AU2005202759A1 - Butene copolymer, resin composition comprising the copolymer and moldings of the composition, and solid titanium catalyst for producing the copolymer and method for preparing the catalyst - Google Patents

Butene copolymer, resin composition comprising the copolymer and moldings of the composition, and solid titanium catalyst for producing the copolymer and method for preparing the catalyst Download PDF

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AU2005202759A1
AU2005202759A1 AU2005202759A AU2005202759A AU2005202759A1 AU 2005202759 A1 AU2005202759 A1 AU 2005202759A1 AU 2005202759 A AU2005202759 A AU 2005202759A AU 2005202759 A AU2005202759 A AU 2005202759A AU 2005202759 A1 AU2005202759 A1 AU 2005202759A1
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butene
olefin
copolymer
compound
butene copolymer
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AU2005202759A
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Shin Tokui
Toshiyuki Tsutsui
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority claimed from AU67915/01A external-priority patent/AU782607C/en
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Priority to AU2005202759A priority Critical patent/AU2005202759A1/en
Publication of AU2005202759A1 publication Critical patent/AU2005202759A1/en
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Description

1
AUSTRALIA
PATENTS ACT 1990 DIVISIONAL APPLICATION NAME OF APPLICANT(S): Mitsui Chemicals, Inc.
ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Nicholson Street Melbourne, 3000.
INVENTION TITLE: "Butene copolymer, resin composition comprising the copolymer and moldings of the composition, and solid titanium catalyst for producing the copolymer and method for preparing the catalyst" The following statement is a full description of this invention, including the best method of performing it known to us:
DESCRIPTION
BUTENE COPOLYMER, RESIN COMPOSITION THEREOF, MOLDED ITEM THEREFROM, SOLID TITANIUM CATALYST FOR PRODUCTION THEREOF AND PROCESS This application is a divisional of Australian Patent Application No. 67915/01, the entire contents of which are incorporated herein by reference.
Field of the Invention The present invention relates to a butene copolymer, a resincompositioncomprising thebutenecopolymer, amolded item from the butene copolymer or resin compositionthereof, a solid titanium catalyst for producing the butene copolymer and a process for producing the same. More particularly, the present invention relates to a butene copolymer which is excellent in heat resistance, thermal creep properties and handling easiness after molding and which.can provide a molded item having appropriate rigidity and excellent low-temperature properties, and relates to a resin composition comprising the butene copolymer, a molded item from the butene copolymer or resin composition thereof., a solid titanium catalyst for producing the butene copolymer and a process for producing the same.
Background of the Invention A galvanized steel pipe, a copper pipe, a lead pipe and other metal pipes are commonly used as a water supply or hot water supply piping element. However, a steel pipe has a drawback in that it rusts to cause occurrence of a red water or black water. A copper pipe has a drawback in that it suffers electrolytic corrosion to thereby cause the pipe to have pin holes and further cause occurrence of a bluewater. Moreover, such a watersupplyorhotwatersupply piping element has such drawbacks that the weight reduction thereof is difficult and it is not easyto achieve an increase of pipe diameter. Therefore, a novel piping material has been demanded. Already, in some areas, use is made of synthetic resin pipes constituted of polyvinyl chloride, polyethylene, crosslinked polyethylene, poly-l-butene, etc., which are free fromrustingand electrolytic corrosion leading to pin holes.
However, the polyvinyl chloride lacks a flexibility as a resin and raises sanitary and environmental problems.
The polyethylene raises such a problem that the pressure resistance and long-term durability thereof are poor.
The poly-l-butene is excellent in pressure resistance strength, internal pressure creep durability at high temperature (40 to 120 0 C) high/low temperature properties and abrasion/wear resistance and is also excellent in flexibility, so that it is a resin suitable for use in water supply/hot water supply pipes. However, the poly-l-butene is slightly unsatisfactory in a balance between flexibility and heat resistance and a balance between rigidity and low-temperature properties. Further, upon melt molding of the poly-l-butene, the molded item is characterized in that the properties thereof are slowly changed anddays or ten-odd days are needed before the molded item exhibits stable properties, therebyraising a problem ofdifficulthandling.
Therefore, there has been a demand for the development of a resin ofhigherlevelperformancewhich, while retaining appropriate rigidity and flexibility, is excellent in a balance of rigidity, etc. and is improved with respect to the handling easiness of molded item.
The inventors presented in a prior application (Japanese Patent Laid-open Publication No. 9(1997)-302038) that a butene-propylene copolymer whose propylene content, crystalmeltingpoint, tensilemodulus, intrinsic viscosity and n-decane soluble content are controlled so as to fall within specified ranges, or the molding of a resin composition comprising the butene-propylene copolymer is excellent inpressu resistance, heat resistance, rigidity, low-temperature properties, molded item handling easiness and dust adherence causing a lowering of handling property, so that the butene-propylene copolymer can be a substitute for the poly-l-butene.
The butene-propylene copolymer, although various improvements can be certainly recognized, has such a problem that the heat resistance, rigidity and thermal creep properties thereof are still not satisfactory.
Apart from the above, a catalyst comprising a titanium compound supported on a magnesium halide being in the active state is known as a catalyst for use in the production of an olefin polymer such as an ethylene homopolymer, an a-olefin homopolymer or an ethylene/a-olefin copolymer.
For example, a catalyst comprising a solid titanium catalyst component, composed of magnesium, titanium, a halogen and an electron donor, and an organometallic compound catalyst component is known.
Various proposals have been presented with respect to the solid titanium catalystcomponent comprising magnesum, titanium, a halogen and an electron donor. It is also known that a highly stereospecific polymer of an a-olefin having 3 or more carbon atoms can be produced in high yield with the use of the solid titanium catalyst component.
For the production of this solid titanium catalyst component, there is known, for example, a process wherein a hydrocarbon solution of halogenous magnesium compound and a liquid titanium compound are brought into contact with each other to thereby form a solid product. Further, there is known a process wherein a solid product is formed from a hydrocarbon solution containing a magnesium halide compound and a titanium compound in the presence of at least one electron donor selected from the group consisting of a polycarboxylic acid, a monocarboxylic acid ester, a polycarboxylic acid ester, a polyhydroxy compound ester, an acid anhydride, a ketone, a fatty acid ether, a fatty acidcarbonate, an alcoholhavinganalkoxygroup, analcohol having an aryloxy group, an organosilicon compound having Si-O-C bond and an organophosphorus compound having
P-O-C
bond.
In particular, it is known that an a-olefin (co)polymer of uniform particle diameter and low fine powder content can be obtained when polymerization is performed in the presence of a solid titanium catalyst produced with the use of a carboxylic acid or a derivative thereof (for example, phthalic anhydride or the like; hereinafter may be referred to simply as "carboxylic acid derivative") as the electron donor.
Further, therehasbeenproposed a process forproducing an a-olefin polymer of narrower particle size distribution, less fine powder content and greater bulk density in the presence of a solid titanium catalyst comprising in a specific composition of magnesium, titanium, a halogen, a compound having at least two ether bonds between which a plurality of atoms are present (hereinafter may be referred to simply as "polyether"), a hydrocarbon and an electron donor other than the polyether (Japanese Patent Laid-open Publication No. 6(1994)-336503).
It is true that a propylene polymer of highly excellent properties can be obtainedwith the use of this solid titanium catalyst. However, the inventors have found that the polymerization of 1-butene in the presence of the solid titanium catalyst raises such problems that 1-butene is isomerized into 2-butene to thereby invite a drop of polymerization activity, and that a carboxylic acid derivative inhibits the action of a stabilizer in a-olefin polymer to thereby cause a long-term strength to be unsatisfactory.
Disclosure of the Invention Accordingly, the first object of the present invention is to provide a butene copolymer which enables enhancing the rigidity, low-temperature property and thermal creep property of a molded item and to provide a resin composition comprising the butene copolymer (A) The second object of the present invention is to provide a molding of the butene copolymer and a molding of the resincomposition comprising thebutenecopolymer which moldings exhibit excellent rigidity, low-temperature property and thermal creep property.
The third object of the present invention is to provide a solid titanium catalyst which enables producing a polymer or copolymer of a-olefin having 4 or more carbon atoms, the polymer or copolymer characterized by uniform particle diameter, less fine powder content, high bulk density and substantially not containing any carboxylic acid, and toprovide a process for producing the polymer or copolymer of a-olefin.
Therefore, according to the first aspect of the present invention, there is provided a butene copolymer
(A)
comprising 99.9 to 80 mol% of copolymer units derived from -butene and 0.1to20mol% ofcopolymerunits derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded), this butene copolymer having: (la) a tensile modulus E (measured at 23 0 C) of 345 MPa or greater and/or (Ib) a tensile modulus E (measured at 95 0 C) of 133 MPa or greater, and a ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of 2 to an intrinsic viscosity (measured in decalin as a solvent at 135 0 C) of 1 to 6 dl/g, and a melting point Tm (measured by a differential scanning calorimeter) of 150 0 C or below.
According to the second aspect of the present invention, there is provided the butene copolymer as defined in the first aspect of the present invention, wherein the tensile modulus E (measured at 23'C) satisfies the relationship: E (MPa) 370 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)) wherein the content of a-olefin having 2 to 10 carbon atoms (provided that l-butene is excluded) is molar percentage based on the butene copolymer According to the third aspect of the present invention, there is provided the butene copolymer as defined in the first or second aspect of the present invention, which exhibits a 1/2 crystal transition time (measured by X-ray diffractometry) of 40 hr or less.
According to the fourth aspect of the present invention, there is provided the butene copolymer as defined in any of the first to third aspects of the present invention, which exhibits: B value determined by 13C-NMR of 0.92 to 1.1, this B value calculated by the formula: B value POB/(2Po-PB) wherein POB represents the ratio of the number of butene-a-olefin chains to the total number of chains, PB represents the molar fraction of butene component, and PO represents the molar fraction of a-olefin component, and an isotactic pentad fraction determined by 13 C-NMR of 91% or greater.
According to the fifth aspect of the present invention, there is provided the butene copolymer as defined in any of the first to fourth aspects of the present invention, whereinthe ratio (Mw/Mn) ofweight-averagemolecularweight (Mw) to number-average molecular weight (Mn) is in the range of 2 to 7.9.
According to the sixth aspect of the present invention, there is provided the butene copolymer as defined in any of the first to fifth aspects of the present invention, wherein the copolymer units derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) are propylene units.
According to the seventh aspect of the present invention, there is provided the butene copolymer as defined in any of the first to sixth aspects of the present invention, which exhibits only one endothermic peak (melting point Tm) in a measurement by means of a differential scanning calorimeter.
According to the eighth aspect of the present invention, there is provided the butene copolymer as defined in any of the first to seventh aspects of the present invention, produced with the use of a catalyst system comprising: a solid titanium catalyst component containing titanium, magnesium, a halogen and a compound having at least two ether bonds represented by the formula:
R
22
R
2
R
24
R
2 C -R 26
R
23 R' R" R 2 wherein each of R 1 to R 2 6 represents a substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, ahalogen, nitrogen, sulfur, phosphorus, boron and silicon, provided that any
R
1 to R 2 6 substituents may form a ring other than benzene ring and that an atom other than carbon may be contained in a main chain of the compound having at least two ether bonds, and wherein n is an integer satisfying the relationship 2 n 10; and an organometallic compound catalyst component (d) containing a metal of Groups I to III of the periodic table.
According to the ninth aspect of the present invention, there is provided a butene copolymer resin composition comprising a butene copolymer comprising 99.9 to 80 mol% of copolymer units derived from l-butene and 0.1 to mol% of copolymer units derived from an a-olefin.having 2 to 10 carbon atoms (provided that 1-butene is excluded), this butene copolymer resin composition having: (la) a tensile modulus E (measured at 23°C) of 360 MPa or greater and/or (Ib) a tensile modulus E (measured at 95 0 C) of 138 MPa or greater, and a ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of 2 to an intrinsic viscosity [ri] (measured in decalin as a solvent at 135"C) of 1 to 6 dl/g, and a melting point Tm (measured by a differential scanning calorimeter) of 110 to 150 0
C.
According to the tenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in the ninth aspect of the present invention, wherein the tensile modulus E (measured at 23 0 C) satisfies the relationship: E (MPa) 400 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that l-butene is excluded) wherein the content of Q-olefin having 2 to 10 carbon atoms (provided that l-butene is excluded) is molar percentage based on the whole butene copolymer resin composition.
According to the eleventh aspect of the present invention, there is provided the butene copolymer resin composition as defined in the ninth or tenth aspect of the present invention, which exhibits a 1/2 crystal transition time (measured by X-ray diffractometry) of 40 hr or less.
According to the twelfth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to eleventh aspects of the present invention, which further comprises a nucleating agent.
According to the thirteenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in the twelfth aspect of the present invention, wherein thenucleating agentis anamidecompound.
According to the fourteenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to thirteenth aspects of the present invention, which exhibits: B value determined by 13C-NMR of 0.90 to 1.08, this B value calculated by the formula: B value POB/(2PO-P
B
wherein POB represents the ratio of the number of butene-a-olefin chains to the total number of chains, PB represents the molar fraction of butene component, and PO represents the molar fraction of a-olefin component, and an isotactic pentad fraction determined by 13C-NMR of 91.5% or greater.
According to the fifteenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to fourteenth aspects of the present invention, wherein the ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) is in therange of 2 to 7.9.
According to the sixteenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to fifteenth aspects ofthepresentinvention, whereinthecopolymer units derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) for constituting the butene copolymer are propylene units.
According to the seventeenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to sixteenth aspects of the present invention, which further comprises poly-1-butene According to the eighteenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to seventeenth aspects of the present invention, which comprises 40 to by weight of butene copolymer and 60 to 10% by weight of poly-l-butene According to the nineteenth aspect of the present invention, there is provided the butene copolymer resin composition as defined in any of the ninth to eighteenth aspects of the present invention, which comprises butene copolymer or butene copolymer together with poly-l-butene these butene copolymer and poly-l-butene produced with the use of a catalyst system comprising: a solid titanium catalyst component containing titanium, magnesium, a halogen and a compound having at least two ether bonds represented by the formula:
R
22 R
R
2 4
R
2 1
-O-C-R
26 I I I
R
2 3 R R"
R
2 wherein each of R 1 to R 26 represents a substituent having at least one element selected from the group consistingof carbon, hydrogen, oxygen, a halogen, nitrogen, sulfur, phosphorus, boron and silicon, provided that any
R
1 to R 2 6 substituents may form a ring other than benzene ring and that an atom other than carbon may be contained in a main chain of the compound having at least two ether bonds, and wherein n is an integer satisfying the relationship 2 s n s 10; and an organometallic compound catalyst component (d) containing a metal of Groups I to III of the periodic table.
According to the twentieth aspect of the present invention, there is provided a molded item comprising the butene copolymer as defined in any of the first to eighth aspects of the present invention or the butene copolymer resin composition as defined in any of the ninth to nineteenth aspects of the present invention.
According to the twenty-first aspect of the present invention, there is provided the molded item as defined in the twentieth aspect of the present invention, which is in the form of a pipe.
According to the twenty-second aspect of the present invention, there is provided the molded item as defined in the twenty-first aspect of the present invention, which exhibits a breaking time of 20 thousand hours or more in a hydrostatic test of pipe (measured at 950C at a hoop stress of 6 MPa) According to the twenty-third aspect of the present invention, there is provided the molded item as defined in the twentieth aspect of the present invention, which is in the form of a pipe joint.
According to the twenty-fourth aspect of the present invention, there is provided a solid titanium catalyst for polymerizing an c-olefin having 4 or more carbon atoms, comprising: to 35% by weight of magnesium 0.3 to 10% by weight of titanium to 75% by weight of a halogen to 30% by weight of a compound having at least two ether bonds between which a plurality of atoms are interposed (d 0.05 to 20% by weight of a hydrocarbon and 0.05 to 7% by weight of a solubilizing agent According to the twenty-fifth aspect of the present invention, there is provided a solid titanium catalyst for polymerizing an a-olefin having 4 or more carbon atoms, produced by bringing a halogenous magnesium compound a solubilizing agent capable ofdissolvingthehalogenous magnesium compound and a first compound having at least two ether bonds between which a plurality of atoms are interposed into mutual contact in a solvent to thereby obtain a solution (II) and contacting a liquid titanium compound with the solution
(II)
According to the twenty-sixth aspect of the present invention, there is provided the solid titanium catalyst for polymerizing an a-olefin having 4 or more carbon atoms as defined in the twenty-fourth or twenty-fifth aspect of the present invention, which substantially does not contain any carboxylic acid derivative.
The carboxylic acid derivative for use in the present invention can be, for example, a carboxylic acid ester or acarboxylicacidanhydride. Theexpression"substantially does not contain any carboxylic acidderivative" used herein means that the content of carboxylic acid derivative in the above solid titanium catalyst for a-olefin polymerization is not greater than 5% by weight. The content of carboxylic acid derivative is preferably 1% by weight or less, still preferably 500 ppm or less, and especially preferably 100 ppm or less.
According to the twenty-seventh aspect of the present invention, there is provided a process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms, comprising polymerizing or copolymerizing an a-olefin having 4 or more carbon atoms in the presence of asolidtitaniumcatalyst andanorganometalliccompound containing a metal selected from among metals of Groups I to ITI of the periodic table optionally together with an electron donor this solid titanium catalyst comprising: to 35% by weight of magnesium 0.3 to 10% by weight of titanium 30 to 75% by weight of a halogen to 30% by weight of a compound having at least two ether bonds between which a plurality of atoms are interposed (d 0.05 to 20% by weight of a hydrocarbon (e'),.and 0.05 to 7% by weight of a solubilizing agent According to the twenty-eighth aspect of the present invention, there is provided a process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms, comprising polymerizing or copolymerizing an a-olefin having 4 or more carbon atoms in the presence of asolidtitaniumcatalyst andanorganometalliccompound containing a metal selected from among metals of Groups I to III of the periodic table optionally together with an electron donor this solid titanium catalyst produced by bringing a halogenous magnesium compound a solubilizing agent capable of dissolving the halogenous magnesium compound and a first compound having at least two ether bonds between which a plurality of atoms are interposed into mutual contact in a solvent to thereby obtain a solution (II) and contacting a liquid titanium compound with the solution
(II).
According to the twenty-nineth aspect of the present invention, there is provided a process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms, comprising polymerizing or copolymerizing an a-olefin having 4 or more carbon atoms in the presence of the solid titanium catalyst as defined in the twenty-seventh or twenty-eighth aspect of the present invention wherein substantially no carboxylic acid derivative is contained and an organometallic compound containing a metal selected from among metals of Groups
I
to III of the periodic table optionally together with an electron donor According to the thirtieth aspect of the present invention, there is provided the process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms as defined in any of the twenty-seventh to twenty-nineth aspects of the present invention, wherein 1-butene or 1-butene together with another a-olefin having 4 or more carbon atoms is polymerized or copolymerized.
According to the thirty-first aspect of the present invention, there is provided a polymer or copolymer of an a-olefin having 4 or more carbon atoms, which has an a-olefin content of 50 mol% or greater and is obtained by the polymerization or copolymerization of an a-olefin having 4 ormore carbon atoms as defined in any of thetwenty-seventh to thirtieth aspects of the present invention.
Preferred Embodiments of the Invention Thebutene copolymer, resin composition comprising the same, molded item therefrom, solid titanium catalyst for producing the butene copolymer and process for producing the butene copolymer according to the present invention will be described in detail below.
Butene copolymer The butene copolymer of the present invention is a copolymer of 1-butene and an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded). The molar constituent ratio of 1-butene to a-olefin having 2 to carbon atoms (provided that 1-butene is excluded) is in the range of 99.9/0.1 to 80/20, preferably 99/1 to 90/10, and still preferably 99/1 to 92/8. It is especially preferred that the butene copolymer be a copolymer of 1-butene and propylene.
The butene copolymer of the present invention may be a mixture of a plurality of copolymers of 1-butene and an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) having different a-olefin contents.
For example, the butene copolymer may be a mixture of two copolymers of 1-butene and an a-olefin having 2 to carbon atoms (provided that 1-butene is excluded), the one having a molar constituent ratio of l-butene/a-olefin ranging from 99.9/0.1 to 80/20 while the other having a molar constituent ratio of l-butene/a-olefin ranging from 80/20 to 99.9/0.1. Moreover, the butene copolymer may be a terpolymer tetrapolymer further containing a third a-olefin in a small amount not detrimental to the properties of the butene copolymer For example, the butene copolymer may be a terpolymer tetrapolymer consisting of a 1-butene/propylene copolymer containing a small amount of 4-methyl-l-pentene, ethylene, hexene, pentene, heptene or octene.
The butene copolymer of the present invention has a tensile modulus E measured at 230C of 345 MPa or greater, preferably 345 to 480 MPa, and still preferably 380 to 450 MPa.
Further, the butene copolymer of the present invention has a tensile modulus E measured at 950C of 133 MPa or greater, preferably 135 to 245 MPa.
The butene copolymer of the present invention must exhibit either or both of these tensile moduli.
The resin composition comprising butene copolymer (A) according to the present invention has a tensile modulus E measured at 230C of 360 MPa or greater, preferably 380 to 550 MPa, and still preferably 400 to 550 MPa.
Further, the resin composition comprising butene copolymer according to the present invention has a tensile modulus E measured at 95°C of 138 MPa or greater, preferably 150 to 245 MPa.
The resin composition comprising butene copolymer (A) according to the present invention must exhibit either or both of these tensile moduli.
The tensile modulus E (measured at 23 0 C) of the butene copolymer of the present invention preferably satisfies the relationship: E (MPa) 370 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)), still preferably E (MPa) 390 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)) In the formulae, thecontent of a-olefinhaving 2 to 10 carbon atoms (provided that 1-butene is excluded) is molar percentage based on the butene copolymer The tensile modulus E (measured at 23°C) of the resin composition comprising butene copolymer according to the present invention preferably satisfies the relationship: E (MPa) 400 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)), still preferably E (MPa) 420 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)).
In the formulae, the content of -olefin having 2 to 10 carbon atoms (provided that l-butene is excluded) is molar percentage based on the whole resin composition.
These inequalities can be obtained by plotting numerical data of Examples and Comparative Examples on a graph wherein the axis of abscissas indicates the content of a-olefin having 2 to 10 carbon atoms (provided that l-butene is excluded) while the axis of ordinates indicates the tensile modulus
E.
When the tensile modulus E of the butene copolymer
(A)
or the resin composition comprising the butene copolymer falls within the above ranges, the pipe obtained by molding thereof has such an appropriate hardness that, upon laying of the pipe, the support for preventing the deformation by the self weight thereof is not excessive.
Further, when the tensile modulus E satisfies the above inequalities with respect to the relationship with the content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded), forexample, thepipeflexibility at the time of laying and the pipe strength after the laying are reconciled to thereby ensure high practical usefulness of the pipe.
With respect to the butene copolymer of the present invention, the ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) is in the range of 2 to 30, preferably 2 to 20, still preferably 2 to 7.9, yet still preferably 2 to 6, and optimally 2 to When special importance is placed on the moldability, it is preferred that the ratio Mw/Mn be in the range of 3 to 30, especially 3 to 20, more especially 3 to 7.9, yet more especially 3 to 6, and most especially 3 to 5. With respect to the resin composition comprising the butene copolymer the ratio Mw/Mn is in the range of 2 to preferably 2 to 20, still preferably 2 to 7.9, yet still preferably 2 to 6, and optimally 2 to 5. When special importance is placed on the moldability, it is preferred that the ratio Mw/Mn be in the range of 3 to 30, especially 3 to 20, more especially 3 to 7.9, yet more especially 3 to 6, and most especially 3 to When the ratio Mw/Mn falls within these ranges, the pipe obtained by molding thereof is excellent in processability, particularly pipe extrudability.
With respect to the butene copolymer or resin composition comprising butene copolymer according to the present invention, the intrinsic viscosity [nl measured in decalin at 135 0 C is in the range of 1 to 6 dl/g, preferably 2 to 4 dl/g. When the intrinsic viscosity falls within these ranges, the pipe obtained by molding thereof has satisfactory strength and is excellent in pipe extrudability.
The crystal melting points Tm, measured by a differential scanning calorimeter, of the butene copolymer and resin composition comprising butene copolymer
(A)
according to the present invention are 150 0 C or below and from 110 to 150°C, respectively. When the crystal melting points Tm fall within these ranges, an excellent balance of processability and heat resistance can be realized with respect to the molding of a pipe therefrom. Herein, the melting point Tm refers to the melting point Tml measured in the following manner.
Specifically, the butene copolymer or resin composition comprising the butene copolymer was sheeted by subjecting the same to melt compression at 200 0
C,
maintaining thecompression for performed while cooling to room temperature at a cooling rate of about 10 0 C/min. The obtained sheet was allowed to stand still at room temperature for one week and applied to a differential scanning calorimeter. The melting peak temperature of I-type crystal exhibited at heating to 2000C at a rate of 10 0 C/min was measured and designated as Tm 1 Because the sample having been subjected to measurement of Tm
I
exhibits a different peak upon further measurement performed in the same manner, it is absolutely necessary to prepare a new sample in the measurement of melting point Tm
I
For example, the melting point Tm 2 appearing when, after the measurement of melting point Tml, the sample has been allowed to stand still for 10 min, cooled from 200°C to 20°C at a rate of 10°C/min, allowed to stand still for 5 min and heated to 200°C at a rate of is different from the melting point Tm 1 and exhibits the melting peak of II-type crystal which lies on the low temperature side as compared with the melting point Tml.
With respect to the butene copolymer or resin composition comprising butene copolymer according to the present invention, it is preferred that the endothermic peak (melting point Tm) of butene copolymer or resin composition as measured by a differential scanning calorimeter be substantially single.
Herein, the expression "endothermic peak is substantially single" means that the ratio of the area of main endothermic peak to the sum of endothermic peak areas around the melting point is 80% or greater. This ratio of main endothermic peak area is preferably 90% or greater, still preferably 95% or greater, and optimally 98% or greater.
With respect to the butene copolymer or resin composition comprising butene copolymer according to the present invention, it is preferred that the 1/2 crystal transition time (measured by X-ray diffractometry) be hr or less, especially 30 hr or less.
With respect to the butene copolymer of the present invention, it is preferred that the B value, as an index of random copolymerization, determined by NMR analysis be in the range of 0.92 to 1.1, especially 0.93 to 1.1, and that the isotactic pentad fraction determined by 13
C-NMR
be 91% or greater, especially 91 to 100%, more especially 92 to 100% and most especially 93 to 100%.
Withrespect to the resin composition comprising butene copolymer according to the present invention, it is preferred that the above B value be in the range of 0.90 to 1.08, especially 0.91 to 1.08, and that the isotactic pentad fraction be 91.
5 or greater, especially 91.5 to 100%, more especially 92 to 100% and most especially 93 to 100%.
The terminology "B value of composition" used herein means a value calculated by the formulae shown on page 63 of this specification (page 96 of English text) from the sum of the areas of peaks ascribed to components of the composition.
When the B value and isotactic pentad fraction fall within the above ranges, the tensile modulus of the butene copolymer or resin composition comprising butene copolymer is preferably increased.
The following Ziegler catalyst ormetallocene catalyst provides a suitable catalyst for use in the production of butene copolymer or butene copolymer and poly-l-butene according to the present invention. The former is preferred. For example, use is made of a catalyst for a-olefin polymerization composed of: a solid Group IVB metal catalyst component containing a metal of Group IVB of the periodic table, a halogen and magnesium, and an organometallic compound catalyst component containing a metal of Groups I to III of the periodic table, optionally together with an organosilicon compound catalyst component containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative of these groups.
The metal of Group IVB of the periodic table may be titanium, zirconium or hafnium. Titanium is preferred.
ThemetalofGroupsIto IIIoftheperiodictable ispreferably aluminum.
As a Group IVB metal compound for use in the preparation of catalyst component there can be mentioned, for example, compounds of the formula: Ti(ORa)gX 4 -g wherein Ra represents a hydrocarbon group having 1 to carbon atoms, X represents a halogen atom, and g is a number satisfying the relationship 0 g 4.
These titanium compounds may be used individually or incombination. Thetitaniumcompounds maybe diluted with, for example, a hydrocarbon or a halogenated hydrocarbon before use.
A magnesium compound which can be employed in the preparation of catalyst component may have or may not have reducingproperties. Themagnesiumcompound, although canbeusedalone, maybe usedinthe form of a complex compound with an organoaluminum compound described later. The magnesium compound may be a liquid or a solid.
Reducing magnesium compound is a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond.
Nonreducing magnesium compound may be a compound derived from the above reducing magnesium compound or a compound derived in the preparation of catalyst component The nonreducing magnesium compound is produced by bringing, for example, acompoundof theformulaMg(ORb)hX2-h (wherein R b represents an alkyl group having 1 to 10 carbon atoms, X represents a halogen, and h is a number satisfying the relationship 0 h<2) or the reducing magnesium compound into contact with a polysiloxane compound, a halogenous silanecompound, ahalogenousaluminum compound oracompound such as an ester or an alcohol. In the present invention, use can be made of a complex compound or double compound formed from the above magnesium compound and another metal, or a mixture of the magnesium compound and another metal compound. Further, use may be made of a mixture of a plurality of magnesium compounds mentioned above.
When use is made of the nonreducing magnesium compound, the nonreducing magnesium compound in liquid form can be reacted with a liquid titanium compound in the presence of an electron donor to thereby precipitate a solid titanium composite. This method is described in, for example, Japanese Patent Laid-open Publication No. 58(1983)-830006.
In the preparation of solid catalyst component further, an electron donor is used. The electron donor can be, for example, an oxygen-containing electron donor such as an alcohol, a phenol, a ketone, an aldehyde, a carboxylic acid, an ester of organic or inorganic acid, an ether, an acid amide or an acid anhydride, or a nitrogenous electron donor such as an ammonia, an amine, anitrile oranisocyanate.
Preferred compound is an ether. Especially preferred compound is a compound having two or more ether bonds, such as the following diether:
R
22 R
R
2 R24 I I I
I
R
2
-O-C-R
26
R
23 R' R" R 2 wherein each of R 1 to R 26 represents a substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, a halogen, nitrogen, sulfur, phosphorus, boron and silicon, provided that any
R
1 to R 2 6 substituents may cooperate to form a ring other than benzene ring and that an atom other than carbon may be contained in a main chain of the compound having at least two ether bonds, and wherein n is an integer satisfying the relationship 2 n The above compound having two or more ether bonds can be, for example,, 2-(2-ethylhexyl)-l,3-dimethoxypropane, 2-isopropyl-l,3-dimethoxypropane, 2-cyclohexyl-l,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-l,3-dimethoxypropane or 2-isobutyl-2-isopropyl-l,3-dimethoxypropane. The compound is preferably a diether such as 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane, 2,2-dicyclohexyl-l,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane or 2-isobutyl-2-isopropyl-l,3-dimethoxypropane.
When the electron donor is an ester, preferred use is made of an ester of the formula:
R
3 -C-COOR' R 3 COOR' R 3
-C-COOR
/C\
R -C-COOR 2
R
4
COOR
2
R
4
-C-COOR
6
R
3
-C-COOR'
or R -C-COOR wherein R1 represents an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms; each of R
R
5 and R 6 represents hydrogen or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms; and each of R 3 and R 4 represents hydrogen or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 and R 4 may be connected to each other.
It is preferred that at least one of R 3 and R 4 represents an unsubstituted or substituted hydrocarbon group. As the substituted hydrocarbon group represented by R 1 toR 6 there can be mentioned those having a heteroatom such as N, O or S, for example, having a group such as C-O-C, COOR, COOH, OH, SO 3 H, -C-N-C-or NH 2 Apreferred example of the organic acid ester is diisobutyl phthalate.
Further, there can be mentioned a monocarboxylic acid ester of the formula R7COOR 8 (wherein each of R 7 and R 8 represents an unsubstituted or substituted hydrocarbyl group having 1 to 10 carbon atoms, at least one thereof being a branched chain (including alicyclic form) or ring-containing chain group). Also, a carbonic acid ester can be selected.
Although it is not necessary to use the electron donor as a starting material in the preparation of solid catalyst component a compound which can be converted to the electron donor during the preparation of solid catalyst component can be used as the same.
The solid catalyst component of the present invention is produced by bringing the above magnesium compound (including metallic magnesium), titanium compound and electron donor into mutual contact. The production can be accomplished by the use of the known process for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor. The above components may be brought into mutual contact in the presence of another reactive agent such as silicon, phosphorus or aluminum.
Although the usage of each of the above components added in the preparation of solid catalyst component is varied depending on the employed preparation method and cannot be generally specified, for example, the electron donor is used in an amount of about 0.01 to 10 mol, preferably 0.05 to mol, while the titanium compound is used in an amount of about 0.01 to 500 mol, preferably 0.05 to 300 mol, per mol of magnesium compound.
Thethus obtainedsolidcatalyst component contains magnesium, titanium, halogen and electron donor.
In the solid catalyst component the atomic ratio of halogen/titanium is in the range of about 4 to 200, preferably about 5 to 100. The molar ratio of electron donor/titanium is in the range of about 0.1to 10, preferably about0. 2 toabout6. Theatomicratio ofmagnesium/titanium is in the range of about 1 to 100, preferably about 2 to The solid catalyst component contains a magnesium halide of crystal size that is smaller than that of commercially available magnesium halide. The specific surface area thereof is about 50 m 2 /g or greater, preferably from about 60 to 1000 m 2 and still preferably from about 100 to 800 m 2 The solid catalyst component is constituted of the above components linked together, so that the composition of the solid catalyst component is substantially not changed by hexane washing.
The solid catalyst component although can be used as it is, can be diluted with, for example, an inorganic or organic compound such as a silicon compound, an aluminum compound or a polyolefin before use.
The process for preparing a highly active titanium catalyst component is disclosed in, for example, Japanese Patent Laid-open Publication Nos. 50(1975)-108385, 50(1975)-126590, 51(1976)-20297, 51(1976)-28189, 51(1976)-64586, 51(1976)-92885, 51(1976)-136625, 52(1977)-87489, 52(1977)-100596, 52(1977)-147688, 52(1977)-104593, 53(1978)-2580, 53(1978)-40093, 53(1978)-40094, 53(1978)-43094, 55(1980)-135102, 55(1980)-135103, 55(1980)-152710, 56(1981)-811, 56(1981)-11908, 56(1981)-18606, 58(1983)-83006, 58(1983)-138705, 58(1983)-138706, 58(1983)-138707, 58(1983)-138708, 58(1983)-138709, 58 (1983)-138710, 58(1983)-138715, 60(1985)-23404, 61(1986)-21109, 61(1986)-37802 and 61(1986)-37803.
A typical example of the organometallic compound catalyst component containing a metal of Groups I to III of the periodic table is an organoaluminum compound catalyst component, which is a compound having at least one aluminum-carbon bond in its molecule. For example, it is an organoaluminum compound of the general formula: RCjAl(ORd)kHmXp (i) wherein'each of Rc and Rd represents a hydrocarbon group having 1 to 15 carbon atoms, provided that these may be identical with or different from each other; X represents a halogen atom; and j, k, m and p are numbers satisfying the relationships: 0 j 3, 0 k 3, 0 m 3 and 0 p 3, respectively, provided that j k m p 3. It is preferred that R c and Rd be hydrocarbon groups each having 1 to 4 carbon atoms.
Also, use can be made of a complex alkylate of Group I metal and aluminum represented by the general formula: M1AIRc 4 (ii) wherein M 1 represents Li, Na or K, and Rc is as defined above.
The organoaluminum compound of the general formula (i) can be, for example, any of those of the formulae: RCj
A
l(ORd)k wherein Rc and R d are as defined above; and j and k are numbers satisfying the relationships: 1.5 j 3 and 0 k 1.5, respectively, provided that j k 3; RcjAIXp wherein R c is as defined above; X represents a halogen atom; and j and p are numbers satisfying the relationships: 0 j 3 and 0 p 3, respectively, provided that j p 3; Rc jAHm wherein Rc is as defined above; H represents hydrogen; and j and m are numbers satisfying the relationships: 2 j 3 and 0 m 1, respectively, provided that j m 3; and RcjAl(ORd)k p wherein Rc and Rd are as defined above; X represents a halogen atom; and j, k and p are numbers satisfying the relationships: 0 j 3, 0 k 3 and 0 <p 3, respectively, provided that j k p 3.
Also, use can be made of an alkylaluminum consisting of a plurality of aluminum compounds bonded together.
The organosilicon compound catalyst component (e) optionally added to the solid catalyst component and the organometallic compoundcatalyst component consists of an organosilicon compound containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative of these groups in its structure. The organosilicon compound can be, for example, a compound of the general formula: ReRfqSi(ORg)3-q wherein Re represents a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative of these groups; each of R f and Rg represents a hydrocarbon group having 1 to 10 carbon atoms, which may be crosslinked with an alkyl group or the like; and q is a number satisfying the relationship: 0 q 3.
Each of R f and Rg can be, for example, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
Specific examples thereof includemethyl, ethyl, isopropyl, phenyl, cyclopentyl, cyclopentenyl and cyclopentadienyl.
R
f and Rg may be identical with or different from each other.
It is preferred to employ an organosilicon compound wherein Re represents a cyclopentyl group, R f represents an alkyl group or a cyclopentyl group, and Rg represents an alkyl group, especially methyl or ethyl.
Also, use can be made of an organosilicon compound of the general formula: RfrSi(OR9)4-r wherein R f and Rg are as defined above, and r is a number satisfying the inequality: 0 r 4.
Rf and R9, although not particularly limited, can be, for example, methyl, ethyl, isopropyl, phenyl, cyclopentyl, cyclopentenyl or cyclopentadienyl.
R
f and Rg may be identical with or different from each other.
Specifically, the organosilicon compound can be, for example, ethyltriethoxysilane, n-propyltriethoxysilane, phenyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane or cyclopentyldimethylmethoxysilane.
Cyclohexylmethyldimethoxysilane or the like can preferably be employed.
The butene copolymer and resin composition comprising butene copolymer according to the present invention are produced by copolymerizing 1-butene and an a-olefin in the presence of the above catalyst. This copolymerization (principal polymerization) may be preceded by the following prepolymerization.
In the prepolymerization, generally, the solid catalyst component is used in combination with at least part of the organometallic compound catalyst component At that time, part or all of the organosilicon compound catalyst component can be present therein.
In the prepolymerization, the catalyst can be used in a concentration which is significantly higher than the catalyst concentration in the principal polymerization system.
In the prepolymerization, the concentration of solid catalyst component is generally in the range of, for example, about 0.5 to 100 mmol, preferably about 1 to mmol, in terms of titaniumatomper lit. of inert hydrocarbon medium described later.
The amount of organometallic compound catalyst component may be such that 0.1 to 500 g, preferably 0.3 to 300 g of a polymer is formed per gram of solid catalyst component For example, the amount is generally in the range of about 0.1 to 100 mol, preferably about 0.5 to mol, per mol of titanium atom of solid catalyst component The prepolymerization is preferably performed under mild conditions with the a-olefin and above catalyst components added to an inert hydrocarbon medium.
As the inert hydrocarbon medium for use in the prepolymerization, there can be mentioned, for example, an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane or kerosine; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclopentane; an aromatichydrocarbon such as benzene, tolueneorxylene; ahalogenatedhydrocarbon suchas ethylene chloride or chlorobenzene; or a mixture of these. Of these inert hydrocarbon mediums, an aliphatic hydrocarbon is preferably employed.
The a-olefin for use in the prepolymerization is one having 2 to 10 carbon atoms, preferably 3 to 10 carbon atoms, which may be identical with or different from the a-olefin to be used in the principal polymerization. A highly crystalline a-olefin polymer is obtained by the prepolymerization.
In the prepolymerization, the reaction temperature is not limited as long as a formed prepolymer is substantially not dissolved inthe inert hydrocarbonmedium. The reaction temperature is generally in the range of about -20 to +80 0
C,
preferably about -20 to +60 0 C, and still preferably 0 to +40 0
C.
A molecular weight modifier such as hydrogen can be used in the prepolymerization.
The molecular weight modifier is used in such an amount that a polymer obtained by the prepolymerization has an intrinsic viscosity measured in decalin at 135 0 C, of about 0.2 dl/g or greater, preferably about 0.5 to 10 dl/g.
The prepolymerization, as mentioned above, is carried out in such a manner that, for example, about 0.1 to 500 g, preferably about 0.3 to 300 g of a polymer is formed per gram of titanium catalyst component.
The prepolymerization can be performed by a batch process or a continuous process.
.The principal polymerization for producing a copolymer of 1-butene and a-olefin having 2 to 10 carbon atoms (excluding 1-butene) according to the present invention is preferably performed in the presence of the catalyst for olefin polymerization prepared fromthe above solid catalyst component organometallic compound catalyst component and organosilicon compound catalyst component after the above prepolymerization or without conducting any prepolymerization.
The principal polymerization can be effected by any of liquidphasepolymerizationprocesses, such as a solution polymerization and a suspension polymerization, and gas phase polymerization processes. With respect to the solvent for use in the solution polymerization, although an inert hydrocarbon solvent is preferred, use can be made ofanolefinwhichisliquid under polymerization conditions.
The molar ratio of a-olefin to 1-butene in the vapor phase within a reaction vessel is in the range of 0.001 to 0.1, preferably 0.002 to 0.08.
The polymerization temperature is not limited as long as a formed polymer is substantially not dissolved in the inert hydrocarbon medium. The polymerization temperature is generally in the range of about -20 to +100 0 C, preferably about -20 to +80 0 C, and still preferably 0 to +40 0 C. The applied pressure is generally in the range of atmospheric pressure to 1 x 10 MPa, preferably 2 x 10-1 to 5 MPa.
Theprincipalpolymerizationcanbe performedby a batch process, a semicontinuous process or a continuous process.
Further, the principal polymerization can be performed by a multistage polymerization process wherein polymerization conditions are varied according to stage.
In the production of the butene copolymer of the present invention, forexample, the solidcatalyst component is generally used in an amount of about 0.005 to mmol, preferably about 0.01to 0.5mmol, in terms of titanium atom per lit. of polymerization volume. The organometallic compound.catalyst component is generally used, for example, in such an amount that metal atoms of the organometallic compound catalyst component amount to about 1 to 2000 mol, preferably about 5 to 500 mol, per mol of titanium atoms contained in the solid catalyst component of the polymerization system. Further, the organosilicon compound catalyst component is generally used in an amount of 0.001 to 2 mol, preferably about 0.001 to 1 mol, and still preferably about 0.001 to 0.5 mol, in terms of Si atoms contained in the organosilicon compound catalyst component per mol of metal atoms of the organometallic compound catalyst component (ii) Resin composition The resin composition comprising butene copolymer
(A)
according tothepresentinvention, althoughgenerallybeing a composition comprising the butene copolymer of the present invention and another polymer, is preferably a resin composition comprising the butene copolymer mixed with an a-olefin homopolymer and/or copolymer obtained by separate polymerization. The polymer mixed into thebutene copolymer of the present invention is preferably a homopolymer or copolymer of a-olefin having 2 to 20 carbon atoms, still preferably a homopolymer or copolymer of a-olefin having 4 to 20 carbon atoms. With respect to the composition ratio, preferably, 40 to 90% by weight of the butene copolymer of the present invention is mixed with to 10% by weight of other polymers. Still preferably, to 90% by weight of the butene copolymer is mixed with 40 to 10% by weight of other polymers.
When it is intended to mold, for example, pipes from the resin composition, it is preferred that the mixed (co)polymer be a butene copolymer different from the butene copolymer of the present invention, especially poly-l-butene and more especially poly-1-butene
(B)
produced by polymerization with the use of the catalyst suitable for the production of butene copolymer The poly-1-butene is mixed in a proportion of 30% by weight or less, preferably 30 to 5% by weight, based on the total resin weight. With respect tothea-olefin content ofbutene copolymer in pipes, an extrudability enhancement can favorably be attained by effecting such a mixing that the propylene content is greater than 1 mol% but less than mol%.
In the present invention, amixture of butene copolymer wherein the content of a-olefin having 2 to 10 carbon atoms (excluding 1-butene) is greater than 1 mol% and poly-l-butene wherein the content of a-olefin having 2 to 10 carbon atoms (excluding 1-butene) is 1 mol% or less is especially preferred.
The mixed poly-l-butene is preferably one whose molecular weight in terms of intrinsic viscosity is in the range of 1 to 5 dl/g. When a composition of butene/propylene copolymer and poly-l-butene is employed, it is preferred that the molecular weights of butene/propylene copolymer and poly-l-butene
(B)
satisfy such a relationship that the ratio of the intrinsic viscosity [g]B of poly-l-butene to the intrinsic viscosity [nlBP of butene/propylene copolymer [n]B/[]BP is in the range of 0.1 to 1.0, especially 0.2 to 0.9, and more especially 0.3 to 0.8.
The butene copolymer or resin composition comprising butene copolymer according to the present inventionmaycontainotherpolymers, forexample, a flexible a-olefin copolymer, such as an ethylene random copolymer ethylene/propylene random copolymer) or a styrene block copolymer SEBS, SBS or SEPS), in an amount not detrimental to the properties to be attained in the present invention.
Moreover, the butenecopolymer orresincomposition according to the present invention may be incorporated with various commonly added compounding agents such as a heat stabilizer, a weathering stabilizer, a slip agent, a nucleating agent, a pigment, a dye and a lubricant.
As the above nucleating agent, there can be mentioned, for example, polyethylene wax, polypropylene wax, polyethylene, polypropylene, polystyrene, nylon (polyamide), polycaprolactone, talc, titanium oxide, 1,8-naphthalimide, phthalimide, alizarin, quinizarin, 1,5-dihydroxy-9,10-anthraquinone, quinalizarin, sodium 2-anthraquinonesulfonate, 2-methyl-9,10-anthroquinone, anthrone, 9-methylanthracene, anthracene, 9,10-dihydroanthracene, 1,4-naphthoquinone, l,l-dinaphthyl, stearic acid, calcium stearate, sodium stearate, potassium stearate, zinc oxide, hydroquinone, anthranilic acid, ethylenebisstearylamide and sorbitol derivatives. Further, there can be mentioned polycarboxylic acid amide compounds, polyamine amide compounds and polyamino acid amide compounds described in Japanese Patent Laid-open Publication No. 8(1996)-48838, and vinylcycloalkane polymers described in Japanese Patent Publication No. 5(1993)-58019.
Of these, amide compounds can especially preferably be employed.
Although the method of preparing the resin composition of the present invention is not particularly limited, for example, the preparation can be performed by the method in which the butene copolymer and polymers to be mixed are melt mixed by means of a single-screw extruder or a multi-screw extruder, or bythemethod inwhichmeltkneading by means of a Banbury mixer or a kneader and granulation or pulverization are sequentially carried out. Further, there can be mentioned the method in which the butene copolymer and polymers to be mixed are produced by separate polymerizations and in which the thus obtained polymer solutions are directly mixed together under agitation.
(iii) Molded item The butene copolymer or resin composition comprising butene copolymer according to the present invention is molded by customary techniques using, for example, a single-screw extruder or amulti-screw extruder.
The butene copolymer or resin composition can be formed into molded items having a wide variety of configurations, examples of which include a pipe, a pipe joint, a sheet and a box.
With respect to the pipe obtained by molding the butene copolymer or resin composition comprising butene copolymer according tothepresentinventionbycustomary techniques using, for example, a single-screw extruder, the ratio of outside diameter to thickness is in the range of to 20, preferably 6 to 18. The breaking time exhibited in a hydrostatic test of the pipe (measured at 95 0 C at a hoop stress of 6 MPa) is 20 thousand hours or more. This means that the pipe has an extremely high pressure resistance strength.
(iv) Solid titanium catalyst The solid titanium catalyst of the present invention is composed of 5 to 35% by weight, preferably 8 to 30% by weight, still preferably 10 to 28% by weight, and optimally 12 to 25% by weight of magnesium 0.3 to by weight, preferably 0.5 to 8% by weight, still preferably 0.8 to 6% byweight, andoptimally 1 to 5%byweight of titanium 30 to 75% by weight, preferably 35 to 75% by weight, still preferably 38 to 72% by weight, and optimally 40 to by weight of a halogen 0.5 to 30% by weight, preferably 1 to 27% by weight, still preferably 3 to by weight, and optimally 5 to 23% by weight of a compound having at least two ether bonds between which a plurality of atoms are interposed 0.05 to 20% by weight, preferably 0.1 to 15% by weight, still preferably 1 to 12% by weight, and optimally 2 to 10% by weight of a hydrocarbon and0.05to7%byweight, preferably0.1to 5% byweight, still preferably 0.15 to 4% by weight, and optimally 0.2 to 3% by weight of a solubilizing agent When the content of hydrocarbon in the solid titanium catalyst exceeds 20% by weight, catalyst particles may be coagulated to thereby deteriorate the 51 particulate properties of the catalyst. Further, the particulate properties of obtained a-olefin polymer may be deteriorated. On the other hand, when the content of hydrocarbon in the solid titanium catalyst is less than 0.05%byweight, not onlymaytheparticulateproperties of the catalyst be deteriorated but also the polymerization activity of a-olefin may be lowered and further the stereoregularityof obtained a-olefinpolymermaybe lowered.
Still further, the bulk density of polymer may be lowered, and fine powder may be increased.
It is preferred that the solid titanium catalyst (A' substantially does not contain carboxylic acid derivatives.
Although the structure of the solid titanium catalyst and the bonding condition of each component thereof have not yet been elucidated, the content of each component can be determined by measurement by means of ICP (atomic absorption spectroscopy), GC, etc. performed after satisfactory washing of the solid titanium catalyst with a large amount of hexane, followed by drying at room temperature under 0.1 to 1 Torr for 2 hr or more.
The solidtitaniumcatalyst maycontaincomponents other than the components to forexample, asupport.
The content of such other components is 50% by weight or less, preferably 40% by weight or less, still preferably by weight or less, and optimally 20% by weight or less.
[Production of solid titanium catalyst The solid titanium catalyst of the present invention can be producedbybringing a halogenousmagnesium compound and a solubilizing agent capable of dissolving the halogenousmagnesiumcompound intomutual contact in a solvent to thereby obtain a solution adding a first compound having at least two ether bonds between which a plurality of atoms are interposed to the solution to thereby obtain a solution and contacting a liquid titanium compound with the solution (II) to thereby obtaina solution (III), optionally followed by separating solids from the soluti'on (III) The solution (II) may be prepared by bringing the halogenous magnesium compound the solubilizing agent and the first compound into mutual contact in the solvent (y) Also, the solid titanium catalyst of the present invention can be produced by bringing a halogenous magnesium compound and a solubilizing agent capable of dissolving the halogenousmagnesiumcompound intomutual contact in a solvent to thereby obtain a solution adding a first compound having at least two ether bonds between which a plurality of atoms are interposed to the solution to thereby obtain a solution (II), contacting a liquid titanium compound with the solution (II) to thereby obtain a solution (III), and adding a second compound having at least two ether bonds between which a plurality of atoms are interposed to the solution (III) to thereby obtain a solution optionally followed by separating solids fromthe solution The solution (II) maybe prepared bybringing the halogenous magnesium compound the solubilizing agent and the first compound (8) into mutual contact in the solvent (y) One example of the process for producing the solid titanium catalyst of the present invention in which an alcohol is used as the solubilizing agent will now be described. Even if a solubilizing agent other than an alcohol is employed, the process will substantially not differ.
A halogenous magnesium compound and an alcohol are brought into mutual contact in a hydrocarbon solvent (y) to thereby obtain a homogeneous solution (halogenous magnesium compound solution) wherein the halogenous magnesium compound has been dissolved in amixed solvent of the alcohol and the hydrocarbon solvent (y) The above alcohol is used in an amount of 1 to 40 mol, preferably 1.5 to 20 mol, per mol of halogenous magnesium compound The hydrocarbon solvent is used in an amount of 1 to 30 mol, preferably 1.5 to 15 mol, per mol of halogenous magnesium compound (a) The temperature at which the above contact is effected is in the range of 60 to 3000C, preferably 100 to 2000C.
The period during which the above contact is effected is in the range of 15 to 300 min, preferably 30 to 120 min.
Subsequently, a firstcompoundhaving atleasttwoether bonds between which a plurality of atoms are interposed (8) is added to the magnesium compound solution to thereby obtain a homogeneous solution (magnesium/polyether solution) The first compound having at least two ether bonds between which a plurality of atoms are interposed helps to solubilize the halogenous magnesium compound (a) in the hydrocarbon solvent The above first compound having at least two ether bonds between which a plurality of atoms are interposed is used in an amount of 0.01 to 1.0 mol, preferably 0.1 to mol, per mol of halogenous magnesium compound contained in the magnesium compound solution The temperature at which the above contact is effected is in the range of -20 to +300°C, preferably 20 to 200°C.
The period during which the above contact is effected is in the range of 5 to 240 min, preferably 10 to 120 min.
Thereafter, the magnesium/polyether solution (II) and liquid titanium compound are brought into mutual contact to thereby obtain a mixture (magnesium/titanium solution) (III) containing the halogenous magnesium compound and the liquid titanium compound The above liquid titanium compound is used in an amount of 2 to 100 gram atoms, preferably 4 to 50 gram atoms, per gram atom of magnesium contained in the magnesium/polyether solution (II).
The temperature at which the above contact is effected is in the range of -70 to +200 0 C, preferably -70 to +50 0
C.
The period during which the above contact is effected is in the range of 5 to 300 min, preferably 30 to 180 min.
The obtained magnesium/titanium solution (III) is heated at 20 to 300 0 C, preferably 50 to 150 0 C, thereby obtaining a suspension of solid titanium catalyst The heating period is in the range of 10 to 360 min, preferably to 300 min.
The suspension of solid titanium catalyst is subjected to solid/liquid separation by filtration or the like, thereby obtaining solid (solid titanium catalyst) Further, this solid maybe brought into contactwitha liquid titanium compound A catalyst for polymerization of an a-olefin having 4 or more carbon atoms can be obtained by drying the thus produced solid titanium catalyst or by washing the same with a hydrocarbon solvent Alternatively, the solid titanium catalyst can be resuspended in a hydrocarbon solvent so as to use the suspension as a catalyst for polymerization of an a-olefin having 4 or more carbon atoms.
In another method, after the magnesium/polyether solution (II) and liquid titanium compound are brought intomutualcontacttotherebyobtainthemagnesium/titanium solution (III), a solubilizing agent may be brought into contact with the magnesium/titanium solution (III). At that time, it is preferred that the magnesium/titanium solution (III) beheatedbeforecontactwiththesolubilizing agent In this method only, a second compound having at least two ether bonds between which a plurality of atoms are interposed can be used as the solubilizing agent
(P)
This solubilizing agent is used in an amount of 0.01 to 5 mol, preferably 0.1 to 1 mol, per mol of halogenous magnesium compound [Raw material of solid titanium catalyst [Halogenous magnesium compound The halogenous magnesium compound for use in the present invention can be, for example, any of magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxymagnesium halides such as methoxymagnesiumchloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride and octoxymagnesium chloride; and aryloxymagnesiumhalides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride. The halogenous magnesium compound may be a complex compound or double compound with another metal or a mixture with another metal compound. Further, the halogenous magnesium compound (a) maybeamixture of a plurality ofthesecompounds. Of these, magnesium halides are preferred. Magnesium chloride is especially preferred. The halogenous magnesium compound constitutes magnesium and halogen of thesolid titanium catalyst of the present invention.
[Solubilizing agent The solubilizing agent for use in the present invention has the function of dissolving the halogenous magnesium compound in the solvent Examples of suitable solubilizing agents includeanalcohol, an ester including a metallic acid ester and an ether other than the compound having at least two ether bonds between which a plurality of atoms are interposed The solubilizing agent corresponds to the solubilizing agent as a constituent of the solid titanium catalyst of the present invention.
As the above alcohol, there can be mentioned, for example, an aliphatic alcohol such as ethylene glycol, methylcarbitol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol or stearyl alcohol; an alicyclic alcohol such as cyclohexanol or methylcyclohexanol; an aromatic alcohol such as benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, a-methylbenzyl alcohol or a,a-dimethylbenzyl alcohol; or an alkoxylated aliphatic alcohol such as n-butyl cellosolve or l-butoxy-2-propanol. Of these, an aliphatic alcohol is preferred. 2-Ethylhexanol is especially preferred.
As the aboveester, there can bementioned, for example, an organic acid ester having 2 to 18 carbon atoms, such as methyl formate, methylacetate, ethylacetate, vinylacetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyldichloroacetate, methylmethacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butylbenzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzylbenzoate, methyltoluate, ethyltoluate, amyltoluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,y-butyrolactone, -valerolactone, coumarin, phthalide or ethyl carbonate.
Metallic acid esters are also effective, and are comprehended in the esters of the present invention.
Examples thereof include titanic acid esters, vanadic acid esters, niobic acid esters and zirconic acid esters.
Examples of the above titanic acid esters include: orthotitanic acid esters such as methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, isopropyl orthotitanate, n-butyl orthotitanate, isobutyl orthotitanate, n-amyl orthotitanate, 2-ethylhexyl orthotitanate, n-octylorthotitanate, phenylorthotitanate and cyclohexyl orthotitanate; and polytitanic acid esters such as methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, isopropyl polytitanate, n-butylpolytitanate, isobutylpolytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate and cyclohexyl polytitanate.
Examples of the above vanadic acid esters, niobic acid esters and zirconic acid esters include those set forth above with respect to the titanic acid esters wherein titanium is replaced by vanadium, niobium and zirconium, respectively.
As the above ether other than the compound having at least two ether bonds between which a plurality of atoms are interposed 6' there can be mentioned, for example, an ether having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole or diphenyl ether.
[Compound having at least two ether bonds between which a plurality of atoms are interposed With respect to the compound having at least two ether bonds between which a plurality of atoms are interposed (hereinafter may be referred to as "polyether" for use in the present invention, the atom (hereinafter may be referred to as "connecting group") interposed between ether bonds is at least one member selected from the group consisting of carbon, silicon, oxygen, nitrogen, sulfur, phosphorus and boron. This connecting group is preferably one having, bonded thereto, a substituent of relatively high bulkiness, for example, a linear, branched or cyclic substituent having 2 or more, preferably 3 or more carbon atoms, still preferably a branched or cyclic substituent having 2 or more, preferably 3 or more carbon atoms. The substituent preferably has two or more, still preferably 3 to 20, yet still preferably 3 to 10, and optimally 3 to 7 carbon atoms. A plurality of different types of polyethers may be used. As the first polyether and the second polyether, identical polyethers can be used, or different polyethers can be used. The polyether corresponds to the compound having at least two ether bonds between which a plurality of atoms are interposed as a constituent of the solidtitanium catalyst of the present invention.
As the polyether there can be mentioned, for example, a compound of the formula: R22 Rn+1. R2n R24
R
2 1 0 C C O C R 2 6 R23 R R" R 2 wherein n is an integer satisfying the relationship 2 n 10; each of R 1 to R 2 6 represents a substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, a halogen, nitrogen, sulfur, phosphorus, boron and silicon, provided that any R 1 to R 2 6 substituents, preferably R 1 to R 2 0 (n 20) substituents, may cooperate to form a ring other than benzene ring and that an atom other than carbon may be contained in a main chain thereof.
The polyether can be, for example, any of 2- (2-ethyihexyl) 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-l, 3-dimethoxypropane, 2-s-butyvl-l, 3-dimethoxypropane, 2-cyclohexyl-l, 3-dimethoxypropane, 2-phenyl-l, 3-dimethoxypropane, 2-cumyl-l,3-dimethoxypropane, 2- (2-phenylethyl) 3-dimethoxypropane, 2- (2-cyclohexylethyl) 3-dimethoxypropane, 2- (p-chlorophenyl) 3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) 3-dimethoxypropane, 2- (2-fluorophenyl) 3-dimethoxypropane, 2- (l-decahydronaphthyl) 3-dimethoxypropane, 2- (p-t-butylphenyi) 3-dimethoxypropane, 2, 2-dicyclohexyl-l, 3-dimethoxypropane, 2, 2-dicyclopentyl-l, 3-dimethoxypropane, 2, 2-diethyl-l, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-dimethoxypropane, 2, 2-diisopropyi-l, 3-dimethoxypropane, 2, 2-dibutyl-1, 3-dimethoxypropale, 2-methyl-2-propyl1, 3-dimethoxypropale, 2-methyl-2-beflzYl1, 3-dimethoxypropale, 2-mrethyl-2-ethyl1, 3-dimethoxypropane, 2-methyl-2-isopropyl-l, 3-dimethoxypropale, 2-methyl-2-pheflyl, 3-dimethoxypropale, 2-rethyl-2-cyclohexyllt 3-dimethoxypropale, 2, 2-bis (p-chlorophelyl) 3-dimethoxypropale, 2, 2-bis (2-cyclohexylethYl) 3-dimethoxypropale, 2-methy1-2-isobutyl-1,3-dimethoxypropale, 2-methyl-2-(2-ethylhexyl1V1,3-dimethoxypropale, 2, 2-diisobutyl-1, 3-dimethoxypropale, 2, 2-diphenyl-1, 3-dimethoxyprpale, 2,2-dibenzyl-1, 3-dimethoxypropale, 2,2-bis(cyclohexylmethY1V-1,3-dimethoxypropafle, 2, 2-diisobutyl-1, 3-diethoxypropane, 2, 2-djisobutyl,3-dibutoxypropale, 2-isobutyl-2-isopropyl-l, 3-dirnethoxypropale, 2-(l-methylbutylV2-isopropyl1,3dimethoxypropale, 2 -(1-methylbutyl)-2-sbutyl-1,3dimethoxypropale, 2, 2-dj-s-butyl-l, 3-dirnethoxypropane, 2, 2-di-t-butyl1, 3-dimethoxypropale, 2, 2-dineopentyl-l, 3-dirnethoxypropale, 2-isopropyl-2-isopeltyl-l, 3-dimethoxypropale, 2-phenyl-2-isopropyl,3-dirnethoxypropale, 2-phenyl-2-s-butyl-l, 3-dimethoxypropale, 2-benzyl-2-isopropyl,3-dimethoxypropale, 2-benzyl-2-s-butYl-1,3-cilmethoxypropale, 2-pheny1-2-befzl-PJ,3-dimetuhoxypropane, 2-cyclopenty12-isopropyll1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-l1 3-dimethoxypropane, 2-cyclohexyl-2-sbutYlilt 3-dimethoxypropane, 2-isopropyl-2-s-butYl1,3-dimethoxypropane, 2-cyclohexyl-2-cyc1ohexylmethyl-1t 3-dimethoxypropale, 2, 3-diphenyl-1, 4-diethoxybutale, 2, 3-dicyclohexy1-1, 4-diethoxybutaie, 2, 2-dibenzyl-1, 4-diethoxybutale, 2, 3-dicyclohexyl-1, 4-diethoxybutane, 2, 3-diisopropyl-l, 4-diethoxybutane, 2, 2-bis (p-rrethylpheflyl) 4-dimethoxybutane, 2, 3-bis (p-chlorophelYl) 4-dimethoxybutane, 2, 3-bis (p-tluorophelyl) 4-dimethoxybutane, 2, 4-diphenyl-1, 2, 5-diphenylil, 2, 4-diisopropyl-l, 2, 4-diisobutyl1, 2, 4-diisoarnyl-1, 3-rethoxyrethyltetrahydrofural, 3-rnethoxymethyldioxale, 1,3-diisobutoxypropale, 1,2-diisobutoxypropane, 1,2-diisobutoxyethale, 1, 3-diisoamyloxypropale, 1, 3-dciisoneopentyloxyethale, 1, 3-dineopentyloxypropale, 2,2-tetramethylefle1, 3-dimethoxypropale, 2, 2-pentamethylefle1, 3-dimethoxypropale, 2, 2-hexamethylele-l, 3-dimethoxypropale, 1, 2-bis (methoxymethyl) cyclohexane, 2, 8-dioxaspiro 3,7.-dioxabicyc1o[3,3,1]ofale, 3, 7-dioxabicyclo octane, 3,3-diisobutyi-1,5-oxononane, 6, 6-dlisobutyldioxyheptane, 1, 1-dimethoxymethylcyc1opeltale, l,1-bis(dimethoxYrnethYl)cyclohexale, 1, 1-bis (methoxymethyl) bicyclo heptane, 1, 1-dimethoxymfethy1cyc1opeltale, 2-methy1-2-methoxyrfethyl-l1 3-dimethoxypropale, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyli2-methoxymethyl1,i3-dimethoxypropale, 2, 2-djjsobutyl-l, 3-dimethoxycyclohexale, 2-isopropyl-2-isoamylil13-dimethoxycycolhexale, 2-cyclohexy1-2-methoxymfethyl1,t3-dimethoxycyclohexale, 2--isopropyl-20-methoxymethy1-1, 3-dimethoxycyclohexale, 2-isobutyl-2-methoxymethyl-l1 3-dimethoxycyclohexale, 2-cyclohexyl2ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-~isopropyl2ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl2ethoxymethyl-1,3-dimethoxycYClohexane, 2 -isobutyl-2-ethoxymethyl-l1 3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethYl-lt 3-dimethoxycyclohexane, tris (p-methoxyphelYl) phosphine, methyipheflylbis (methoxymethyl) silane, dipheriylbis (methoxyrnethyl) silane, methylcyclohexYlbiS (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, cyclchexylit-butYlbis (methoxyrnethyl) silane and (methoxymethyl) silane. These polyethers 6' can be used in combination.
Of the above compounds, 1,3-diethers are preferred.
Especially preferred compounds are 2, 2-diisobutyl1, 3-dimethoxypropane, 2-isopropyli2-isopentyl-lf 3-dimethoxypropane, 2, 2-dicyclohexylil1 3-dimethoxypropane, 2, 2-bis (cyclohexylmethYl) 3-dimethoxYpropane, 2-isopropy1-2Ocyclohexyl-1,3-dimethoxypropane, 2-isopropyl2sbutyl-1,3-dimethoxypropale, 2, 2-diphenyl-l, 3-dimethoxypropale and 2-isopropyli2-cyclopentyllt 3-dimethoxypropale.
[Liquid titanium compound() As the liquid titanium compound foruseinthepreSent invention, there can be mentioned, forexample, atetravalent halogenous titanium compound of the formula: Ti(QR)MX4..m wherein R represents a hydrocarbon group, X represents a halogen atom, an sanme satisfying the relationship 0 <m <4.
The halogenous titanium compouind can be, for example, any of titanium tetrahalides such as TiCl 4 TiBr 4 and Ti1 4 alkoxytitaflium trihalides such as Ti(OCH 3 )C1 3 Ti(0C 2
H
5 )C1 3 Ti(On-0 4
H
9 )Cl 3 Ti(0C 2 H)tan Ti(Oi5OC4
H
9 )Br3; alkoxytitanium dihalides such as Ti(OCH 3 2 C1 2 Ti(0C 2
H
5 2 C1 2 Ti(On-C4 H9) 2 C1 2 and Ti(0C 2
H
5 2 Br 2 alkoxytitanium monohalides such as Ti(OCH 3 3 C1, Ti(0C 2
HS)
3 C1, Ti(On-C4 H9) 3 C1 and Ti (0C 2
H
5 3 Br; and tetraalkoxytitaniums such as Ti (OCH- 3 4 Ti(0C 2
H_
5 4 Ti(On-C4
H
9 4 Ti(Oi5O-C4
H
9 4 and Ti (O-2-ethylhexyl) 4. Of these, titanium tetrahalides are preferred. Titanium tetrachloride is especially preferred.
These titanium compounds may be used individually or in combination. Alternatively, they may be used in the form of a dilution in the following solvent [Solvent As the solvent for use in the present invention, therecanbementioned, forexample, analiphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane or kerosine; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclopentane; an aromatic hydrocarbon such as benzene, toluene or xylene; a halogenated hydrocarbon such as ethylene chloride or chlorobenzene; oramixtureof these. Of these, analiphatic hydrocarbon is preferred. Decane is especially preferred.
The solvent corresponds to the hydrocarbon of the solid titanium catalyst of the present invention.
[Polymerization catalyst] The solid titanium catalyst is combined with a catalyst component comprising an organometallic compound containing a metal of Groups I'to III of the periodic table and used to polymerize an a-olefin having 4 or more carbon atoms. For example, an a-olefin is polymerized with the use of a first polymerization catalyst prepared from the solid titanium catalyst and an organoaluminum compound optionally together with an electron donor Also, an a-olefin is polymerized with the use of a second polymerization catalyst prepared from a prepolymerization catalyst obtained by prepolymerizationof an a-olefin in the presence of the solid titanium catalyst and an organoaluminumcompound optionally together with an organoaluminum compound and/or an electron donor [Organometallic compound containing a metal of Groups I to III of the periodic table] As the organometallic compound containing a metal of Groups I to III of the periodic table, for use in the polymerization of the present invention, there can be mentioned, for example, an organoaluminum compound of the formula: RanAIX 3 -n wherein Ra represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen or hydrogen, and n is a number of 1 to 3.
In this formula, Ra represents a hydrocarbon group, for example, an alkyl group, a cycloalkyl group or an aryl group, having 1 to 12 carbon atoms. Ra can be, for example, anyof methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl groups.
As the organoaluminum compound, there can be mentioned, for example, any of trialkylaluminums such as trimethylalumifum, triethylaluminum, triisopropylaluminum, triisobutylalurinum, trioctylaluminUm and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diechylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminUm sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichioride, isopropylaluminum sesquichloride, butylaluminum sesquichioride and ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminumdichloride, isopropylaluminumdichloride and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.
Also, as the organoaluminum compound, use can be made of a compound of the formula: RanAlY3-n wherein Ra is as defined above; Y represents a group of the formula ORb, -OS'(Rc) 3 -OARd 2 -NRe 2 P -SiR 3 or -N(Rg)Ah 2; and n is a number of 1 to 2. Each of Rb, Rc, Rd and Rh represents, for example, methyl, ethyl, isopropyl, isobutyl, cyclohexyl or phenyl. Re represents, for example, hydrogen,. methyl, ethyl, isopropyl, phenyl or trimethylsilyl. Eaho fadR represents, for example, methyl or ethyl.
The above organoaluminum compound can be, for example, any of: compounds of the formula RanAl(ORb)3-n, such as dimethylalumiflum methoxide, diethylaluminum ethoxide and dilsobutylaluminum methoxiie; compounds of the formula RanAl(OSiRc3 such as Et 2 Al(OSiMe 3 (iso-Bu) 2 A1(OSiMe 3 and (iso-Eu) 2 A1(OSiBL 3 compounds of the formula RanAl(OAlRd 2 such as Et 2 AlOAlEt 2 and (iso-Bu) 2 AlOAl(iso-Bu) 2 compounds of the formula Ranp l(NRe 2 such as Me 2 AlNEt 2 Et 2 AlNHMe, Me 2 AlNHEt, Et 2 AlN(Me 3 Si) 2 and (iso-Eu) 2 AlN (Me 3 Si) 2; compounds of the formula RanAl(SiRf 3 3 such as (iso-Bu) 2 AlSiMe3; and compounds of the formula RanAl(N(Rg)AlRh 2 3 such as Et 2 AlN(Me)AlEt 2 and (iso-Bu) 2 AlN(Et)Al(i50-Bu) 2 Organoaluminum compounds of the formulae Ra 3 A1, RanAl(ORb 3 and RanAl(OAlRd 2 )3-n are preferred.
The organometallic compound containing a metal of Groups I to III of the periodic table, whose representatives are the above organoaluminum compounds, is also used in the production of a prepolymerization catalyst.
[Electron donor The electrondonor for use in thepresent invention can be, for example, the solubilizing agent employed in the preparation of the solid titanium catalyst component or a silicon compound of the formula: R7nSi(OR8)4-n (i) wherein n is 1, 2 or 3; when n is 1, R 7 represents a secondary or tertiary hydrocarbon group; when n is 2 or 3, at least one of R 7 s represents a secondary or tertiary hydrocarbon group, provided that R7s may be identical with or different fromeachother; andR 8 representsa hydrocarbon group having 1 to 4 carbon atoms, provided that, when 4-n is 2 or 3, R8s may be identical with or different from each other.
With respect to the silicon compound represented by the formula the secondary or tertiaryhydrocarbon group can be an unsubstituted or substituted cyclopentyl, cyclopentenyl or cyclopentadienyl group, or a hydrocarbon group having silicon and, neighboring thereto, a secondary or tertiary carbon.
The above substituted cyclopentyl group can be, for example, an alkylated cyclopentyl group such as 2-methylcyclopentYl, 3-methylcyclopentyl, 2-ethylcyclopentYl, 2-n-butylcyclopentyl, 2, 3-dimethylcyclopentYl, 2, 4-dimethylcyclopentYl, 2, 5-dimethylcyclopentyl, 2, 3-diethylcyclopentyl, 2,3,4.-trimethylcYClopentYl, 2,3,5-trimethylcyclopentYl, 2,3, 4-triethylcyclopentYl, tetramethylcyclopentyl or tetraethylcyclopentYl.
The above substituted cyclopentenyl group can be, for example, an alkylated cyclopentenyl group such as 2-methylcyclopentenyl, 3-methylcyclopentenyl, 2-ethylcyclopentenyl, 2-n-butylcyclopentenYl, 2,3-dimethylcyclopentenYl, 2,4-dimethylcyclopentenyl, 2,5-dimethylcyclopentenYl, 2,3,4-trimethylcYclopentenYl, 2,3, 2, 3, 4-triethylcYclopentenYl, tetramethylcyclopentenyl or tetraethylcyclopentenYl.
The above substituted cyclopentadienYl group can be, for example, an alkylated cyclopentadienyl group such as 2-methylcYclopentadienyl, 3-methylcyclopentadienyl, 2-ethylcyclopefltadienyl, 2-n-butylcyclopentadienyl, 2, 3-imethylcyclopentadienYl, 2, 4-dimethylcYclopentadienYl, 2, 2, 3-diethylcyclopentadienyl, 2,3, 4-trimethylcYClopentadienYl, 2,3, 2,3, 4-triethylcyclopefltadienyl, 2,3, 4, 2,3,4, 5-tetraethy1cyc1opeltadienyl, 1,2, 3, 4, 5-pentamethy1cyclopefltadienyl or 1,2, 3, 4, 5pentaethylcyclop( ntadienyl.
The above hydrocarbon group having silicon and, neighboring thereto, a secondary carbon can be, for example, isopropyl, s-butyl, s-amyl or c-methylbenzyl. The above hydrocarbon group having silicon and, neighboring thereto, a tertiary carbon can be, for example, t-butyl, t-amyl, a,c'-dimethylbenzyl or adamantyl.
The silicon compound represented by the formula when n is 1, can be, for example, a trialkoxysilane such as cyclopentyltrimethoxYsi lane, 2 -methylcyclopentyltrimethoxysilane, 2, 3 -dimethylcyclopentYltrimethoxYsilane, cyclopentyltriethoxysilane, isobutyltriethoxysilane, t-~butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxys-ilane or 2-norbornanetriethoxysilane.
The silicon compound represented by the formula (i) when n is 2, can be, for example, a dialkoxySilane such as dicyclopentyldiethoxysilane, t-uymtydm-~oyiae t-butylmethyldiethoxysilane, t-amylmethyldiethoxYsilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane or 2 -norbornaflemethYldimethoxYs ilane.
When n is 2, it is preferred that the silicon compound represented by the formula be a dimethoxy compound of the formula: R
OCH,
S i (ii) R
OCH,
wherein each of R' and R' independently represents an unsubstituted or substituted cyclopentyl group, an unsubstituted or substituted cyclopentenyl group or an unsubstituted or substituted cyclopentadienyl group, or a hydrocarbon group having silicon and, neighboring thereto, a secondary or tertiary carbon.
The silicon compound represented by the formula (ii) can be, for example, dicyclopentyldimethoxysilane, djcyclopentenyldimethoxysilane, djcyclopentadienyldimethoxysilane, ditbtlietoyiae di (2-methylcyclopentyl) dimethoxysilane, di(3mtycclpny~ietoyiae di 2 -ethylcyclopentyl)dimethoxysilane, di (2,3-iehlylpnyldmtoyiae di 4-dimethylcyclopentyl) dimethoxysilane, di 3 -djethylcyclopentyl)dimethoxysilane, dj( 2 3 4 -trimethylcyclopentyl)dimethoxysilane, di(2, 3, 5 -trimethylcyclopefltyl)dimethoxysilane, di 4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di2mtyccoetnldmtoyiae di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyc1opentenyl) dimethoxysilane, di (2-~nbutylcYClopefltenyl) dimethoxysilane, di 3-dimethylcyclopeltenyl) dimethoxysilane, di 4-dimethy1c'JciopentenYl) dimethoxysilale, di 5-dimethylcyclopeltenYl) dimethoxysilale, di 4-trimethy1cyclopentenyl) dimethoxysilale, di 5.trimethy1cycJlopentelYl) dimethoxysilale, di( 2 3 4 -triethylcyclopefltefyl)dimethoxysilae di (tetramethYlcyclopenteli) dimethoxysilale, di (tetraethylcyclOPeltelYl) dimethoxysilale, di (2-methy1cyc1opeltadielyl) dimethoxysilale, di (3-methy1cyc1opefltadielyl) dimethoxysilale, di 2 -ethylcyc1opefltadiefl)dimethoxysilale, di 2 -n-lbutYlcyc1opeftadieflYl) dimethoxysilale, di 3-dirnethy1cyc1opeltadielyl) dimethoxySilale, di 4-dirnethy1cyc1opeltadielYl) dimethoxysilale, di 5 -dimethy1cyc1opeltadiefl)dimethoxysilale, di( 2 3 -diethy1Oycopeltadiefl)dimethoxysilaflf di( 2 3 4 -trimethycycopeftadiefly1)dimethoxilas di 5 -trimethylccYCopeltadiefl)dimethoxysilale, di( 2 3 4 -triethy1cyclopefltadienyl)dimethoxysilane, di 5 -tetramethylcYclopeltadiefiyl)dimethoxysilale, di( 2 3 4 ,5-tetraethY1cycoPefltaeyldifl hoxydimethoY di 3, 4, 5-pentamethy1cyc1opeltadielyl) dimethoxysilai e di 5-pefltaethyly1cYCopetadielyl) dimethoxysilale, di-t-amyldimethoxysilale, di (acx'-Ydimethylbeflzyl) dimethoxysi lane, di (adarantyl)dimethoxysilafle, adamantyl-t-butyldimethoxysilane, cyclopentylit-butYldimethoxYsilane, diisopropyldimethoxysilane, di-s-butyldimethoxYSilale, di-s-amyldimethoxysilale or isopropyl-s-butyldimethoxysilane.
When n is 3, the silicon compound can be, for example, a monoalkoxysilane such as tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethYlmethoxysi lane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethYlmethoxYsilane, cyclopentyldiethylmethoxysilane or cyclopentyldimethYlethoxYsilane.
Method of polymerizing a-olefin [Principal polymerization] The polymerizationof anaxolef in having 4ormorecarbon atoms according to the present invention can be carried out inthepresenceof the first polymerization catalyst prepared f rom the solid titanium catalyst and the organometallic compound containing a metal of Groups I to III of the periodic table optionally together with the electron donor (C In this principal polymerization, the solid titanium catalyst is generally used in an amount, in terms of titanium atom, of about 0.001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol, per liter of charged volume. The organometallic compound containing a metal of Groups I to III of the periodic table is used so that the amount of metal atoms is generally in the range of about 1 to 2000 mol, preferably about 5 to 500 mol, per mol of titanium atoms contained in the solid titanium catalyst of the polymerization system. The electron donor is generallyusedinanamountofabout0.01to10mol, preferably 0.01 to 2 mol, per mol of metal atoms of the organometallic compound containing a metal of Groups I to III of the periodic table.
The a-olefin having 4 or more carbon atoms for use in the principal polymerization can be, for example, any of 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and l-eicosene, and further any of cyclic olefins having 5 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-l,2,3,4,4a,5,8,8a-octahydron aphthalene. These can be used in combination. Moreover, for example, styrene, vinylcyclohexane, diene, ethylene or propylene can be used as a comonomer. Especially, a copolymer of 1-butene and propylene can be used for general purposes and is a desirable combination of monomers. The a-olefin content is 50 mol% or greater. For satisfactory exertion of the characteristics of the polymerization catalyst of the present invention, the a-olefin content is in the range of 70 to 100 mol%, especially 80 to 100 mol%.
The use of a molecular weight modifier such as hydrogen in the polymerization enables regulating the molecular weight of polymer obtained from an a-olefin having 4 or more carbon atoms. Thus, a polymer of high melt flow rate can be obtained.
The polymerization temperature is generally set for about 20to200C, preferablyabout 50tol50°C. The applied pressure is generally set for atmospheric pressure to MPa, preferably about 2 x 10-1 to 5 MPa.
The polymerization can be performed by any of a batch process, a semicontinuous process and a continuous process.
Further, the polymerization can be performed by a 2 or more stage polymerization process wherein reaction conditions are varied according to stage.
Thepolymerizationofana-olefinhaving 4 ormorecarbon atoms according to the present invention can be effected by any of liquid phase polymerization processes, such as suspension polymerization, and gas phase polymerization processes.
When the principal polymerization is performed by liquid phase polymerization processes, as the solvent, use can be made of an inert hydrocarbon as employed in the following prepolymerization. Also, use can be made of an olefin having 4 or more carbon atoms which is liquid under polymerization conditions.
[Prepolymerization] Thepolymerizationofana-olefinhaving4rmorecarbon atoms according to the present invention can also be effected with the use of the second polymerization catalyst prepared from the prepolymerization catalyst obtained by prepolymerization of an a-olefin in the presence of the solid titanium catalyst and the organometallic compound containing a metal of Groups I to III of the periodic table, optionally together with the organometallic compound containing a metal of Groups I to III of the periodic table and/or the electron donor The process for preparing the second polymerization catalyst (prepolymerization catalyst) and this second polymerization method will be described in detail below. These are substantially not different from the process for preparing the first polymerization catalyst and the polymerizationmethod using the first polymerization catalyst.
With respect to the prepolymerization, the solid titanium catalyst the organometallic compound containing a metal of Groups I to III of the periodic table, the electron donor etc. are reacted together in an inert hydrocarbon medium, and the a-olefin having 4 or more carbon atoms is added to the reaction mixture and prepolymerized under such mild conditions that the temperature is generally in the range of about -20 to +1000C, preferably about -20 to +800C, and still preferably 0 to In the prepolymerization, it is generally preferred that the concentration of solid titanium catalyst be in the range of about 0.001 to 200 mmol, especially about 0.01 to 50 mmol, and more especially 0.1 to 20 mmol, in terms of titanium atom per liter of the inert hydrocarbon medium.
In the prepolymerization, the employed catalyst concentration can be higher than in the principal polymerization.
Inthe prepolymerization, the amount of organometallic compound containing a metal of Groups I to III of the periodic table can be such that 0.1 to 1000 g, preferably 0.3 to 500 g of a polymer of a-olefin having 4 or more carbon atoms is formed per gram of solid titanium catalyst It is generally preferred that the amount be in the range of about 0.1 to 300 mol, especially about 0.5 to 100 mol, and more especially 1 to 50 mol, per mol of titanium atom of solid titanium catalyst According to necessity, the electron donor may be added in the prepolymerization. The electron donor for use in the prepolymerization is, for example, a nitrogenous compound, an oxygen-containing compound or a phosphorous compound. The electron donor is used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, and still preferably 1 to 10 mol, per mol of titanium atom of solid titanium catalyst The above nitrogenous compound can be, for example, any of 2,6-substituted piperidines of the formulae: isoC- H?
H
isoCH, isoCH ,isoC 4
H
9
H
CH3 isoC 3
H,
isoC 3
H,
CH
H H H ~C H
H
C 2 H C 2 Hs cH 3 C H 3 C H 3 C 2 Hs C H
CH
3 C H C 2
H
5
H
CH
3
H
C H C EL
OH
3 COH3
CH
3 CH3 C H 3
N
C H 3 1 C H C H3 C H 3 C CH
CH
3 C H C H 3 C H3 CH 3 C H CH3 C H 3CO0O C 6 H 5 CO0O C H C H C H 3 C H 3 H CH3
OG
8
H
1 1 C00 C H CH 3 C H, I C H 3 A 1(C 2 HS 2
CH
3 H CH 3 CH, H pyrrolidines of the formulae: i soC,-H 7 isoC 3H 7 C H C H H H H
CH
3 H H
CH
3 CH3
CH
3 CH3 NT
N
CH
3 CHs
CH
3 I CH3 C H 3 C 2
H
substituted methylenedianines such as N,NNI,N'-tetramfethyimethyleflediamine and N,N,N' ,N'-tetraethylmethYieflediamile; and substituted imidazolidines such as 1, 3-dibenzylimidazolidile and 1, 3-dibenzyl-2-phelimidazol2-dile.
The above phosphorous compound is preferably a phosphorous acid ester such as triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite or diethyl phenyl phosphite.
As the above oxygen-containing compound, there can be employed, for example, any of 2,6-substituted tetrahydropyrans and 2, 5-substituted tetrahydrofurans of the formulae: C H 3 C H3 C H C 2
H
C 'CfH
CH
3 Cl-H 3 C H
CH
3 CH 3 CzH C H, CH 3 0
C
2
H
5 T C 2 Hs C H 3 C H 3
CH
5
C
2
H
CH 3 Ll 0
C
C H C H As the inert hydrocarbon as a medium for the prepolymerization, there can be mentioned, for example, an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane or kerosine; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclopentane; anaromatichydrocarbonsuch asbenzene, tolueneorxylene; ahalogenatedhydrocarbon suchas ethylene chloride or chlorobenzene; or a mixture of these. Of these inert hydrocarbons, an aliphatic hydrocarbon is preferably employed. When an inert hydrocarbon medium is employed, the prepolymerization is preferably performed by a batch process. The prepolymerization can be performed with the use of an a-olefin having 4 or more carbon atoms per se as a solvent, or can be performed in substantiallysolvent-free condition.
A molecular weight modifier such as hydrogen can be used in the prepolymerization. It is preferred that the molecular weight modifier be used in such an amount that the a-olefin polymer obtained by the prepolymerization has an intrinsic viscosity measured in decalin at 1350C, of about 0.2 dl/g or higher, especially about 0.5 to 10 dl/g.
The a-olefin for use in the prepolymerization may be identical with or different from the a-olefin having 4 or more carbon atoms to be used in the principal polymerization.
In particular, propylene is preferred.
The prepolymerization is terminated about when 0.1 to 1000 g, preferably 0.3 to 500 g, and still preferably 1 to 200 g of an a-olefin polymer has been formed per gram of solid titanium catalyst The solid titanium catalyst and organometallic compound containing a metal of Groups I to III of the periodictable for use in theprepolymerizationareidentical with the solid titanium catalyst and organometallic compound containing a metal of Groups I to III of the periodic table for use in the principal polymerization, respectively.
The solid titanium catalyst of the present invention substantially does not contain carboxylic acid derivatives. Examples of the carboxylic acid derivatives include carboxylic acid esters and carboxylic acid anhydrides. Theexpression"substantiallydoesnotcontain carboxylic acid derivatives" used herein means that the content of carboxylic acid derivatives in the solid titanium catalyst is 5% by weight or less. The content of carboxylic acid derivatives is preferably 1% by weight or less, still preferably 500 ppm or less, and optimally 100 ppm or less.
Therefore, in the polymer or copolymer of a-olefin having 4 or more carbon atoms obtained by the polymerization of the present invention, not only is the content of carboxylic acid derivatives, which are electron donor compounds low but also the content of olefins obtained by isomerization of a-olefin is low.
Theintrinsicviscosity ofthispolymerorcopolymer is in the range of 0.01 to 100 dl/g, preferably 0.1 to dl/g.
Examples The present inventionwillbe further illustratedbelow with reference to the following Examples, which in no way limit the scope of the invention.
Example 1 [Preparation of solid titanium catalyst component kg (63 mol) of anhydrous magnesium chloride, 26.6 lit. ofdecaneand29.2 lit. (189mol) of2-ethylhexylalcohol were heated at 1400C for 4 hr so as to effect a reaction thereof, thereby obtaining a homogeneous solution.
Subsequently, 1.59 kg (7.88 mol) of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added to the homogeneous solution, and agitated at 110°C for 1 hr.
The thus obtained homogeneous solution was cooled to room temperature, and 37.0 kg thereof was dropped into 120 lit. (1080mol) oftitaniumtetrachloridemaintainedat- 2 4
°C
over a period of 2.5 hr. The thus obtained solution was heatedoveraperiodof6hr, and, whenthetemperaturethereof reached 110°C, 0.68 kg (3.37 mol) of 2-isopropyl-2-isobutyl-l,3-dimethoxypropane was added thereto.
Further, the solution was agitated at 110°C for 2 hr so as to effect a reaction. Solid was collected from the reaction mixture by hot filtration, placed in 132 lit. of titanium tetrachloride, and agitated into a slurry. The slurry was heated at 110°C for 2 hr so as to effect a further reaction.
Solid was again collected from the reaction mixture by hot filtration and washed with 900C decane and hexane.
Washingwasterminatedwhentitaniumcompoundswereno longer detected in the washing fluid. Thus, solid titanium catalyst component was obtained.
Part of a hexane slurry of solid titanium catalyst component was sampled and dried, and a dried sample was analyzed. The quantitative composition by weight of solid titanium catalyst component exhibited 3.0% of titanium, 57% of chlorine, 17% of magnesium and 18.0% of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane.
[Copolymerization of 1-butene and propylene] Copolymerizationof 1-butene andpropylenewas carried out by feeding a continuous polymerization reactor of 200 lit. internal volume with 73 lit./hr of hexane, 16 kg/hr of 1-butene, 0.07 kg/hrof propylene, 0 Nlit./hrof hydrogen, 0.38 mmol (in terms of titanium atom)/hr of solid titanium catalyst component 38 mmol/hr of triethylaluminum and 1.3mmol/hrof cyclohexylmethyldimethoxysilane. Thus, a copolymer was obtained at a rate of 4.8 kg/hr. In that copolymerization, the temperature was 60 0 C, the average residence time 0.8 hr, and the total pressure 3x10 1 MPa-G.
The properties of obtained copolymer (propylene content, intrinsic viscosity molecular weight distribution Mw/Mn, melting point Tm, isotactic pentad fraction, 1/2 crystal transition time, tensile modulus E and B value) are listed in Table 1.
[Production of resin composition] The thus obtained 1-butene/propylene copolymer was mixed with poly-1-butene (melting point: 124°C, intrinsic viscosity: 1.2, Mw/Mn: 3.6, 1/2 crystal transition time: hr and isotactic pentad fraction: 94.1%) in a weight ratio of 4:1. 100 parts by weight of obtained resin composition was incorporated with 0.2 part by weight of high density polyethylene (MFR: 13 g/10 min and density: 965 kg/m 3 as a nucleating agent and further with a heat stabilizer, and melt blended by means of a single-screw extruder of 40 mm screw diameter. Thus, there was obtained a resin composition, the properties of which are listed in Table 1.
[Production of pipe] The thus obtained resin composition was incorporated with heat stabilizer (phenolic, benzotriazole-based, metallic soap) and pelletized by means of a single-screw extruder. Obtained pellets were extruded into pipes of 27 mm inside diameter and 2.4 mm wall thickness by means of a pipe forming machine of 90 mm screw diameter under such conditions that the preset temperature, cooling water temperature and pipe forming speed were 180°C, 11°C and 3 m/min, respectively.
A hydrostatic test of pipes was performed, and the results thereof are also listed in Table 1.
[Measuring method] The properties of butene/propylene copolymer, resin composition containing butene/propylene copolymer and pipes were measured in the following manner.
Content of propylene in butene/propylene copolymer to 50 mg of copolymer was dissolved in 0.5 cm 3 of hexachlorobutadiene and measured by means of superconducting NMR (model GSH-270, manufactured by JEOL LTD.) under such conditions that the measuring temperature was 115 to 120 0 C, the measured range 180 ppm, the cumulative frequency 500 to 10,000, the pulse separation 4.5 to 5 sec, and the pulse duration 450.
Melting point Tm 1 Copolymer was sandwiched by means of 50 m thick polyester sheets, 100 ~m thick aluminum plates and 1 mm thick iron plates with the use of a metal frame of 0.1 mm thickness, heated at 190°C for 5 min, deaerated under 5 MPa, maintained at 5 MPa for 5 min, and cooled by means of a cooling press water-cooled at 20°C under 5 MPa for 5 min. Thus, a sheet was obtained.
The sheet was allowed to stand still at room temperature for 7 days, and 4 to 5 mg thereof was charged in a sample pan of differential scanning calorimeter (model DSC-2, manufactured by Perkin-Elmer Corp.). The temperature was raised from 20°C to 200°C at a rate of 10'C/min. The temperature at melting peak apex during the temperature rise was designated as Tm 1 The melting point is a scale of heat resistance.
Tensile modulus
E
Copolymer was formed into a 2 mm thick sheet in the same manner as in the measurement of melting point except that a metal frame of 2 mm thickness was used, allowed to stand still for 7 days, and used as a measuring sample. The obtained sample was measured by the use of universal testing machine, model ASTM IV, manufactured by Instron under such conditions that the chuck spacing was 64 mm, and the stress rate 50 mm/min.
The tensile modulus E at 23 0 C indicates the hardness in use condition and is a scale of the pressure resistance strength of pipe. The tensile modulus E at 95 0 C indicates the hardness at high temperature and is a scale of the heat resistance.
Molecular weight distribution Mw/Mn Using standard polystyrenes of known molecular weights (monodisperse polystyrenes, produced by Tosoh Corporation), GPC (gel permeation chromatography) counts corresponding to polystyrene molecular weights M were measured, and a calibration curve of molecular weight M and EV (elution volume) was prepared.
(ii) Gel permeation chromatogram of a sample was measured by GPC, and, with the use of calibration curve prepared in above, the number average molecular weight defined by the formula Mn ZMiNi INi and the weight average molecular weight defined by the formula Mw EMi 2 Ni ZMiNi were calculated. Thus, Mw/Mn was determined.
The molecular weight distribution is a scale of flexibility and extrudability.
Intrinsic viscosity [n] The specific viscosity of a decalin solution of each sample was measured at 135C by the use of Atlanticviscometer, and the intrinsic viscosity was calculated from the specific viscosity.
The intrinsic viscosity is a scale of strength and extrudability.
1/2 crystal transition time The ratio of I-type crystal (100) face reflection peak intensity to II-type crystal (200) face reflection peak intensity was measured by the use of X-ray diffractometer (model RU-300 manufactured by Rigaku Denki Co., Ltd., Cu target, 50 kV, 300 mA), and the time required to reach 1/2 of an intensity ratio saturation value was determined.
The 1/2 crystal transition time is a scale of the cure time after molding.
B value BB, BP and PP diad molar fractions were determined by measuring 40.2 ppm (ascribed to BB diad) 43.3ppm (ascribed to BP diad) and 46.4 ppm (ascribed to PP diad) skeletal methylene peak areas on the NMR spectrum obtained by means of NMR analyzer (model LA-500 FT-NMR, manufactured by JEOL LTD.) under such conditions that the measuring temperature: 1200C, the solvent: o-dichlorobenzene, the internal standard: deuterobenzene, the pulse mode: proton complete decoupling, the pulse duration: 450, and the pulse separation: 5.5 sec. Fromthe obtaineddiadmolar fractions, the B (1-butene) content was calculated by the formula B BB BP 2, the P (propylene) content by the formula P =PP+BP/2, andtheBvaluebytheformulaBvalue=BP/(2xBxP) Herein, BB represents a 1-butene chain, BP a bonding of 1-butene and propylene, and PP a propylene chain.
The B value is a scale of the randomness of copolymer.
The increase of B value means the shortening of 1-butene chain or propylene chain, and hence means the increase of the uniformity of 1-butene and propylene distribution.
Isotactic pentad fraction The isotactic pentad fraction was measured by means of NMR analyzer (model LA-500 FT-NMR, manufactured by JEOL LTD.) under such conditions that the measuring temperature: 120 0 C, the solvent: hexachlorobutadiene, and the internal standard: deuterobenzene.
The isotactic pentad fraction indicates the stereoregularity of (co)polymer.
Hydrostatic strength of pipe The hydrostatic strength of pipe was measured at 95 0
C
and at a hoop stress of 6 MPa in accordance with ISO 167.
The results are also listed in Table 1. In the Examples, the hydrostatic strengths exceeded 20 thousand hours. Thus, the pipes have satisfactory practical strength.
Example 2 [Preparation of solid titanium catalyst component 4.28 kg (45 mol) of anhydrous magnesium chloride, 26.6 lit. ofdecaneand21.11it. (135mol) of2-ethylhexylalcohol were heated at 140 0 C for 5 hr so as to effect a reaction thereof, thereby obtaining a homogeneous solution.
Subsequently, 1kg (6.78mol) of phthalicanhydridewas added to the homogeneous solution, and agitated at 130 0 C for 1 hr to thereby obtain a homogeneous solution.
The thus obtained homogeneous solution was cooled to room temperature, and was dropped into 120 lit. (1080 mol) of titanium tetrachloride maintained at -20'C over a period of2 hr. The thus obtained solution was heated over a period of 4 hr, and, when the temperature thereof reached 110'C, 3.02 lit. (11.3 mol) of diisobutyl phthalate was added thereto.
Further, the solution was agitated at 110 0 C for 2 hr so as to effect a reaction. Solid was collected from the reaction mixture by hot filtration, placed in 165 lit. of titanium tetrachloride, and agitated into a slurry. The slurry was heated at 110°C for 2 hr so as to effect a further reaction.
Solid was again collected from the reaction mixture by hot filtration and washed with 110 0 C decane and hexane.
Washingwasterminatedwhentitanium compoundswereno longer detected in the washing fluid. Thus, solid titanium catalyst component was obtained.
Part of a hexane slurry of solid titanium catalyst component was sampled and dried, and a dried sample was analyzed. The quantitative composition by weight of solid titanium catalyst component exhibited 2.5% of titanium, 58% of chlorine, 18% of magnesium and 13.8% of diisobutyl phthalate.
[Copolymerization of 1-butene and propylene] A 1-butene/propylene copolymer was produced by carrying out copolymerization in the same manner as in Example 1, except that dicyclopentyldimethoxysilane was used in place of cyclohexylmethyldimethoxysilane as organosilicon compound catalyst component and that the copolymerization was conducted at 57.5°C. The copolymerization conditions are listed in Table 1.
[Production of resin composition and pipe] In the same manner as in Example 1, the thus obtained copolymer was mixed with poly-1-butene, a nucleating agent and additives to thereby obtain a resin composition, and the resin composition was formed into a pipe.
The properties of obtained copolymer and resin composition and the pipe hydrostatic test results are listed in Table 1.
Example 3 Poly-l-butene having the properties specified in Table 1 was produced according to the same process for producing a butene/propylene copolymer as in Example 2, except that, as the organometallic compound catalyst component triisobutylaluminum was used in place of triethylaluminum, and cyclohexylmethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane and that the polymerization was carried out under conditions specified in Table 1.
In the same manner as in Example 1 except that 0.05 part by weight of ethylenebisstearylamide was used in place of 0.2 part by weight of high density polyethylene as the nucleating agent, the obtained polymer was mixed with 1 101 poly-l-butene to thereby obtain a resin composition, and the resin composition was formed into a pipe.
Thepropertiesof obtainedpolymerandresincomposition and the pipe hydrostatic test results are listed in Table 1.
Comparative Example 1 Poly-l-butene having the properties specified in Table 1 was produced according to the same process for producing a butene/propylene copolymer as in Example 2, except that propylene as a copolymer component was not used, that, as the organometallic compound catalyst component triisobutylaluminum was used in place of triethylaluminum, and cyclohexylmethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane, and that the polymerization was carried out under conditions specified in Table 1.
In the same manner as in Example 1, the thus obtained polymer was mixed with poly-l-butene to thereby obtain a resin composition, and the resin compositionwas formed into a pipe.
The properties of obtained polymer and resin composition and the pipe hydrostatic test results are listed in Table 1.
Comparative Example 2 A butene/propylene copolymer having the properties specified in Table 1 was produced according to the same process for producing a butene/propylene copolymer as in Example 2, except that, as the organometallic compound catalyst component triisobutylaluminum was used in place of triethylaluminum, and cyclohexylmethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane, and that the copolymerization was carried out under conditions specified in Table 1.
In the same manner as in Example 1, the thus obtained copolymer was mixed with poly-l-butene to thereby obtain a resin composition, and the resin composition was formed into a pipe.
The properties of obtained copolymer and resin composition and the pipe hydrostatic test results are listed in Table 1.
Al/donor pressure polyml. temp.
-residence time amt. of polymer formed activity C3 content M. P.
intrinsic viscosity unit ratio molar ratio kg/cm 2 0oC h kg/h kg/mol -Ti mol% 0oc dl /g Table 1 Examp, Examp Examp Comp. COMP.
-le 1 -le 2 -le 3 Ex. 1 Ex. 2_ butene copolymer
(A)
c-1 c-2 c-2 c-2 c-2 TEA TEA TIBA ITIBA_ TIBA *1 *2 *1 *1 *1 100 100 100 100 100 3 30 30 30 3 60 10.8 4 4.8 3 57 5 0. 8 4. 8 3 3 60 -1 4 .8 3 F4 48 10000 1 10000 1 3000 3000 3000 2.8 126 3 3. 5 93. 3 3. 6 3. 5 93.5 5.4 118 3 3.8 89. 5 3. 8 90 .8 5 .4 118 3 3.8 89. 6 M Pa 40 16 2 I300 2-75 MPa 11 400 23__ 86 90 86 MPa unit pts .wt pts .wt mol% 351 1346 ~334 j370 334 23 10 7 48 -7 0.95 0. 98 0.91 0. 91 resin compsn. 0.2 0.2 0 0.2 0.2 0 0 0.05 0 0 2.2 2.9 4.3 0 4.3
M.P.
intrinsic viscosity Mw/Mn i3otactic pentad fraction 1/2 crystal transition time tensile modulus 23"C tensile modulus 2 3 0 C 400--66.6677xxC3 st tic ,mp, s t gt Fhydrostatic trength 00 95'Cx6MPa B value c 126 dl/g 2.5 125 126 2.5 2. 5 403 4. 1 93.3 389. 8 2. 5 4 .05 91.2 12 3 2. 4. 1 8 9.8 4 .02 93 .7 E h 20 85 40 MPa 480 520 330 320 300 MPa 145 160 140 120 115 MPa h 385 381 371 >24526 >24526 2 157 4 -0 .9 3-O 0.9 6 0.8 9 400 371 13985 11725 0.89 Note) Formulation of resin composition: butene copolymer/poly-lbutene 4/1 (weight ratio), cyclohexylmethyldimethoxysilane, dicyclopentYldimethoxYsilanet high density polyethylene. (MFR: 13 g/l~min, and density: 965 kg/rn and ethylenebisstearYlamide.
Example 4 [Preparationl of solid titanium catalyst component
I
6. 0 kg (63 mol) of anhydrous magnesium chloride, 2 6. 6 lit. of decane and 29.2 lit. (189 mol) of 2-ethyihexanol were heated at 140°C for 4 hr so as to effect a reaction thereof, thereby obtaininga homogeneous magnesium compound solution Subsequently, 1.59 kg (1.88 mol) of 2-isopropyl-2-isobutyl-l,3-dimethoxypropane was added to the solution and agitated at 110 0 C for 1 hr.
The thus obtained homogeneous magnesium/polyether solution (II) was cooled to room temperature, and 37.0 kg thereof was dropped into 120 lit. (1080 mol) of titanium tetrachloride maintained at -24°C over a period of 2.5 hr.
The thus obtained magnesium/titanium solution (III) was heated overaperiodof 6 hr, and, when thetemperaturethereof reached 1100C, 0.68 kg (3.37 mol) of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added thereto. Further, the resultant solution (IV) was agitated at 110 0 C for 2 hr so as to effect a reaction. Solid was collectedfromthereactionmixtureby hot filtration, placed in 132 lit. of titanium tetrachloride, and agitated into a slurry. The slurry was heated at 110°C for 2 hr so as to effect a further reaction.
Solid was again collected from the reaction mixture by hot filtration and washed with 1100C decane and hexane.
Washing was terminatedwhentitanium compoundswereno longer detected in the washing fluid. Thus, solid titanium catalyst was obtained.
Part of a hexane slurry of solid titanium catalyst was sampledanddried, and a driedsamplewas analyzed.
The quantitative composition by weight of solid titanium catalyst exhibited3. 0% of titanium, 17%of magnesium, 57% of chlorine and 18.0% of 2-isopropyl-2-isobutyl-l,3-dimethoxypropane.
Diisobutyl phthalate was not detected.
[Polymerization] Copolymerization of 1-butene andpropylenewas carried out by feeding a continuous polymerization reactor of 200 lit. internal volume with 73 lit./hr of hexane, 16 kg/hr of 1-butene, 0.07 kg/hr of propylene, 10 Nlit./hr of hydrogen, 0.38 mmol (in terms of titanium atom)/hr of solid titanium catalyst 38 mmol/hr of triethylaluminum and 1. 3mmol/hr of cyclohexylmethyldimethoxysilane (CMMS) Thus, a copolymer was obtained at a rate of 4.8 kg/hr. In that copolymerization, the temperature was 60 0 C, theaverage residence time 0.8 hr, and the total pressure 3x10-1 MPa-g.
The properties of obtained copolymer (propylene content, melting point, intrinsic viscosity and molecular weight Sdistribution) are listed in Table 2.
The content of propylene in butene/propylene copolymer was measured in the following manner.
to 50 mg of obtained copolymer was dissolved in cm 3 of hexachlorobutadiene and measured by means of superconducting NMR (model GSH-270, manufactured by JEOL LTD. under such conditions that the measuring temperature was 115 to 120'C, the measured range 180 ppm, the cumulative frequency 500 to 10,000, the pulse separation 4.5 to 5 sec, and the pulse duration The melting point Tml was measured in the following manner.
Copolymer was sandwiched by means of 50 pm thick polyester sheets, 100 um thick aluminum plates and 1 mm thick iron plates with the use of a metal frame of 0.lmm thickness, heated at 190 0 C for 5 min, deaerated under 5 MPa, maintained at 5 MPa for 5 min, and cooled by means of a cooling press water-cooled at 20 0 C under 5 MPa for 5 min. Thus, a sheet was obtained. The sheet was allowed to stand still at room temperature for 7 days, and 4 to 5 mg thereof was charged in a sample pan of differential scanning calorimeter (model DSC-2, manufactured by Perkin-Elmer Corp.). The temperature wasraisedfrom200Cto 200Cat a rateof The temperature at melting peak apex during the temperature rise was designated as Tm 1 The melting point is a scale of heat resistance.
The intrinsic viscosity was measured in the following manner.
The specific viscosity of a decalin solution of each samplewasmeasuredat 135C by the use of Atlanticviscometer, and the intrinsic viscosity was calculated from the specific viscosity.
The intrinsic viscosity is a scale of strength and extrudability.
The amount of 2-butene formed was measured in the following manner.
The amount of 2-butene formed during polymerization was determinedbymeasuring the amount of 2-butene contained in the gas phase within the polymerization reactor by gas chromatography.
Comparative Example 3 [Preparation of solid titanium catalyst component 4.28 kg (45 mol) of anhydrous magnesium chloride, 22.5 lit. of decane and 21.1 lit. (135 mol) of 2-ethylhexanol were heated at 140 0 C for 5 hr so as to effect a reaction t-hereof, thereby obtaining a homogeneous magnesium compound solution Subsequently, 1 kg (6.78 mol) of phthalic anhydride was added to the solution and agitated at 130 0 C for 1 hr to thereby effect dissolution of phthalic anhydride.
The thus obtained homogeneous magnesium/phthalic anhydride solution was cooled to room temperature, and lit. of the homogeneous solution was dropped into 120 lit.
(1080 mol) of titanium tetrachloride maintained at -20 0
C
over a period of 2 hr. The thus obtained magnesium/titanium solution was heated over a period of 4 hr, and, when the temperature thereof reached 110 0 C, 3.02 lit. (11.3 mol) of diisobutyl phthalate was added thereto. Further, the solution was agitated at 110 0 C for 2 hr so as to effect a reaction. Solid was collected from the reaction mixture by hot filtration, placed in 165 lit. of titanium tetrachloride, and agitated into a slurry. The slurry was heated at 110 0 C for 2 hr so as to effect a further reaction.
Solid was again collected from the reaction mixture by hot filtration and washed with 110 0 C decane and hexane.
Washingwasterminatedwhentitaniumcompoundswerenolonger detected in the washing fluid. Thus, solid titanium catalyst was obtained.
Part of a hexane slurry of solid titanium catalyst was sampledanddried, and a driedsamplewas analyzed.
The quantitative composition by weight of solid titanium catalyst exhibited2.4%of titanium, of chlorine and 13.0% of diisobutyl phthalate.
Therefore, the content of carboxylic acid derivative is 13.0%.
Withrespecttothecontentof phthalicacidderivatives, itwas measuredby gas chromatography. Specifically, about g of a sample was weighed into a 50 ml measuring flask.
Acetone was added thereto so as to dissolve the sample. An internal standard substance was added and agitated. 13% aqueous ammonia was dropped thereinto so as to effect a decomposition. The liquid was allowed to stand still so as to effect a separation, and the upper layer portion was taken out as a sample. The sample was separated into component fractions with the use of a fused silica capillary column as a separation column, and the amounts thereof were determined by an internal standard method.
[Polymerization] A butene/propylene copolymer was produced by conducting copolymerization in the same manner as in Example 4, except that solid titanium catalyst was used. The results are listed in Table 2.
Table 2 Solid titanium catalyst and activity Properties of polymer Designation Mg Ti halogen polyether hydrocarbon ethylhexanol carboxylic acid deriv.
(diisobutyl phthalate) polymn. activity 3.0 57 18.0 2.2 2.8 0 2.4 0 2.6 13.0 3000 43 2.8 120 3 3.8 10000 amt. of 2-butene ppm formed propylenecontent mol% m.p.
°C
intrinsic visc. dl/g Mw/Mn 2.8 126 3 3.5 A molded item which is excellent in heat resistance, low-temperature properties and handling easiness and which exhibits extremely enhanced thermal creep property can be obtained from the butene copolymer or resin composition comprising butene copolymer according to the present invention. Therefore, the molded item of the present invention, especially pipe, is excellent in not only heat resistance, low-temperature properties and handling easiness but also thermal creep property.
Moreover, a polymer or copolymer of an c-olefin having 4ormorecarbon atoms, including the abovebutenecopolymer, which is characterized by uniform particle size, less fine powder, high bulk density and substantially not containing carboxylic acids can be easily produced with high polymerization activity by the use of the solid titanium catalyst and a-olefin polymerization process according to the present invention.
Industrial Applicability A molded item which is excellent in heat resistance, low-temperature properties and handling easiness and which exhibits extremely enhanced thermal creep property can be obtained from the butene copolymer or resin composition comprising butene copolymer according to the present invention. Therefore, the molded item of the present invention, especially pipe, is excellent in not only heat resistance, low-temperature properties and handling easiness but also thermal creep property, thereby ensuring high industrial applicability.
Moreover, a polymer or copolymer of an a-olefin having 4 or more carbon atoms, including the above butene copolymer, which is characterized by uniform particle size, less fine powder, high bulk density and substantially not containing carboxylic acids can be easily produced with high polymerization activity by the use of the solid titanium catalyst and a-olefin polymerization process according to the present invention, thereby ensuring high industrial applicability.

Claims (9)

1. A butene copolymer comprising 99.9 to 80 mol% of copolymer units derived from 1-butene and 0.1 to 20 mol% of copolymer units derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded), said butene copolymer having: (la) a tensile modulus E (measured at 23°C) of 345 MPa or greater and/or (Ib) a tensile modulus E (measured at 950C) of 133 MPa or greater, and a ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of 2 to an intrinsic viscosity (measured in decalin as a solvent at 135°C) of 1 to 6 dl/g, and a melting point Tm (measured by a differential scanning calorimeter) of 1500C or below.
2. The butene copolymer as claimed in claim 1, wherein the tensile modulus E (measured at 230C) satisfies the relationship: E (MPa) 370 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)) wherein the content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) is molar percentage based on the butene copolymer
3. The butene copolymer as claimed in claim 1 or 2, which exhibits a 1/2 crystal transition time (measured by X-ray diffractometry) of 40 hr or less.
4. The butene copolymer as claimed in any of claims 1 to 3, which exhibits: B value determined by 13 C-NMR of 0.92 to 1.1, said B value calculated by the formula: B value POB/(2PO-P B wherein POB represents the ratio of the number of butene-a-olefin chains to the total number of chains, Pg represents the molar fraction of butene component, and PO represents the molar fraction of a-olefin component, and an isotactic pentad fraction determined by 1 3 C-NMR of 91% or greater. 'The butene copolymer as claimed in any of claims 1to4, whereinthe ratio (Mw/Mn) ofweight-averagemolecular weight (Mw) to number-average molecular weight (Mn) is in the range of 2 to 7.9.
6. The butene copolymer as claimed in any of claims 1 to 5, wherein the copolymer units derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) are propylene units.
7. The butene copolymer as claimed in any of claims 1 to 6, which exhibits only one endothermic peak (melting pointTm) in a measurementbymeansof a differentialscanning calorimeter.
8. The butene copolymer as claimed in any of claims 1to7, produced withtheuseofa catalyst system comprising: a solid titanium catalyst component containing titanium, magnesium, a halogen and a compound having at least two ether bonds represented by the formula: R 22 Rn R 2 R 2 4 I I I I R 2 -O-C-R 26 R" 2 R' R" R 2 wherein each of R 1 to R 26 represents a substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, ahalogen, nitrogen, sulfur, phosphorus, boron and silicon, provided that any R 1 to R 2 6 substituents may form a ring other than benzene ring and that an atom other than carbon may be contained in a main chain of the compound having at least two ether bonds, and wherein n is an integer satisfying the relationship 2 s n 10; and an organometallic compound catalyst component (d) containing a metal of Groups I to III of the periodic table.
9. A butene copolymer resin composition comprising a butene copolymer comprising
99.9 to 80 mol% of copolymer units derived from -buteneand 0. 1 to20 mol%ofcopolymer units derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded), said butene copolymer resin composition having: (la) a tensile modulus E (measured at 23 0 C) of 360 MPa or greater and/or (lb) a tensile modulus E-(measured at 95 0 C) of 138 MPa or greater, and a ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of 2 to an intrinsic viscosity (measured in decalin as a solvent at 1350C) of 1 to 6 dl/g, and a melting point Tm (measured by a differential scanning calorimeter) of 110 to 1500C. The butene copolymer resin composition as claimed in claim 9, wherein the tensile modulus E (measured at 230C) satisfies the relationship: E (MPa) 400 6.67 x (content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded)) wherein the content of a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) is molar percentage based on the whole butene copolymer resin composition. 11. The butene copolymer resin composition as claimed in claim 9 or 10, which exhibits a 1/2 crystal transition time (measured by X-ray diffractometry) of 40 hr or less. 12. The butene copolymer resin composition as claimed in any of claims 9 to 11, which further comprises a nucleating agent. 13. The butene copolymer resin composition as claimed in claim 12, wherein the nucleating agent is an amide compound. 14. The butene copolymer resin composition as claimed in any of claims 9 to 13, which exhibits: B value determined by 1 3 C-NMR of 0.90 to 1.08, said B value calculated by the formula: B value POB/(2PO'PB) wherein POB represents the ratio of the number of butene-a-olefin chains to the total number of chains, PB represents the molar fraction of butene component, and Po represents the molar fraction of a-olefin component, and an isotactic pentad fraction determined by 1 3 C-NMR of 91.5% or greater. The butene copolymer resin composition as claimed in any of claims 9 to 14, wherein the ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) is in the range of 2 to 7.9. 16. The-butene copolymer as claimed in any of claims 9 to 15, wherein the copolymer units derived from an a-olefin having 2 to 10 carbon atoms (provided that 1-butene is excluded) for constituting the butene copolymer are propylene units. 17. The butene copolymer resin composition as claimed in any of claims 9 to 16, which further comprises poly-l-butene 18. The butene copolymer resin composition as claimed in any of claims 9 to 17, which comprises 40 to 90% by weight of butene copolymer and 60 to 10% by weight of poly-l-butene 19. The butene copolymer resin composition as claimed in any of claims 9 to 18, which comprises butene copolymer or butene copolymer together with poly-l-butene saidbutenecopolymer andsaidpoly-1-butene produced with the use of a catalyst system comprising: a solid titanium catalyst component containing titanium, magnesium, a halogen and a compound having at least two ether bonds represented by the formula: R 22 R 2 R 24 I I I R2-C-O- C-R 26 R 2 R R" R 2 wherein each of R 1 to R 2 6 represents a substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, ahalogen, nitrogen, sulfur, phosphorus, boron and silicon, provided that any R 1 to R 2 6 substituents may form a ring other than benzene ring and that an atom other than carbon may be contained in a main chain of the compound having at least two ether bonds, and wherein n is an integer satisfying the relationship 2 n 10; and an organometallic compound catalyst component (d) containing a metal of Groups I to III of the periodic table. A molded item comprising the butene copolymer (A) according to any of claims 1 to 8 or the butene copolymer resin composition according to any of claims 9 to 19. 21. The molded item as claimed in claim 20, which is in the form of a pipe. 22. The molded item as claimed in claim 21, which exhibits a breaking time of 20 thousand hours or more in a hydrostatic test of pipe (measured at 95 0 C at a hoop stress of 6 MPa) 23. The molded item as claimed in claim 20, which is in the form of a pipe joint. 24. A solid titanium catalyst for polymerizing an a-olefin having 4 or more carbon atoms, comprising: to 35% by weight of magnesium 0.3 to 10% by weight of titanium to 75% by weight of a halogen to 30% by weight of a compound having at least two ether bonds between which a plurality of atoms are interposed (d 0.05 to 20% by weight of a hydrocarbon and 0.05 to 7% by weight of a solubilizing agent 25. A solid titanium catalyst for polymerizing an a-olefin having 4 orkmore carbon atoms, produced by bringing a halogenous magnesium compound a solubilizing agent (P) capable of dissolving the halogenous magnesium compound (a) and a first compound having at least two ether bonds between which a plurality of atoms are interposed into mutual contact in a solvent to thereby obtain a solution (II) and contacting a liquid titanium compound with the solution (II). 26. The solid titanium catalyst for polymerizing an a-olefin having 4 or more carbon atoms as claimed in claim 24 or25, which substantially does not contain any carboxylic acid derivative. 27. A process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms, comprising polymerizing or copolymerizing an a-olefin having 4 or more carbon atoms in the presence of a solid titanium catalyst and an organometallic compound containing a metal selected from among metals of Groups I to III of the periodic table optionally together with an electron donor said solid titanium catalyst comprising: to 35% by weight of magnesium 0.3 to 10% by weight of titanium to 75%- by weight of a halogen to 30% by weight of a compound having at least two ether bonds between which a plurality of atoms are interposed (d 0.05 to 20% by weight of a hydrocarbon and 0.05 to 7% by weight of a solubilizing agent 28. A process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms, comprising polymerizing or copolymerizing an a-olefin having 4 or more carbon atoms in the presence of a solid titanium catalyst and an organometallic compound containing a metal selected from among metals of Groups I to III of the periodic table optionally together with an electron donor said solid titanium catalyst produced by bringing a halogenous magnesium compound a solubilizing agent capable of dissolving the halogenous magnesium compound and a first compound having at least two ether bonds between which a plurality of atoms are interposed into mutual contact in a solvent to thereby obtain a solution (II) and contacting a liquid titanium compound with the solution (II). 29. A process for producing a polymer or copolymer of an a-olefin having-4 or more carbon atoms, comprising polymerizing or copolymerizing an a-olefin having 4 or more carbon atoms in the presence of the solid titanium catalyst of claim 27 or 28 wherein substantially no carboxylic acid derivative is contained and an organometallic compound containing a metal selected from among metals of Groups I to III of the periodic table optionally together with an electron donor The process for producing a polymer or copolymer of an a-olefin having 4 or more carbon atoms as claimed in any of claims 27 to 29, wherein 1-butene or 1-butene together with another a-olefin having 4 or more carbon atoms is polymerized or copolymerized. 31. A polymer or copolymer of an a-olefin having 4 or more carbon atoms, which has an a-olefin content of 50 mol% or greater and is obtained by the polymerization or copolymerization ofan a-olefin having 4 ormorecarbon atoms as claimed in any of claims 27 to DATED this 2 3 rd day of June, 2005 MITSUI CHEMICALS, INC. by DAVIES COLLISON CAVE Patent Attorneys.for the Applicant(s)
AU2005202759A 2000-07-03 2005-06-23 Butene copolymer, resin composition comprising the copolymer and moldings of the composition, and solid titanium catalyst for producing the copolymer and method for preparing the catalyst Abandoned AU2005202759A1 (en)

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AU67915/01A AU782607C (en) 2000-07-03 2001-07-03 Butene copolymer, resin composition comprising the copolymer and moldings of the composition, and solid titanium catalyst for producing the copolymer and method for preparing the catalyst
AU2005202759A AU2005202759A1 (en) 2000-07-03 2005-06-23 Butene copolymer, resin composition comprising the copolymer and moldings of the composition, and solid titanium catalyst for producing the copolymer and method for preparing the catalyst

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