Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-09-18
2003-05-13
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...
C526S161000, C526S172000, C526S348000, C525S323000
Reexamination Certificate
active
06562930
ABSTRACT:
TECHNICAL FIELD
This invention is directed to bis(salicylaldiminato)titanium complex catalysts, and highly syndiotactic polypropylene makable therewith by a chain-end control mechanism, and block copolymers containing the syndiotactic polypropylene and poly(ethylene-co-propylene) and/or poly(alpha-olefin-co-propylene), as well as to living olefin polymers and to olefin terminated to oligomers and polymers and to methods of making syndiotactic polypropylene, block copolymers and olefin-terminated oligomers and polymers from propylene.
BACKGROUND OF THE INVENTION
The kind of polypropylene in general use, for example, for packaging and container functionality, is isotactic polypropylene. It is typically described as having the methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer. Isotactic polypropylene lacks clarity and thus is not useful in cases where this is important.
Another kind of polypropylene is syndiotactic polypropylene. It may be described as having the methyl groups attached to the tertiary carbon of successive monomeric units on alternate sides of a hypothetical plane through the main chain of the polymer. Syndiotactic polypropylene is clear, that is it does not have the lack of clarity characteristic of isotactic polypropylene.
There are two types of syndiotactic polypropylene. One of these types is referred to as being made by a chain-end control mechanism and contains defects of the rmr type. NMR analysis for this kind of structure is shown in Zambelli, et al., Macromolecules, 13, 267-270 (1980). The most syndiospecific polypropylene of this type made before this invention has [rrrr] pentad content of 0.63 (described in Pellecchia, C., et al., Macromol. Rapid Commun. 17, 333-338 (1996)) which limits the usage since the lower the [rrrr] pentad content, the lower the melting point. For example, a container made from polypropylene with [rrrr] pentad content of 0.63 will melt on contact with boiling water and thus is unuseful for containers for hot liquids. We turn now to the other type of syndiotactic polypropylene. It is referred to as being made by a site-control mechanism and as containing defects of the rmmr type. This type of polypropylene is described in European Patent Application Publication 0351391 A2 (published Jan. 17, 1990). Highly syndiotactic polypropylene ([rrrr]=0.97) has been made by a site-control mechanism. See Ewen, J. A., et al., J. Am. Chem. Soc., 110, 6255-6256 (1988), Herzog, T. A., et al., J. Am. Chem. Soc. 118, 11988-11989 (1996), and Veghini, D., et al., J. Am. Chem. Soc. 121, 564-573 (1999). This kind of syndiotactic polypropylene has not yet been commercialized apparently because of processing and/or economic factors.
SUMMARY OF THE INVENTION
It has been discovered herein that highly syndiospecific polypropylene can be made by a chain-control mechanism by utilizing certain bis(salicylaldiminato)titanium complex compounds as catalysts as well as block copolymers containing block(s) of the syndiotactic polypropylene and block(s) of poly(ethylene-co-propylene) and/or poly(alpha-olefin-co-propylene) and that living polymerization can be obtained and that certain of the catalysts are useful in the production of olefin terminated polymers and oligomers from propylene.
The invention herein in one embodiment, denoted the first embodiment, is directed to a bis(salicylaldiminato)titanium complex having the structure:
where R is selected from the group consisting of halogen atoms, C
1
-C
10
branched or straight chain alkyl groups, C
1
-C
6
branched or straight chain alkoxide groups, and C
1
-C
6
branched or straight chain amido groups, R
1
is phenyl substituted with C
1
-C
6
branched or straight chain alkyl group or electron withdrawing atom or group at the 2-position and optionally substituted with C
1
-C
6
branched or straight chain alkyl groups or electron withdrawinig atom or group at one or more of the 3-, 4-, 5- and 6-positions, or is C
1
-C
10
branched, cyclic or straight chain alkyl group, and R
2
and R
3
are the same or different and are selected from the group consisting of C
4
-C
6
tertiary alkyl groups; or cationic form thereof The complexes are useful as catalysts for polymerization of olefins and are especially useful for polymerization of propylene.
The invention herein in another embodiment, denoted the second embodiment, is directed to syndiotactic polypropylene having M
w
ranging from 10,000 to 500,000 and defects of the type rmr and [rrrr] pentad content greater than 0.70. The syndiotactic polypropylene is useful, for example, for packaging and container functionality.
The invention herein in another embodiment, denoted the third embodiment, is directed to syndiotactic poly(C
4
-C
6
-alpha olefins) having a M
w
ranging from 10,000 to 500,000 and M
w
/M
n
ranging from 1.0 to 2.0. These syndiotactic polyolefins are useful for films and sheets because of their flexibility and transparency.
The invention herein in another embodiment, denoted the fourth embodiment, is directed to a method of preparing syndiotactic polypropylene having M
w
ranging from 10,000 to 500,000 and defects of the type rmr and [rrrr] pentad content greater than 0.50 comprising polymerizing propylene dissolved in an aprotic solvent in the presence of a catalytically effective amount of a complex having the structure:
where R is selected from the group consisting of halogen atoms, C
1
-C
10
branched or straight chain alkyl groups, C
1
-C
6
branched or straight chain alkoxide groups, and C
1
-C
6
branched or straight chain amido groups, R
1
is phenyl optionally substituted with one to five C
1
-C
6
branched or straight chain alkyl groups or one to five electron withdrawing atoms or groups, or is C
1
-C
10
branched, cyclic or straight chain alkyl group, and R
2
and R
3
are the same or different and are selected from the group consisting of H or C
1
-C
6
branched or straight chain alkyl group, and an activating effective amount of compound that converts titanium of the complex to cationic form. The syndiotactic polypropylene product has packaging and container functionality.
The invention herein in still another embodiment, denoted the fifth embodiment, is directed to olefin terminated polymers and oligomers of propylene having the structure:
where n ranges from 1 to 750. These compounds are useful, for example, to add as so-called ‘macromonomers’ to other polymerizations and can be incorporated about as well as hexene.
The invention in another embodiment denoted the sixth embodiment is directed to a method of preparing polymers and oligomers of propylene having the structure (II) where n ranges from 1 to 750 comprising polymerizing propylene in an aprotic solvent in the presence of a catalytically effective amount of complex having the structure (I) where R is selected from the group consisting of halogen atoms, C
1
-C
10
branched or straight chain alkyl groups, C
1
-C
6
branched or straight chain alkoxide groups, and C
1
-C
6
branched or straight chain amido groups, R
1
is phenyl optionally substituted at one or more of the 3-, 4-, and 5-positions but not at the 2- and 6-positions, the optional substitution at one or more of the 3-, 4- and 5-positions being with C
1
-C
6
branched or straight chain alkyl group or electron withdrawing atom or group, and R
2
and R
3
are the same or different and are selected from the group consisting of H and C
1
-C
6
branched or straight chain alkyl groups and an activating effective amount of compound that converts titanium of the complex to cationic form, and quenching the reaction when olefin-terminated polymer or oligomer of desired number of monomer units is formed.
The invention herein in still another embodiment, denoted the seventh embodiment, is directed to block copolymer having M
w
ranging from 10,000 to 500,000 comprising at least one block of syndiotactic polypropylene and at least one block of poly(ethylene/pro
Coates Geoffrey W.
Hustad Phillip D.
Tian Jun
Cornell Research Foundation Inc.
Rabago R.
Wu David W.
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