Process to make a monovinylaromatic polymer and said...

Details Process to make a monovinylaromatic polymer and said... Process to make a monovinylaromatic polymer and said...

1999-03-31

2001-05-15

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S347100, C526S347200, C526S943000, C502S152000

Reexamination Certificate

active

06232414

ABSTRACT:

FIELD OF THE INVENTION
This invention is related to the field of polymers.
BACKGROUND OF THE INVENTION
One of the most important processes for the production of homopolymers of ethylene or copolymers of ethylene/monoolefin is called the slurry polymerization process. Usually, this process employs a diluent, such as, for example, isobutane. However, while this process is very versatile in producing these polymers, it has long been desirable to produce other polymers using this process. This is because of the cost saving that can be realized by utilizing the same commercial operating equipment to produce different polymers.
The invention herein is a step towards this direction.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a process to produce a monovinylaromatic polymer.
It is another object of this invention to provide a monovinylaromatic polymer.
In accordance with this invention a process to produce a monovinylaromatic polymer is provided. Said process comprises polymerizing at least one monovinylaromatic to form a monovinylaromatic polymer, wherein said polymerizing:
(1) is conducted using at least one M-catalyst;
(2) is conducted under polymerization conditions, where said polymerization conditions comprise a temperature from about 0° C. to about 300° C. and a pressure from about 100 kPa to about 1000 kPa;
(3) is conducted in a polymerization zone; and
(4) is conducted in the presence of isobutane.
In accordance with this invention a monovinylaromatic polymer is provided. Said monovinylaromatic polymer is produced by said process.
These objects and other objects of this invention are further disclosed in the following.
DETAILED DESCRIPTION OF THE INVENTION
The monovinylaromatic monomers that can be used in this invention contain from about 8 to about 20 carbon atoms. However, it is more preferred when these monomers contain about 8 to about 12 carbon atoms. Suitable examples of such monomers are styrene, alpha-methyl styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 2-t-butylstyrene, 2,4-dimethylstyrene, and 4-cyclohexylstyrene. Styrene is currently most preferred.
These monomers are polymerized using at least one M-catalyst. For the purposes of this invention M-catalyst is defined as those catalysts that have the following general formula.
FORMULA ONE: (X
1
)(X
2
)(X
3
)(X
4
)M
1
In this formula, M
1
is selected from the group consisting of titanium, zirconium, and hafnium. Currently, it is most preferred when M
1
is titanium.
In this formula (X
1
) is independently selected from the group consisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, such as, for example, tetrahydroindenyls, and substituted fluorenyls, such as, for example, octahydrofluorenyls.
The substituents on the substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, can be aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, as long as these groups do not substantially, and adversely, affect the polymerization activity of the catalyst. Additionally, hydrogen can be a substituent.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Additionally, alkylsilyl groups where each alkyl contains 1-12 carbon atoms, alkyl halide groups where each alkyl contains 1-12 carbon atoms, or halides, can also be used.
Suitable examples of such substituents are methyl, ethyl, propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chloro, bromo, and iodo.
In this formula (X
3
) and (X
4
) are independently selected from the group consisting of (hereafter “Group OMC-II”) halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and oxyaliphatic groups, as long as these groups do not substantially, and adversely, affect the polymerization activity of the catalyst.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Currently, it is preferred when (X
3
) and (X
4
) are selected from the group consisting of halides and hydrocarbyls, where such hydrocarbyls have from 1 to 10 carbon atoms. However, it is most preferred when (X
3
) and (X
4
) are selected from the group consisting of fluoro, chloro, methoxy, and methyl.
In this formula, (X
2
) can be selected from either Group OMC-I or Group OMC-II. However, it is most preferred when (X
2
) is selected from Group OMC-II. This is because “half-sandwich” metallocenes are most preferred.
When (X
2
) is selected from Group OMC-I, it should be noted that (X
1
) and (X
2
) can be joined with a bridging group, such as, for example, aliphatic bridging groups, cyclic bridging groups, combinations of aliphatic and cyclic bridging groups, and organometallic bridging groups, as long as the bridging group does not substantially, and adversely, affect the polymerization activity of the catalyst. However, currently bridging groups are not preferred.
Suitable examples of aliphatic bridging groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic bridging groups are cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Additionally, it should be noted that substituted silicon and germanium radicals can also be used as bridging units.
Various processes are known to make these catalysts. See, for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817; 5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592; 5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284; 5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203; 5,654,454; 5,705,579; 5,623,034; and 5,668,230; the entire disclosures of which are hereby incorporated by reference.
Specific examples of metallocenes that can be used to make such catalysts are as follows:
(cyclopentadienyl) titanium trichloride;
ethyl(indenyl) titanium trichloride;
ethyl(tetrahydroindenyl) titanium trichloride;
n-butylcyclopentadienyl titanium trichloride;
cyclopentadienyl titanium trichloride; and
indenyl titanium methoxy dichloride.
Organoaluminum compounds can be used in this invention and they have the following general formula.
FORMULA TWO: Al(X
5
)
n
(X
6
)
3−n
In this formula (X
5
) is a hydrocarbyl having from 1-20 carbon atoms. Currently, it is preferred when (X
5
) is an alkyl having from 1 to 10 carbon atoms. However, it is most preferred when (X
5
) is selected from the group consisting of methyl, ethyl, propyl, butyl, and isobutyl.
In this formula (X
6
) is a halide, hydride, or alkoxide. Currently, it is preferred when (X
6
) is independently selected from the group consisting of fluoro and chloro. However, it is most preferred when (x
6
) is chloro.
In this formula “n” is a number from 1 to 3 inclusive. However, it is preferred when “n” is 3.
Examples of such compounds are as follows:
trimethylaluminum;
triethylaluminum;
tripropylaluminum;
tributylaluminum;
triisobutylaluminum hydride; and
triisobutylaluminum.
Currently, triisobutylaluminum is preferred.
The polymerizing is conducted under polymerization conditions. These polymerization conditions comprises a temperature and a pressure.
The temperature is from about 0° C. to about 300° C. However, it is more preferred when the temperature is from about 20° C. to about 200° C. and it is most preferred when the temperature is from 50° C. to 112° C.
The pressure is from about 100 kPa to about 10000 kPa. However, it is more preferred when the pressure is from about 500 kPa to about 6000 kPa and it is most preferred when the pressure is from 500 kPa to 5000 kPa.
The polymerizing is conducted in a polymerization zone. Currently, any rea

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