Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-12-19
2004-02-10
Choi, Ling-Siu (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S125300, C526S128000, C526S348000, C526S124300, C526S901000, C526S902000, C502S103000, C502S118000, C502S158000
Reexamination Certificate
active
06689849
ABSTRACT:
TECHNICAL FIELD
The present invention relates to catalysts for bulk polymerization and vapor-phase polymerization of an &agr;-olefin compound, methods for polymerizing an &agr;-olefin compound by using the catalysts, and olefin polymers obtained by using the catalysts.
To say in detail, the present invention relates to catalysts for bulk polymerization and vapor-phase polymerization, each of the catalysts has high polymerization activity during bulk or vapor-phase polymerization of an &agr;-olefin compound as a raw material monomer, and each of the catalysts provides an olefin polymer having excellent properties in melt flow rate and stereoregularity by adding a small amount of hydrogen; methods for polymerizing an &agr;-olefin compound by using the catalysts; and olefin polymers obtained by using the catalysts.
BACKGROUND ART
Up to now, as a catalyst for polymerizing an &agr;-olefin compound and fabricating an olefin polymer, Ziegler type catalyst is well known. Examples of these catalysts are disclosed in Japanese publication of unexamined patent application No. Hei-2-163104 and Japanese publication of unexamined international patent application No. Hei-8-509263.
To give an actual example, the catalyst, disclosed in Japanese publication of unexamined patent application No. Hei-2-163104, comprises the following ingredients (A1) to (C1).
(A1) a solid catalyst ingredient including trivalent titanium, the ingredient is obtained by the following steps;
reducing halogenated titanium by an organomagnesium compound under a presence of an organosilicon compound having a Si—O bonding to thereby form a solid product,
treating the solid product with an ester compound, and then
treating the solid compound with a mixture of an ether compound, titanium tetrachloride, and an ester compound;
(B1) an organoaluminum compound; and
(C1) dialkyldialkoxysilane and the like.
The catalyst, disclosed in Japanese publication of unexamined international patent application No. Hei-8-509263, comprises the following ingredients (A2) to (C2).
(A2) a solid compound including magnesium atoms, halogen atoms, and transition metal atoms such as titanium;
(B2) an organoaluminum derivative; and
(C2) dialkyldialkoxysilane and the like.
By the way, in general, when an &agr;-olefin compound is bulk polymerized or vapor-phase polymerized, a melt flow rate (MFR) is heighten by using a chain transfer agent, such as hydrogen, and thereby lower a molecular weight of an olefin polymer.
However, the catalysts, disclosed in Japanese publication of unexamined patent application No. Hei-2-163104 and Japanese publication of unexamined international patent application No. Hei-8-509263, have the following problems.
(1) Although an olefin polymer having an excellent stereoregularity is obtained by bulk polymerization or vapor-phase polymerization, a melt flow rate against the hydrogen using amount is small. As a result, the catalyst is unfavorable for fabricating an olefin polymer having a high melt flow rate.
To give an actual example, referring to
FIG. 1
, when hydrogen partial pressure during bulk polymerization is 0.25 MPa (gauge), MFR (in accordance with JIS-K7210) of the obtained olefin polymer is about 1.2 g/10 min. Whereas, when hydrogen partial pressure is increased to 1 MPa (gauge), MFR of the obtained olefin polymer is about 14 g/10 min
Further, referring to
FIG. 2
, when hydrogen partial pressure during vapor-phase polymerization is 0.01 MPa (gauge), MFR (in accordance with JIS-K7210) of the obtained olefin polymer is about 0.03 g/10 min. Whereas, when hydrogen partial pressure is increased to 0.09 MPa (gauge), MFR of the obtained olefin polymer is about 2.5 g/10 min
That is to say, with respect to the conventional catalyst, a large quantity of hydrogen should be used in order to lower the melt flow rate of the olefin polymer.
(2) When an olefin polymer having a high melt flow rate is fabricated by bulk polymerization or vapor-phase polymerization by using the above catalyst, the stereoregularity of the obtained olefin polymer is deteriorated.
That is to say, since the stereoregularity and the melt flow rate of the olefin polymer are conflict properties in general, in order to fabricate an olefin polymer having a high melt flow rate, the stereoregularity is deteriorated. As a result, heat resistance and creep resistance of the olefin polymer are deteriorated.
(3) When an olefin polymer having a high melt flow rate is fabricated by bulk polymerization or vapor-phase polymerization by using the above catalyst, much more hydrogen is needed. As a result, in view of safety, high pressure resistance of the manufacturing equipment should be needed.
(4) Further, with respect to the catalyst, when a large quantity of hydrogen is used, hydrogen partial pressure during bulk polymerization or vapor-phase polymerization is heightened and thereby partial pressure of the monomer is lowered. As a result, productivity of the olefin polymer is deteriorated.
Under the circumstances, catalysts, having high polymerization activity during bulk polymerization or vapor-phase polymerization, and providing an olefin polymer having desired molecular weight and melt flow rate by adding a small amount of hydrogen, is needed.
Therefore, the present invention is acquired in view of the above problems. The object in accordance with the present invention is to provide a catalyst for bulk polymerization or vapor-phase polymerization, the catalyst having high polymerization activity during bulk polymerization or vapor-phase polymerization and providing an olefin polymer having excellent properties in melt flow rate and stereoregularity by adding a small amount of hydrogen by combining a specific solid catalyst, an organoaluminum compound and a specific organosilicon compound.
In addition, the object in accordance with the present invention is to provide methods for bulk polymerization and vapor-phase polymerization, the methods effectively provide an olefin polymer having excellent properties in melt flow rate and stereoregularity by using the catalysts for bulk polymerization and vapor-phase polymerization.
In addition, the object in accordance with the present invention is to provide an olefin polymer, having excellent properties in melt flow rate and stereoregularity, obtained by using the catalysts for bulk polymerization and vapor-phase polymerization.
DISCLOSURE OF THE INVENTION
[1] One embodiment in accordance with the present invention (First invention) is a catalyst for bulk polymerization of an &agr;-olefin compound under a presence of hydrogen, the catalyst is made by contacting the following ingredients (A) to (C). Further, the other embodiment in accordance with the present invention (Second invention) is a catalyst for vapor-phase polymerization of an &agr;-olefin compound under a presence of hydrogen, the catalyst is made by contacting the following ingredients (A) to (C).
(A) a solid catalyst ingredient, comprising:
(a) a magnesium compound,
(b) titanium tetrachloride, and
(c) dialkyl phthalate (Each of the alkyl groups denotes a straight-chain or branched-chain hydrocarbon group having a carbon number of 3 to 20.);
(B) an organoaluminum compound; and
(C) an organosilicon compound, which is expressed by the following general chemical formula (1).
(R
1
)(R
2
CH
2
)Si(OR
3
)(OR
4
) (1)
[In the general chemical formula (1), R
1
denotes a alicyclic hydrocarbon group having a carbon number of 3 to 12, R
2
denotes a branched-chain hydrocarbon group having a carbon number of 3 to 20, and each of R
3
and R
4
denotes a hydrocarbon group having a carbon number of 1 to 20, respectively.]
As an ingredient (C), by using the specific alicyclicalkyldialkoxysilane as an outside donor, polymerization activity may be improved. As a result, a catalyst for bulk polymerization or vapor-phase polymerization, which provides an olefin polymer having excellent properties in melt flow rate and stereoregularity by adding a small amount of hydrogen, may be provided.
[2] In accordance with the first invention or the s
Funabashi Hideo
Kanamaru Masami
Ota Tsuyoshi
Sadashima Takanori
Choi Ling-Siu
Idemitsu Petrochemical Co. Ltd.
Parkhurst & Wendel L.L.P.
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