U.S. patent application number 09/882414 was filed with the patent office on 2002-04-11 for novel polyvinyl chloride resins.
Invention is credited to Costello, Christine Ann, Lohse, David John, Matturro, Michael Gerard, Patil, Abhimanyu Onkar, Schlosberg, Richard Henry, Schulz, Donald Norman, Varma-Nair, Manika.
Application Number | 20020042475 09/882414 |
Document ID | / |
Family ID | 24476667 |
Filed Date | 2002-04-11 |
United States Patent
Application |
20020042475 |
Kind Code |
A1 |
Patil, Abhimanyu Onkar ; et
al. |
April 11, 2002 |
Novel polyvinyl chloride resins
Abstract
The invention is directed towards a PVC resin composition
comprising polyvinyl chloride and a plasticizer selected from the
group consisting of: a non-linear, paraffin-soluble olefin-CO
copolymer; ii) a non-linear olefin-CO copolymer derived from
non-pure feeds; iii) an olefin-CO-X terpolymer derived from
non-pure feeds; and iv) a non-linear CO-X terpolymer. A method of
preparing the resins is also described.
Inventors: |
Patil, Abhimanyu Onkar;
(Westfield, NJ) ; Schulz, Donald Norman;
(Annandale, NJ) ; Varma-Nair, Manika; (Warren,
NJ) ; Lohse, David John; (Bridgewater, NJ) ;
Costello, Christine Ann; (Easton, PA) ; Schlosberg,
Richard Henry; (Bridgewater, NJ) ; Matturro, Michael
Gerard; (Lambertville, NJ) |
Correspondence
Address: |
ExxonMobil Research and Engineering Company
P.O. Box 900
Annandale
NJ
08801-0900
US
|
Family ID: |
24476667 |
Appl. No.: |
09/882414 |
Filed: |
June 15, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09882414 |
Jun 15, 2001 |
|
|
|
09618186 |
Jul 18, 2000 |
|
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Current U.S.
Class: |
525/185 |
Current CPC
Class: |
C08L 27/06 20130101;
C08G 67/02 20130101; C08L 73/00 20130101; C08L 27/06 20130101; C08L
2666/14 20130101; C08L 73/00 20130101; C08L 2666/04 20130101 |
Class at
Publication: |
525/185 |
International
Class: |
C08L 001/00 |
Claims
What is claimed is:
1. A PVC resin composition comprising polyvinyl chloride and a
plasticizer selected from the group consisting of: i) a non-linear,
paraffin-soluble olefin-CO copolymer; ii) a non-linear olefin-CO
copolymer derived from non-pure feeds; iii) an olefin-CO-X
terpolymer derived from non-pure feeds; and iv) a non-linear CO-X
terpolymer and mixtures thereof; wherein X is selected from the
group consisting of free radically polymerizable vinyl monomers and
mixtures thereof and wherein a non-pure feed comprises a first feed
comprising olefins and a second feed comprising carbon monoxide and
wherein when said polymer is (ii) and (iii) the amount of carbon
monoxide and olefin combined in said non-pure feed is less than or
equal to 95% and wherein said olefins in said first feed comprising
olefins are selected from the group consisting of linear and
branched C.sub.2 to C.sub.30 olefins, diolefins and mixtures
thereof.
2. The composition of claim 1 wherein said plasticizer is a
non-linear, paraffin-soluble olefin-CO copolymer.
3. The composition of claim 1 wherein said plasticizer is a
non-linear olefin-CO copolymer derived from non-pure feeds.
4. The composition of claim 1 wherein said plasticizer is an
olefin-CO-X terpolymer derived from non-pure.
5. The composition of claim 1 wherein said plasticizer is a
non-linear CO-X terpolymer.
6. The composition according to claim 1 further comprising a
co-plasticizer selected from the group consisting of dialkyl
phthalate, dialkyl isophthalate, dialkyl terephthalate, trialkyl
trimellitate, tetraalkyl pyromellitate, monoalkhyl benzoate,
dialkyl azelate, dialkyl sebacate, dialkyl adipate, and mixtures
thereof.
7. The composition according to claim 6 wherein said compound's
alkyl groups each have about 4 to 20 carbon atoms.
8. The composition according to claim 6 wherein the weight ratio of
said plasticizer to said co-plasticizer is in the range of about
1:9 to 9:1.
9. The composition according to claim 6 wherein said co-plasticizer
and said plasticizer comprise about 0.01 to 75 wt % of the PVC
resin composition.
10. The composition of claim 1 or 6 further comprising a stabilizer
selected from the group consisting of calcium, barium, cadmium,
zinc, lead, and mixture thereof.
11. The composition of claim 10 further comprising a filler
selected from the group consisting of calcium carbonate, clay, and
mixture thereof.
12. The composition of claim 1 or 6 further comprising a filler
selected from the group consisting of calcium carbonate, clay, and
mixture thereof.
13. The composition of claim 1 wherein said polyvinyl chloride
comprises from about 25 to 99.99 wt % of the PVC resin and said
plasticizer comprises from about 0.01 to 75 wt % of the PVC
resin.
14. An article formed from the PVC resin composition according to
claim 1.
15. A method for a preparing a PVC resin comprising blending
polyvinyl chloride with a plasticizer selected from the group
consisting of: i) a non-linear, paraffin-soluble olefin-CO
copolymer; ii) a non-linear olefin-CO copolymer derived from
non-pure feeds; iii) an olefin-CO-X terpolymer derived from
non-pure; and iv) a non-linear CO-X terpolymer; and mixtures
thereof and wherein X is selected from the group consisting of free
radically polymerizable vinyl monomers and mixtures thereof and
wherein a non-pure feed comprises a first feed comprising olefins
and a second feed comprising carbon monoxide and wherein when said
polymer is (ii) and (iii) the amount of carbon monoxide and olefin
combined in said non-pure feed is less than or equal to 95% and
wherein said olefins in said first feed comprising olefins are
selected from the group consisting of linear and branched C.sub.2
to C.sub.30 olefins, diolefins and mixtures thereof.
16. The method according to claim 15 further comprising the step of
blending a co-plasticizer selected from the group consisting of
dialkyl phthalate, dialkyl isophthalate, dialkyl terephthalate,
trialkyl trimellitate, tetraalkyl pyromellitate, monoalkhyl
benzoate, dialkyl azelate, dialkyl sebacate, dialkyl adipate, and
mixtures thereof.
17. The method of claim 15 or 16 further comprising the step of
blending a stabilizer selected from the group consisting of
calcium, barium, cadmium, zinc, lead, and mixture thereof.
18. The method of claim 15 or 16 further comprising the step of
blending a filler selected from the group consisting of calcium
carbonate, clay, and mixture thereof.
19. The method of claim 17 further comprising the step of blending
a filler selected from the group consisting of calcium carbonate,
clay, and mixture thereof.
20. The method according to claim 15 wherein said plasticizer is a
non-linear, paraffin-soluble olefin carbon monoxide copolymer.
21. The method according to claim 15 wherein said plasticizer
further comprises an acetylenically unsaturated monomer units.
22. The product formed by the method of claim 15.
23. The product formed by the method of claim 16.
24. The method according to claim 15 further comprising forming an
article from the PVC resin.
25. The method of claim 1 or 15 wherein said second feed comprising
carbon monoxide contains components selected from the group
consisting of hydrogen, Carbon Monoxide, methane, acetylene,
paraffins and mixtures thereof.
Description
[0001] This application is based on a Continuation-in-Part of U.S.
Ser. No. 09/618,186 filed Jul. 18, 2000.
FIELD OF THE INVENTION
[0002] The invention is directed towards novel carbon monoxide
containing compositions effective as plasticizers for polyvinyl
chloride resins.
BACKGROUND
[0003] Polyvinyl chloride (PVC) is a versatile polymer which is
used in many applications such as water piping, floor tile,
exterior vinyl siding, electrical wire insulation, shower curtains
and synthetic leather. Plasticizers are added to PVC to improve
flow, and therefore processability, as well as to reduce the
brittleness of the product. A plasticizer is a material
incorporated in a plastic to increase its workability and its
flexibility or distensibility (i.e., elongation). This is achieved
by lowering the glass transition temperature ("T.sub.g"), thereby
producing a change in properties from those of a hard, brittle,
glasslike solid to those of a soft, flexible, tough material. The
vast majority of plasticizers used today are monomeric ester-types.
Phthalates such as diisononyl phthalate, diisodecyl phthalate and
di(2-ethylhexyl) phthalate (dioctyl phthalate, DOP) are well known
and commonly used plasticizers. Further, plasticizers are usually
added to PVC on hot rolls or in a hot mixer such as a Banbury. The
plasticizer content varies widely depending on the end use of the
material; however, typically plasticizer content will be
approximately 5 to approximately 50% by weight.
[0004] When evaluating which plasticizers should be used for a
particular application, the permanence of the plasticizer, in
addition to miscibility with the PVC, is crucial. Permanence refers
to the stability of plasticizer within the blend. More
specifically, plasticizers, especially those with low molecular
weights, tend to be migratory in that they tend to move to the
surface of the blend where they subsequently evaporate and/or may
be removed by soapy water, solvents, oils, etc. These problems are
minimized by using high molecular weight polymers. Unfortunately,
very high molecular weight polymers may present processing and
compatibility problems, cause poor low temperature flexibility, and
become costly.
[0005] Copolymers of ethylene, carbon monoxide and a termonomer(s),
such as vinyl acetate, have been used as plasticizers in blends
with PVC to produce flexible films, as well as, rigid and
semi-rigid materials. These plasticizers are compatible with PVC,
lower the T.sub.g and possess adequate permanence. However, while
these plasticizers have proved to be effective, they are prepared
using pure feeds of the individual monomers which can be costly.
Hence, there is still a need to investigate other PVC plasticizers
which are compatible with PVC and sufficiently lower the PVC
resin's T.sub.g. Additionally, less expensive avenues to produce
known plasticizers should also be pursued.
SUMMARY OF INVENTION
[0006] The instant invention provides novel polyvinyl chloride
compositions having CO-containing polymers which act as
plasticizers. Depending on the particular plasticizer(s) used and
the type of PVC, percentage mix, etc., advantages of the instant
invention include: lower plasticizer volatility and accompanying
lower migration; lower cost than conventional monomeric
plasticizers; improved processability and compatibility; and
effective lowering of the PVC resin glass transition temperature
("T.sub.g").
[0007] In one embodiment, the invention is a PVC resin composition
comprising polyvinyl chloride and a plasticizer wherein said
plasticizer is selected from the group consisting of: i) a
non-linear, paraffin-soluble olefin-CO copolymer; ii) a non-linear
olefin-CO copolymer derived from non-pure feeds; iii) an
olefin-CO-X terpolymer derived from non-pure feeds; and iv) a
non-linear CO-X terpolymer; and mixtures thereof and wherein X is
selected from the group consisting of free radically polymerizable
vinyl monomers and mixtures thereof and wherein a non-pure feed
comprises a first feed comprising olefins and a second feed
comprising carbon monoxide and wherein when said polymer is (ii)
and (iii) the amount of carbon monoxide and olefin combined in said
non-pure feed is less than or equal to 95% and wherein said olefins
in said first feed comprising olefins are selected from the group
consisting of linear and branched C.sub.2 to C.sub.30 olefins,
diolefins and mixtures thereof.
[0008] The composition may further comprise a compound selected
from the group consisting of dialkyl phthalate, dialkyl
isophthalate, dialkyl terephthalate, trialkyl trimellitate,
tetraalkyl pyromellitate, monoalkhyl benzoate, dialkyl azelate,
dialkyl sebacate, dialkyl adipate, and mixtures thereof. Such
compounds are commonly referred to as co-plasticizers. The
composition may also further comprising a stabilizer or filler
selected from the group consisting of calcium, barium, cadmium,
zinc, lead, calcium carbonate, clay, and mixtures thereof.
[0009] In another embodiment, the invention is a product prepared
from the PVC resin as described above wherein said product is
selected from the group consisting of a film, a sheet, an extruded
item, a molded item a cast item and mixtures thereof.
[0010] In yet another embodiment, the invention is a method for a
preparing a PVC resin comprising blending polyvinyl chloride with a
plasticizer selected from the group consisting of: i) a non-linear,
paraffin-soluble olefin-CO copolymer; ii) a non-linear olefin-CO
copolymer derived from non-pure feeds; iii) an olefin-CO-X
terpolymer derived from non-pure feeds; and iv) a non-linear CO-X
terpolymer; and mixtures thereof and wherein X is selected from the
group consisting of free radically polymerizable vinyl monomers and
mixtures thereof and wherein a non-pure feed comprises a first feed
comprising olefins and a second feed comprising carbon monoxide and
wherein when said polymer is (ii) and (iii) the amount of carbon
monoxide and olefin combined in said non-pure feed is less than or
equal to 95 mole % and wherein said olefins in said first feed
comprising olefins are selected from the group consisting of linear
and branched C.sub.2 to C.sub.30 olefins, diolefins and mixtures
thereof.
[0011] This method may further comprise the step of blending a
compound selected from the group consisting of dialkyl phthalate,
dialkyl isophthalate, dialkyl terephthalate, trialkyl trimellitate,
tetraalkyl pyromellitate, monoalkyl benzoate, dialkyl azelate,
dialkyl sebacate, dialkyl adipate, and mixtures thereof.
[0012] These and other features, aspects and advantages of the
present invention will become better understood with regard to the
following description and appended claims.
DESCRIPTION
[0013] The instant invention relates to novel PVC/plasticizer
blends and the method of producing such blends based on carbon
monoxide ("CO") containing plasticizers. As used herein, a non-pure
feedstream is a feedstream comprising a first feed comprising
olefins and a second feed comprising carbon monoxide where the
amount of olefins and carbon monoxide combined is less than or
equal to 95 mole %. The non-pure feed can be either a combination
of the first and second feed or a co-feed of the first and second
feed.
[0014] Hence, for the non-pure feeds, it is possible for either of
the first olefinic feed or the second CO feed to be a pure feed so
long as once the feeds are combined, the amount of olefin in
combination with CO is less than or equal to 95 mole %.
Additionally, when the feed comprising CO contains .gtoreq.90 mole
is % CO, the remaining 90% of the feed will preferably comprise at
least 90 mole % hydrogen. It is also, therefore, possible for each
of the first olefinic feed and second CO feed to contain other
components. For example, while the first olefinic feed may be a
pure feed of vinyl monomers, including olefins, the CO feed may
comprise synthesis gas ("syngas") or multi-component synthesis gas
("MCS"). Alternatively, for example, the CO may originate from MCS
feeds which contain at least one olefin, carbon monoxide, hydrogen,
carbon dioxide, methane and optionally acetylene or paraffins.
Typically the first feed comprising olefins will contain C.sub.3 to
C.sub.6 olefins or dienes. If the CO feedstream is not pure and
contains components other than CO, it will typically contain up to
90-mole % CO, preferably up to 95-mole % CO
[0015] These CO-containing polymers are low molecular weight ("MW")
copolymers. Low MW means less than 50,000, preferably less than
30,000 and most preferably between about 200 to 30,000. It should
be appreciated by those skilled in the art that use of the general
term "copolymers" includes terpolymers and other polymers having
various combinations of different monomer units. It should also be
appreciated that the term "polyvinyl chloride" or "PVC" means
homopolymers of vinyl chloride, as well as, copolymers thereof
containing up to about 20% of other monomers including, but not
limited to, vinyl acetate, propylene, ethylene, butyl vinyl ether,
diethyl maleate, dimethyl fumarate, etc. CO feeds utilizable herein
are described in U.S. Pat. No. 6,049,011 to Kiss et al. Preferably,
the feedstream comprising CO will be syngas or multicomponent
syngas. The non-pure feeds will typically contain at least about
10% CO, preferably at least about 15% and at least about 50%
olefin, preferable at least about 60%.
[0016] The plasticizers of this invention may be synthesized using
well known free radical polymerization techniques. For example, the
CO containing polymers are formed in free radical polymerization
processes using organic peroxides as a free radical initiator
according to conventional methods. Representative initiators
include, but are not limited to, dialkyl peroxides such as
ditertiary-butyl peroxide, 2,5-dimethyl-2,
5-ditertiary-butyl-peroxyhexane, dicumyl peroxide; alkyl peroxides
such as tertiary-butyl hydroperoxide, tertiary-octyl hydroperoxide,
cumene hydroperoxide; aroyl peroxides such as benzoyl peroxide;
peroxy esters such as tertiary-butyl peroxypivalate,
tertiary-butyl-perbenzoate; and compounds such as
azo-bis-isobutyronitril- e. Free radical initiators with an
appropriate half-life at reaction temperatures ranging from about
50.degree. C. to about 230.degree. C. can be used. Of these,
t-butyl peroxypivalate, which has a half-life of about 10 hours at
66.degree. C., is preferred.
[0017] Such feeds and initiators are useful for forming
CO-containing polymers under copolymerization conditions at
temperatures ranging from about 50 to about 230.degree. C.,
preferably from about 50 to about 100.degree. C., pressures ranging
from about 100 to about 30,000 psig, preferably from about 100 to
about 3,000 psig, and in the presence of a free radical
initiator.
[0018] The term co-polymer is used herein according to its broad
meaning of a macromolecule formed from two or more momomer sources.
The term polymer as used herein according to its broad meaning of a
macromolecule formed from at least one monomer source.
[0019] Preferably the reaction occurs in the presence of a solvent.
Suitable solvents include toluene, benzene, dioxane, pentane,
heptane, hexane, propylene oxide, cyclohexane, etc. Hexane is
preferred.
[0020] The polymers and co-polymers utilized herein may be
recovered using conventional methods, for example, filtration or
evaporation of the diluent. They may be brought into the desired
shape using standard forming techniques, such as cold or hot
pressing. Alternatively, the polymerization is carried out in such
a way that the copolymer is formed in the desired shape, such as by
solution polymerization in a thin layer and subsequent removal of
the diluent, which yields the co-polymer in the form of a film.
[0021] The number average molecular weight ("Mn") of the copolymers
utilizable in accordance with the invention can range from about
less than 50,000, preferably about 200 to about 30,000.
[0022] Free radical polymerizable vinyl monomers include Vinyl
monomers useful in the invention include styrene and styrene
derivatives such as a-methylstyrene, p-methylstyrene, vinyl
acetate, vinyl chloride, isobutyl vinyl ether, methyl vinyl ketone,
1-vinylpyrrolidone, acrylic acid, methacrylic acid, methylacrylate,
methylmethacrylate, acrylonitrile, acrylamide, acrolein, allyl
alcohol, allyl chloride, allyl acetate, mixtures thereof, and
similar materials.
[0023] Because the instant invention employs free-radical
polymerization to form its non-linear copolymers, the resulting
non-linear copolymers may also be characterized as being
non-alternating.
[0024] The instant invention provides novel polyvinyl chloride
compositions having CO-containing polymers which act as
plasticizers. These CO-containing polymers are low molecular weight
copolymers. Depending on the particular plasticizer(s) used and the
type of PVC, percentage mix, etc., advantages of the instant
invention include: lower plasticizer volatility; lower cost than
conventional monomeric plasticizers; improved processability and
compatibility; and effective lowering of the PVC resin glass
transition temperature ("T.sub.g").
[0025] The composition of the invention is a PVC resin which
contains a novel plasticizer. More specifically, the plasticizer is
selected from the following:
[0026] 1) A non-linear, paraffin-soluble olefin-CO copolymer. A
more detailed description of these co-polymers can be found in U.S.
Pat. No. 6,156,872 herein incorporated by reference.
[0027] 2) A non-linear olefin-CO copolymer derived from non-pure
feeds.
[0028] 3) An olefin-CO-X terpolymer derived from non-pure feeds.
Here again, it should be noted that defining this copolymer as
being "derived from non-pure feeds", it is meant to also include
co-feeds. For example, one feed could be syngas or multicomponent
syngas while the other feed is a pure vinyl acetate. The two feeds
combined are the non-pure feed described herein. These copolymers
may include paraffin-soluble as well as paraffin insoluble
varieties. Typical molecular weights will be in the range of about
less than 50,000, more typically about 200 to about 30,000. In a
preferred embodiment, the olefin is ethylene.
[0029] 4) A non-linear CO-X copolymer where X is a free radically
polymerizable vinyl monomer.
[0030] 5) Mixtures of the plasticizers defined in 1-4.
[0031] The composition may optionally contain, in addition to the
plasticizers defined above, a dialkyl phthalate, or other suitable
monomeric esters such as dialkyl isophthalates, dialkyl
terephthalates, benzoates, trialkyl trimellitates, and the like.
Preferred dialkyl phthalates are those having alkyl groups with
approximately 4 to 20 carbons. In a preferred embodiment, the ratio
of plasticizer to dialkyl phthalates will be in the range of 9:1 to
1:9 and the mix of these plasticizers will account for about 0.01
to 75 weight percent of the PVC resin composition. Thus, in this
preferred embodiment, the polyvinyl chloride will make up
approximately 25 to 99.99 weight percent of the PVC resin
composition. The composition may also further comprise stabilizers,
fillers, and/or other well-known additives that are commonly used
in the art. Suitable stabilizers include, but are not limited to,
calcium, barium, cadmium, zinc, lead and mixtures thereof.
Preferably, the stabilizers will make up approximately 0.01 to 7
weight percent of the PVC resin. Suitable fillers include, but are
not limited to, calcium carbonate, clay and mixture thereof.
Preferably, fillers will be approximately 0.01 to 6 weight percent
of the PVC resin.
[0032] In another embodiment, the invention is an article produced
from the PVC resin composition described above. For instance, the
PVC resin composition could be made into a film or a sheet.
Articles can also be extruded, molded or cast from the PVC resin
composition.
[0033] Also provided for is a method for preparing a PVC resin
comprising blending polyvinyl chloride with a plasticizer, as
defined above. The method may further include the step of blending
a dialkyl phthalate. Additionally, stabilizers and/or fillers may
also be blended. Standard PVC/plasticizer blending techniques, well
known to those skilled in the art, may be used such as adding the
plasticizers to PVC on hot rolls or in a hot mixture such as a
Banbury. Typical temperatures for such blending techniques are in
the range of about 20 to 300.degree. C. Preferred temperature
ranges are from about 50 to 230.degree. C. Typical pressures for
these blending techniques can range widely from about 100 to 60000
psi. Preferred pressure ranges are in the range of about 100 to
30000 psi. Processing aids, such as stearic acid, may optionally be
used. Thus, small amounts of these processing aids may, or may not,
become incorporated into the composition. Additionally, as
illustrated in the examples below, the copolymer and terpolymers
can be dissolved in organic solvents along with the PVC and then
cast to form a film.
[0034] The invention is further described in the following
non-limiting examples.
EXAMPLES
Example 1
Synthesis of Ethylene-CO Polymers using MCS Feed
[0035] CO containing polymers using a dilute MCS feed was
synthesized according to free-radical polymerization techniques as
follows:
[0036] A 300 ml autoclave reactor was charged with 150 ml pure
n-hexane and 0.6 g of a 75% solution of t-butyl peroxypivalate in
mineral spirits. (t-Butyl peroxypivalate has a 10 hour half-life at
55.degree. C. in a 0.2 M benzene solution, Swem, Organic Peroxides,
John Wiley and Sons, 1970, Vol. 1, pp. 82, 87). The reactor was
sealed and purged with purified nitrogen. The reactor was then
pressurized with the MCS mixture (ethylene 5.4 mole %, carbon
monoxide 1.3 mole %, carbon dioxide 7.4 mole %, hydrogen 4.6 mole %
and methane 81.3 mole %) to 700 psig. The temperature was raised to
66.degree. C. while stirring and the pressure was maintained for 24
hours. The reactor was allowed to cool to room temperature and was
then depressurized. The hexane was removed on a rotary evaporator
to obtain the product.
[0037] The product was characterized by IR, NMR and GPC. The FTIR
spectrum of the product showed a very strong peak at 1715 cm.sup.-1
due to carbonyl group, indicating incorporation of carbon monoxide
in the product. The .sup.13C NMR of the product indicated that the
polymer had 5.1% CO incorporation and a non-linear (branched)
polyethylene structure, as indicated by a broad multiplet in the
.sup.13C NMR for the alkyl region at 9-48 ppm and a multiplet at
206-218 for the CO resonance. The GPC of the product indicated a Mn
of 320 and a Mw of 420.
Example 2
Synthesis of Ethylene-CO-1-octene Terpolymers
[0038] CO containing polymers using a dilute MCS as co-feed with
1-octene was synthesized according to free-radical polymerization
techniques as follows:
[0039] The polymerization conditions were similar to those set
forth in Example 1. A 300 ml autoclave reactor was charged with 150
ml pure n-hexane and 0.6 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. 20 g 1-octene was added in the
reactor. The reactor was sealed and purged with purified nitrogen.
The reactor was then pressurized with the MCS mixture (ethylene 5.4
mole %, carbon monoxide 1.3 mole %, carbon dioxide 7.4 mole %,
hydrogen 4.6 mole % and methane 81.3 mole %) to 700 psig. The
temperature was raised to 66.degree. C. while stirring and the
pressure was maintained for 24 hours. The reactor was allowed to
cool to room temperature and was then depressurized. The hexane and
unreacted octene was removed on a rotary evaporator to obtain the
2.9 g of product.
[0040] The product was characterized by IR, NMR and GPC. The FTIR
spectrum of the product showed a very strong peak at 1715 cm.sup.-1
due to carbonyl group, indicating incorporation of carbon monoxide
in the product. The GPC of the product indicated a Mn of 860 and a
Mw of 1010.
Example 3
Synthesis of Ethylene-CO-vinyl Acetate Terpolymers
[0041] CO containing polymers using a dilute MCS as co-feed with
vinyl acetate was synthesized according to free-radical
polymerization techniques as follows:
[0042] The polymerization conditions were similar to those set
forth in Example 1. A 300 ml autoclave reactor was charged with 150
ml pure n-hexane and 0.6 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. 2 g vinyl acetate was added in
the reactor. The reactor was sealed and purged with purified
nitrogen. The reactor was then pressurized with the MCS mixture
(ethylene 5.4 mole %, carbon monoxide 1.3 mole %, carbon dioxide
7.4 mole %, hydrogen 4.6 mole % and methane 81.3 mole %) to 700
psig. The temperature was raised to 66.degree. C. while stirring
and the pressure was maintained for 24 hours. The reactor was
allowed to cool to room temperature and was then depressurized. The
hexane and unreacted octene was removed on a rotary evaporator to
obtain the 2.5 g of product.
[0043] The product was characterized by IR, NMR and GPC. The
.sup.13C NMR of the product indicated that the polymer had 9 mole %
CO, 56 mole % ethylene and 35 mole % vinyl acetate. The GPC of the
product indicated a Mn of 730 and a Mw of 1620.
Example 4
Synthesis of ethylene-CO-vinyl Neo-10 ester terpolymers
[0044] CO containing polymers using a dilute MCS as co-feed with
neo vinyl ester (Exxar.TM. Neo-10) was synthesized according to
free-radical polymerization techniques as follows:
[0045] The polymerization conditions were similar to those set
forth in Example 1. A 300 ml autoclave reactor was charged with 150
ml pure n-hexane and 0.6 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. 5 g neo vinyl ester (Exxar.TM.
Neo-10) was added in the reactor. The reactor was sealed and purged
with purified nitrogen. The reactor was then pressurized with the
MCS mixture (ethylene 5.4 mole %, carbon monoxide 1.3 mole %,
carbon dioxide 7.4 mole %, hydrogen 4.6 mole % and methane 81.3
mole %) to 700 psig. The temperature was raised to 66.degree. C.
while stirring and the pressure was maintained for 24 hours. The
reactor was allowed to cool to room temperature and was then
depressurized. The hexane and unreacted neo vinyl ester was removed
initially on a rotary evaporator and then on Kugelrohr apparatus to
obtain the 1.9 g of product.
[0046] The .sup.13C NMR of the product indicated that the polymer
had 4.6 mole % CO, 48 mole % ethylene and 47.4 mole % neo vinyl
ester (Exxar.TM. Neo-10). The GPC of the product indicated a Mn of
1450 and a Mw of 2100.
Example 5
Synthesis of Ethylene-CO-vinyl Neo-10 Ester Terpolymers
[0047] CO containing polymers using a dilute MCS as co-feed with
neo vinyl ester (Exxar.TM. Neo-10) was synthesized according to
free-radical polymerization techniques as follows:
[0048] The polymerization conditions were similar to those set
forth in Example 1. A 300 ml autoclave reactor was charged with 150
ml pure n-hexane and 0.6 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. 2 g neo vinyl ester (Exxar.TM.
Neo-10) was added in the reactor. The reactor was sealed and purged
with purified nitrogen. The reactor was then pressurized with the
MCS mixture (ethylene 5.4 mole %, carbon monoxide 1.3 mole %,
carbon dioxide 7.4 mole % hydrogen 4.6 mole % and methane 81.3 mole
%) to 700 psig. The temperature was raised to 66.degree. C. while
stirring and the pressure was maintained for 24 hours. The reactor
was allowed to cool to room temperature and was then depressurized.
The hexane and unreacted neo vinyl ester was removed initially on a
rotary evaporator and then on Kugelrohr apparatus to obtain the
product.
[0049] The .sup.13C NMR of the product indicated that the polymer
had 7.9 mole % CO, 55.6 mole % ethylene and 36.4 mole % neo vinyl
ester (Exxar.TM. Neo-10). The GPC of the product indicated a Mn of
970 and a Mw of 1300.
Example 6
Synthesis of CO-1-octene Copolymer
[0050] A 300 ml autoclave reactor was charged with 150 ml pure
n-hexane and 0.6 g of a 75% solution of t-butyl peroxypivalate in
mineral spirits. 10 g 1-octene was added in the reactor. The
reactor was sealed and purged with purified nitrogen. The reactor
was then pressurized with CO to 700 psig. The temperature was
raised to 66.degree. C. while stirring and the pressure was
maintained for 24 hours. The reactor was allowed to cool to room
temperature and was then depressurized. The hexane and unreacted
octene was removed on a rotary evaporator to obtain the 1.38 g of
product.
[0051] The FTIR spectrum of the product showed a very strong peak
at 1711 cm.sup.-1 due to carbonyl group, indicating incorporation
of carbon monoxide in the product. The .sup.13C NMR of the product
indicated that the polymer had 27 mole % CO and 73 mole % 1-octene.
The GPC of the product indicated a Mn of 965 and a Mw of 1175.
Example 7
Plasticization Study using Plasticizers Derived from MCS
[0052] In order to demonstrate in a simple manner the effect of
plasticization, films of the PVC resin were prepared as follows: 10
g PVC polymer (Aldrich, 233,000) was dissolved in 150 ml THF and
the solution was stirred at room temperature for 24 hrs to obtain a
stock solution. 2.5 ml of PVC solution was mixed with appropriate
concentration of plasticizer (as THF solution) to give plasticizer
content from 10 to 50%. The mixer was stirred for 12 hours at room
temperature and the resultant solution poured on to horizontal
aluminum or glass container. The solvent was allowed to evaporate
slowly under nitrogen. After 12 hours the films were peeled away
from the container. They were dried in a vacuum over at 50.degree.
C. for 12 hours. The flexibility of the films was compared by
bending back and forth between the fingers; also their glass
transition temperatures ("T.sub.g") were evaluated using a
differential scanning calorimeter ("DSC").
[0053] Relaxation in PVC resin from glassy to the plastic state and
effect of various chemical plasticizers was measured
calorimetrically using a DSC. The Tg was evaluated from the step
change in heat capacity, Cp (value at half .DELTA.Cp is reported),
when the sample was heated at a controlled heating rate of 10
K/min. All samples analyzed were treated to similar thermal history
prior to measurement. The films obtained from the PVC and carbon
monoxide containing polymers described above were transparent.
1TABLE 1 Effect of plasticizers on the Tg of PVC Plasticizer
Example Sample PVC Concentration .DELTA. Tg Number Description Tg
(.degree. C.) (wt %) (.degree. C.) PVC Aldrich (Mw 233,000) 82 --
-- 1 ECO (MCS) -- 10 19 2 ECO (MCS)/Octene -- 20 20 3 ECO (MCS)-VA
-- 20 28 5 ECO (MCS)-Neo-10 -- 10 12 ester 6 CO/1-octene -- 20 12
Phthalate -- 20 40
[0054] The decrease in the T.sub.g of the PVC with carbon
monoxide-containing polymers provides evidence that these
compositions are active as PVC plasticizer.
Example 8
The synthesis of Ethylene-CO Copolymers Using Ethylene and
Syngas
[0055] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. The reactor was then pressurized
with an ethylene and syngas mixture (ethylene:carbon
monoxide:hydrogen 50:25:25, respectively). The temperature was
raised to 66.degree. C. while stirring, and the pressure was
maintained for 24 hours. The reactor was allowed to cool to room
temperature and then depressurized. The hexane was removed on a
rotary evaporator, leaving 7.8 g of product.
[0056] The IR spectrum of the product shows a very strong peak at
1705 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggests that
the polymer has 39.5% CO incorporation. The GPC of the product
indicates a Mn of 1100 and Mw of 2300 (polystyrene standards, THF
solvent).
Example 9
Synthesis of Ethylene-CO copolymers Using Ethylene and Syngas
[0057] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. The reactor was then pressurized
with an ethylene and syngas mixture (ethylene:carbon
monoxide:hydrogen 70:15:15, respectively). The temperature was
raised to 66.degree. C. while stirring, and the pressure was
maintained for 24 hours. The reactor was allowed to cool to room
temperature and then depressurized. The hexane was removed on a
rotary evaporator leaving 9.3 g of product.
[0058] The IR spectrum of the product shows a very strong peak at
1709 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggests that
the polymer has 33.9% CO incorporation. The GPC of the product
indicates a Mn of 1600 and Mw of 3200 (polystyrene standards, THF
solvent).
Example 10
Synthesis of Ethylene-CO Copolymers Using Ethylene and Syngas
[0059] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of t-butyl peroxide in mineral spirits.
The reactor was sealed and purged with purified nitrogen. The
reactor was then pressurized with an ethylene and syngas mixture
(ethylene:carbon monoxide:hydrogen 70:15:15, respectively). The
temperature was raised to 120.degree. C. while stirring, and the
pressure was maintained for 24 hours. The reactor was allowed to
cool to room temperature and then depressurized. The hexane was
removed on a rotary evaporator leaving 4.3 g of product.
[0060] The IR spectrum of the product shows a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggests that
polymer had 19.3% CO incorporation. The GPC of the product
indicates a Mn of 590 and Mw of 1100 (polystyrene standards, THF
solvent).
Example 11
Plasticization Study Using Ethylene-CO Plasticizers Derived from
Syngas
[0061] To demonstrate in a simple manner the effect of
plasticization, films of the polymers were prepared as follows: 10
g PVC polymer (Aldrich, 233,000) were dissolved in 150 ml THF and
the solution was stirred at room temperature for 24 hours to obtain
a stock solution. Then 2.5 ml of PVC solution were mixed with an
appropriate concentration of plasticizer (as THF solution,
sometimes hot THF solution) to give plasticizer content from 10 to
50%. The solvent was allowed to evaporate under nitrogen. After 12
hours the films were peeled away from the container. They were
dried in a vacuum oven at 50.degree. C. for 12 hours. Film
flexibility was compared by bending the films back and forth
between the fingers; also, their T.sub.g was evaluated.
[0062] Relaxation in PVC from glassy to the plastic state and the
effect of various chemical plasticizers were measured
calorimetrically using a DSC. The Tg was evaluated from the step
change in heat capacity, Cp (value at half .DELTA.Cp is reported),
when the sample was heated at a controlled heating rate of 10
K/min. All samples analyzed were exposed to a similar thermal
history before measurement. The films obtained from the PVC and
carbon-monoxide-containing polymers described above were
transparent.
[0063] Table 2 shows the decrease in the T.sub.g of PVC upon
addition of various levels of ethylene-CO copolymers. The
commercial plasticizer ditridecyl phthalate (DTDP) is also plotted
as a reference.
2TABLE 2 Effect of ethylene-CO plasticizers on the Tg of PVC
Plasticizer Tg of Tg of PVC + Tg of PVC + Tg of PVC + Concentra-
PVC + ECO polymer ECO polymer ECO polymer tion (wt %) DTDP of
Example 8 of Example 9 of Example 10 0 82 82 82 82 10 60 63 61 52
20 43 47 46 34 30 27 29 33 21 40 -- -- 27 13 50 10 -- -- 4
[0064] The decrease in the T.sub.g of the PVC with ethylene/carbon
monoxide copolymers provides evidence that these compositions are
active as PVC plasticizers.
Example 12
Synthesis of Ethylene-CO-alpha-olefin Terpolymers Using Syngas
[0065] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. The reactor was then pressurized
with ethylene and syngas mixture (ethylene:carbon
monoxide:hyrdrogen 70:15:15, respectively). Then 10.8 g of 1-butene
was added, the temperature was raised to 66.degree. C. while
stirring, and the pressure was maintained for 24 hours. The reactor
was allowed to cool to room temperature and then depressurized. The
hexane was removed on a rotary evaporator, leaving 4.9 g of the
product.
[0066] The IR spectrum of the product shows a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggests that
the polymer has 25.8% CO incorporation. The NMR spectrum of the
terpolymer suggested that it has 134.9 branches per 1000 carbons
versus 65.5 branches per 1000 carbons for a control experiment
without 1-butene termonomer. This observation indicates that
increased in branching may result from alpha-olefin incorporation
in the polymer. The GPC of the product indicates a Mn of 1000 and
Mw of 2000 (polystyrene standards, THF solvent).
Example 13
Synthesis of Ethylene-CO-alpha-olefin Terpolymers Using Syngas
[0067] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. The reactor was then pressurized
with an ethylene and syngas mixture (ethylene:carbon
monoxide:hydrogen 70:15:15, respectively). Then 5.9 g of 1-butene
was added, the temperature was raised to 66.degree. C. while
stirring, and the pressure was maintained for 24 hours. The reactor
was allowed to cool to room temperature and then depressurized. The
hexane was removed on a rotary evaporator leaving 7.0 g of the
product.
[0068] The IR spectrum of the product showed a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggested that
the polymer had 29.6% CO incorporation. The NMR spectrum of the
terpolymer suggested that it has 101 branches per 1000 carbons
versus 65.5 branches per 1000 carbons obtained in a control
experiment without the 1-butene termonomer. This observation
indicates that increased branching may result from alpha-olefin
incorporation in the polymer. The GPC of the product indicates a Mn
of 500 and Mw of 1000 (polystyrene standards, THF solvent).
Example 14
Synthesis of Ethylene-CO-alpha-olefin Terpolymers Using Syngas
[0069] A 300-mL autoclave engineer's reactor was charged with
150-mL pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. The reactor was then pressurized
with an ethylene and syngas mixture (ethylene:carbon
monoxide:hydrogen 70:15:15, respectively). Then 5.9 g of propylene
was added, the temperature was raised to 66.degree. C. while
stirring, and the pressure was maintained for 24 hours. The reactor
was allowed to cool to room temperature and was then depressurized.
The hexane was removed on a rotary evaporator, leaving 7.6 g of the
product.
[0070] The IR spectrum of the product showed a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggested that
the polymer had 17.5% CO incorporation. The NMR spectrum of the
terpolymer suggested that it has 72.8 branches per 1000 carbons
versus 65.5 branches per 1000 carbons obtained in a control
experiment without the propylene termonomer. This observation
indicates that increased branching may result from alpha-olefin
incorporation in the polymer. The GPC of the product indicated a Mn
of 500 and Mw of 1000 (polystyrene standards, THF solvent).
Example 15
Synthesis of Ethylene-CO-alpha-olefin Terpolymers Using Syngas
[0071] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. The reactor was then pressurized
with an ethylene and syngas (ethylene:carbon monoxide:hydrogen
70:15:15, respectively) mixture. Then 10.8 g of 2-butene was added,
the temperature was raised to 66.degree. C. while stirring, and the
pressure was maintained for 24 hours. The reactor was allowed to
cool to room temperature and then depressurized. The hexane was
removed on a rotary evaporator, leaving 6.7 g of the product.
[0072] The IR spectrum of the product showed a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. The NMR of the product suggested that
the polymer had 18.2% CO incorporation. The NMR spectrum of the
terpolymer suggested that it has 93.2 branches per 1000 carbons
versus 65.5 branches per 1000 carbons obtained in a control
experiment without 2-butene termonomer. This observation indicates
that increased branching may result from alpha-olefin incorporation
in the polymer. The GPC of the product indicated a Mn of 590 and Mw
of 1120 (polystyrene standards, THF solvent).
Example 16
Plasticization Study Using Ethylene-CO-alpha-olefin Plasticizers
Derived from Syngas
[0073] To demonstrate in a simple manner the effect of
plasticization, films of the polymers were prepared as follows: 10
g PVC polymer (Aldrich, 233,000) were dissolved in 150 ml THF and
the solution was stirred at room temperature for 24 hours to obtain
a stock solution. Then 2.5 ml of PVC solution was mixed with an
appropriate concentration of plasticizer (as THF solution,
sometimes hot THF solution) to give a plasticizer content from 10
to 50%. The solvent was allowed to evaporate under nitrogen. After
12 hours the films were peeled away from the container. They were
dried in a vacuum oven at 50.degree. C. for 12 hours. Film
flexibility was compared by bending the films back and forth
between the fingers; also, their T.sub.g was evaluated.
[0074] Relaxation in PVC from glassy to the plastic state and the
effect of various chemical plasticizers were measured
calorimetrically using DSC. The T.sub.g was evaluated from the step
change in heat capacity, Cp (value at half .DELTA.Cp is reported),
when the sample was heated at a controlled heating rate of 10
K/min. All samples analyzed were exposed to a similar thermal
history before measurement. The films obtained from the PVC and
carbon-monoxide-containing polymers described above were
transparent.
[0075] Table 3 shows the decrease in the T.sub.g of PVC upon
addition of various levels of these terpolymers. The commercial
plasticizer, di-tridecyl phthalate (DTDP) is also plotted as a
reference.
3TABLE 3 Effect of ethylene-CO-alpha-olefin plasticizers on the Tg
of PVC Tg of PVC + Tg of PVC + Tg of PVC + Tg of PVC + Plasticizer
Tg of terpolymer terpolymer terpolymer terpolymer Concentra- PVC +
of Example of Example of Example of Example tion (wt %) DTDP 12 13
14 15 0 82 82 82 82 82 10 60 55 63.66 63.25 64.16 20 43 42 50.79
48.07 51.12 30 27 31 40.91 41.1 39.9 40 -- 25 31.7 29.7 50 10 20
28.4 24.62 23.35
[0076] The decrease in the T.sub.g of the PVC resin with
ethylene/carbon monoxide copolymers provides evidence that these
compositions are active as PVC plasticizers.
[0077] The foregoing examples clearly demonstrate that the instant
invention provides compatible CO-containing platsticizers for use
with PVC. More specifically, the PVC resins of the instant
invention have decreased T.sub.g. Additionally, the compositions
produced in the non-limiting examples showed no evidence of phase
separation which suggests adequate compatibility. Finally, the
instant invention can be synthesized using relatively inexpensive
non-pure fees such as syngas and MCS. Hence, the desirable
characteristics (e.g., low Tg, compatibility and lower cost)
discussed in the background section are satisfied by the instant
invention.
Example 17
Synthesis of Ethylene-CO Copolymer
[0078] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.5 g of t-butyl peroxide. The reactor was
sealed and purged with purified nitrogen. The reactor was then
pressurized with ethylene and carbon monoxide (80:20) mixture. The
temperature was raised to 120.degree. C. while stirring, and the
pressure was maintained at 700 psig for 24 hours. The reactor was
allowed to cool to room temperature and depressurized. Hexane was
removed using a rotary evaporator, leaving 6.91 g of the
product.
[0079] The IR spectrum of the product showed a very strong peak at
1706 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. NMR of the product suggested that the
polymer had 25.9% CO incorporation. The NMR also suggested that
there are 96 branches/1000C. GPC of the product indicated a Mn of
350 and Mw of 750 (polystyrene standards, THF solvent).
Example 18
Synthesis of Ethylene-CO Copolymer Using Syngas Feed
[0080] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.5 g of t-butyl peroxide. The reactor was
sealed and purged with purified nitrogen. The reactor was then
pressurized with ethylene and syngas (ethylene:carbon
monoxide:hydrogen 70:15:15, respectively) mixture. The temperature
was raised to 120.degree. C. while stirring, and the pressure was
maintained at 700 psig for 24 hours. The reactor was allowed to
cool to room temperature and depressurized. Hexane was removed
using a rotary evaporator, leaving 4.3 g of the product.
[0081] The IR spectrum of the product showed a very strong peak at
1709 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. NMR of the product suggested that the
polymer had 19.3% CO incorporation. The NMR also suggested that
there are 172 branches/1000C. GPC of the product indicated a Mn of
590 and Mw of 1100 (polystyrene standards, THF solvent).
Example 19
Synthesis of 1-butene-CO Copolymer Using Syngas Feed
[0082] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.5 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. 4.89 g of 1-butene was added into
stainless steel addition vessel and attached to the reactor. The
reactor was then pressurized with syngas (carbon monoxide:hydrogen
50:50) mixture to 700 psig. The temperature was raised to
66.degree. C. while stirring. The butene was then introduced into
the reactor from the addition vessel and the pressure was
maintained at 700 psig for 24 hours. The reactor was allowed to
cool to room temperature and depressurized. Hexane was removed
using a rotary evaporator, leaving 0.98 g of the product. The IR
spectrum of the product showed a very strong peak at 1709 cm.sup.-1
due to the carbonyl group. Thus, CO has been incorporated in the
product.
Example 20
Synthesis of Ethylen-CO-butene Terpolymer Using Syngas Feed
[0083] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. 5.93 g of 1-butene was added into
stainless steel addition vessel and attached to the reactor. The
reactor was then pressurized with ethylene and syngas
(ethylene:carbon monoxide:hydrogen 70:15:15, respectively) mixture.
The temperature was raised to 66.degree. C. while stirring. The
butene was then introduced into the reactor from the addition
vessel and the pressure was maintained at 700 psig for 24 hours.
The reactor was allowed to cool to room temperature and
depressurized. Hexane was removed using a rotary evaporator,
leaving 7.01 g of the product.
[0084] NMR of the product suggested that the polymer had 29.6% CO
incorporation. The NMR also suggested that there are 101
branches/1000C. GPC of the product indicated a Mn of 500 and Mw of
1000 (polystyrene standards, THF solvent).
Example 21
Synthesis of 1-butene-CO Copolymer
[0085] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. 10.172 g of 1-butene was added into
stainless steel addition vessel and attached to the reactor. The
reactor was then pressurized with carbon monoxide to 350 psig and
the temperature was raised to 66.degree. C. while stirring. The
butene was then introduced into the reactor from the addition
vessel and the pressure was increased with carbon monoxide to 700
pisg and maintained at 700 psig for 24 hours. The reactor was
allowed to cool to room temperature and depressurized. Hexane was
removed using a rotary evaporator, leaving 1.4 g of the
product.
[0086] The IR spectrum of the product showed a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product. NMR of the product suggested that the
polymer had 24% CO incorporation. The NMR also suggested that there
are 223 branches/1000C. GPC of the product indicated a Mn of 470
and Mw of 600 (polystyrene standards, THF solvent).
Example 22
Synthesis of Propylene-CO Copolymer
[0087] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. 10.682 g of propylene was added into
stainless steel addition vessel and attached to the reactor. The
reactor was then pressurized with carbon monoxide to 350 psig and
the temperature was raised to 66.degree. C. while stirring. The
propylene was then introduced into the reactor from the addition
vessel and the pressure was increased with carbon monoxide to 700
pisg and maintained at 700 psig for 24 hours. The reactor was
allowed to cool to room temperature and depressurized. Hexane was
removed using a rotary evaporator, leaving 1.5 g of the
product.
[0088] The IR spectrum of the product showed a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product.
Example 23
Synthesis of CO-containing Polymer from Raf II and CO Feed
[0089] A 300-mL autoclave engineer's reactor was charged with 150
ml pure n-hexane and 0.64 g of a 75% solution of t-butyl
peroxypivalate in mineral spirits. The reactor was sealed and
purged with purified nitrogen. 10.475 g of RAF II mixture (mole %
cis 2-butene: 17%, trans 2-butene 17%, Isobutylene 5.51%,
1,3-butadiene 5237 ppm and remaining 1-butene) was added into
stainless steel addition vessel and attached to the reactor. The
reactor was then pressurized with carbon monoxide to 350 psig and
the temperature was raised to 66.degree. C. while stirring. The RAF
II was then introduced into the reactor from the addition vessel
and the pressure was increased with carbon monoxide to 700 pisg and
maintained at 700 psig for 24 hours. The reactor was allowed to
cool to room temperature and depressurized. Hexane was removed
using a rotary evaporator, leaving 1.33 g of the product.
[0090] The IR spectrum of the product showed a very strong peak at
1711 cm.sup.-1 due to the carbonyl group. Thus, CO has been
incorporated in the product.
* * * * *