon atoms, a sat
urated aliphatic hydrocarbon radical containing 2 to 12
carbon atoms and a saturated cycloaliphatic hydrocarbon
radical containing 3 to 12 carbon atoms, each of R1 and
4-allyl-1-cyclohexene with 4-vinyl-l-cyclohexene, together
R2 is a member selected from the group consisting of
with a catalyst consisting essentially of a halide of a tran
hydrogen, a saturated aliphatic hydrocarbon radical con
sition metal selected from the group consisting of group 75 taining 2 to 12 carbon atoms, a saturated cycloaliphatic
3,091,601
17
18
and 4-cyclohexyl-1-‘butene having a high degree of crystal
hydrocarbon radical containing 3 to 10 carbon atoms and
an aromatic hydrocarbon radical containing 6 to 12 carbon
atoms, and halogen when no hydrogen is linked directly
linity over the entire composition range as determined by
its X-ray diffraction pattern.
25. A solid cocrystalline copolymer of allylcyclohexane
to the metallic nucleus, and heating said mixture at a
temperature of from 0° C. to 150° C. to cause the forma
and styrene having a high degree of crystallinity over the
entire composition range as determined by its X-ray dif
tion of a substantially crystalline copolymer of allylcyclo
hexane and vinylcyclohexane.
tract-ion pattern.
26. A solid cocrystalline copolymer of l-allylnaphtha
17. The method ‘for producing a solid cocrystalline co
lene and 2-vinylnaphthalene having a high degree of
polymer of 4,4-dimethyl-1-pentene and 5,5-dimethy-l-1
hexene having a high degree of crystall-inity ‘over the en 10 crystallinity over the entire composition range as deter
mined by its X-ray diifraction pattern.
27. A solid coc-rystalline copolymer of allylbenzene and
4-phenyl-14butene having a high degree of crystallinity
tire composition range as determined by its X-ray diffrac
tion pattern which comprises forming a mixture of 4,4
dimethyl-l-pentene and 5,5-dimethyl-1-hexene, together
over the entire composition range as determined by its
with 1a catalyst consisting essentially ‘of a halide of a transi
tion metal selected from the ‘group consisting of group 15 X-ray di?raction pattern.
28. A solid cocrystalline copolymer of styrene and al
lV-B, ‘group V-B and group VI-B ‘of the periodic table
lylbenzene having a high degree of crystallinity over the
and a compound selected from the group consisting of:
entire composition range as determined by its X-ray dif
fraction pattern.
and R-Li
20
wherein Al is aluminum, Mg is magnesium, Zn is zinc, Be
29. A solid cocrystalline copolymer of 4-(2-naphthyl)
l-butene and l-allylnaphthalene having a high degree of
crystallinity over the entire composition range as deter
is beryllium, vLi is 'lithium, R is a member selected from
the group consisting of hydrogen, an aromatic hydrocar
hon radical containing from 6 to 12 carbon atoms, a- sat
mined by its X-ray diifraction pattern.
30. A solid cocrystalline copolymer of l-allylnaphth-a
lene and 44(1-naphthy-D-1-butene having a high degree of
urated aliphatic hydrocarbon radical containing 2 to 12 25 crystallinity
over the entire composition range as deter
carbon atoms and a saturated cycloaliphatic hydrocarbon
mined
by
its
X-ray di?raction pattern.
radical containing 3 to 12 carbon atoms, each of R1 and R2
31. A solid cocrystalline copolymer of 4-(1-naphthyl)
is a member selected from the group consisting of hydro
1~butene and 4-(2-naphthyl)-l-butene having a high degree
gen, a saturated aliphatic hydrocarbon radical containing
of crystalli-nity over the entire composition range as deter
2 to 12 carbon ‘atoms, a saturated cycloaliphatic hydrocar 30
mined by its X-ray diiiraction pattern.
32. A solid cocrystalline copolymer of 9-allyl?uorene
and 2Jallyliluorene having a high degree of crystallinity
bon radical containing 3 to 10 carbon atoms and an aro
matic hydrocarbon radical containing 6 to 12 carbon
atoms, and halogen when no hydrogen is linked directly
over the entire composition range as determined by its
to the metallic nucleus, and heating said mixture at a.
X-ray diffraction pattern.
35
temperature of from 0° C. to 150° C. to cause the forma
33. A solid cocrysta-lline copolymer of 4-allyl-1-cyclo
tion of a substantially crystalline copolymer of 4,4-di
methyl-l-pentene and 5 ,S-dimethyl-lhexene.
hexene and 4-vinyl-1-cyclohexene having a high degree of
crystallinity over the entire composition range as deter
18. A method which comprises ‘forming a mixture of
mined by its X-ray di?raction pattern.
3-methyl-l-butene and 4-methyl-1-pentene, a hydrocarbon
34. A solid cocrystalline copolymer of 4-allyl-1-cyclo
diluent and 1a catalyst consisting essentially ‘of titanium 40 hexene and rallylcyclohexane having a high degree of crys
trichloride and triisobutyl-aluminum and heating said mix
ta-llinity over the entire composition range as determined
ture from a temperature of 25° C. to 120° C. to cause the
by its X-ray diffraction pattern.
formation of a substantially cocrystalline copolymer of 3
35. A solid cocrystalline copolymer of allylcyclohexane
methyl-l-butene and 4-methyl-lepentene having a high
vinylcyclohexane having a high degree of crystallinity
degree of crystallinity over the entire composition range 4:5 and
over the entire composition range as determined by its
as determined by its X-ray di?raction pattern.
'X-ray diiTract-ion pattern.
19. A method which comprises forming a mixture of
36. A solid cocrystalline copolymer of 4,4-dimethyl-1
3-rnethyl-1Jbutene and 4-methyl-1-pentene, a hydrocarbon
pentene and 5,5-dimethyl-1-hexene having a high degree
diluent and a catalyst consisting essentially of vanadium
trichloride and tr-iisobutyl-aluminum and heating said mix 50 of crystallinity over the entire composition range as deter
mined by its X-ray ditfraction pattern.
ture from a temperature of 25° C. to 120° C. to cause
the formation of a substantially cocrystal-line copolymer
of 3~methyl-1-butene and 4-methyl-1-pentene having a
high degree ‘of crystallinity over the entire composition
range as determined by its X-ray diffraction pattern.
References Cited in the ?le of this patent
UNITED STATES PATENTS
55
20. A solid cocrystalline copolymer of 3-methyl-1-bu
tene and 4-methyl-l- pentene having a high degree of
crystallinity over the entire composition range as deter
mined by its X-ray diffraction pattern.
21. A solid cocrystalline copolymer of 3-methyl-1-pen 60
tene and 4-methyl-1-pentene having a high degree of
crystallinity over the entire composition range as deter
mined by its X-ray diffraction pattern.
22. A solid cocrystalline copolymer of 3-methyl-1-hex
ene and 4~methyl~1~pentene having a high degree of crys 65
tallinity over the entire composition range as determined
by its X-ray diffraction pattern.
23. A solid cocrystalline copolymer of allylcyclopentane
and allylcyclohexane having a high degree of crystallinity
2,181,640
2,259,934
2,274,749
2,540,949
2,568,656
2,731,450
2,773,052
2,822,357
2,827,445
Deanesly et a1 _________ __ Nov. 28,
Huijser et al. __________ __ Oct. 21,
Smyers ________________ __ Mar. 3,
Jones _________________ __ Feb. 6,
Parrish ______________ __ Sept. 18,
Serniuk _______________ __ Jan. 17,
Cohen ________________ __ Dec. 4,
Brebner et ‘a1 ____________ __ ‘Feb. 4,
Bartolomeo et a1 _______ __ Mar. 18,
2,827,446
2,827,447
Breslow ______________ __ Mar. 18, 1958
Nowlin et a1 ___________ __ Mar. 18, 1958
2,832,759
‘2,842,474
2,842,532
2,868,772
Nowlin ______________ __ Apr. 29,
Pratt __________________ __ July 8,
Campbell ______________ __ July 8,
Ray __________________ __ Jan. 13,
over the entire composition range ‘as determined by its 70
X-ray diffraction pattern.
24. A solid cocrystalline copolymer of allylcyclohexane
1939
1941
1942
1951
1951
1956
1956
1958
1958
1958
1958
1958
1959
FOREIGN PATENTS
538,782
lBelgium ______________ __ Dec. 6, 1955
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