Patent Application
20070010639
The present invention relates to a novel telechelic polyolefin.
Polyolefins such as polyethylene (PE) and polypropylene (PP) are light and inexpensive and further have characteristics of having excellent physical properties and workability. On the other hand, high chemical stability of polyolefins is an obstacle for giving, thereto, high functionalities, typical examples of which include printability, paintability, heat resistance and impact resistance, and a function for improving compatibility thereof with other polar polymers. There are known methods for making up for such drawbacks and causing polyolefins to have functionalities. Examples thereof include a method of polymerizing an olefin with a polar monomer such as vinyl acetate or a methacrylic acid ester by radical polymerization; and a method of grafting a polar monomer such as maleic anhydride to a polyolefin in the presence of a peroxide. However, according to these methods, it is generally difficult to control minutely the structure of olefin chain moieties in the resultant polymers. As a result, excellent, original physical properties of polyolefin may be damaged.
In general, it is well known that a process using living polymerization is useful as a process for producing such a polymer. In the case of highly-controlled living polymerization, a growing terminal of the polymer quantitatively keeps reactivity. It is therefore known that the reactivity is used to cause the terminal to react directly with a polar-group-containing monomer, whereby a polymer having a functional group at its terminal position can be effectively produced.
However, in the case of polymerizing any olefin by living polymerization, chain transfer reaction of the growing polymer chain is frequently caused under ordinary conditions; therefore, it is very difficult to produce an olefin polymer by living polymerization. Some examples wherein an α-olefin is subjected to living polymerization have been reported so far. However, in any one of the examples, the polymerization is conducted at a very low temperature in order to control chain transfer reaction. The polymerization activity thereof is also a low value. The molecular weight thereof is also at most several tens of thousands. Furthermore, monomers that can be polymerized are restricted in many cases. It is particularly difficult to produce industrially important ethylene-based (co) polymers or block copolymers. Concerning stereoregular polymerizations of α-olefins, living polymerizations exhibiting a high stereoregularity are hardly known (see, for example, “Kobunshi”, 1988, 47(2), 74-77).
Under such situations, the Applicant already discloses a transition metal compound having a salicylaldimine ligand as a novel catalyst for olefin polymerization (see Japanese Patent Application Laid-Open No. 11-315109, and further suggests a process of using the transition metal compound to produce a novel single-terminal vinyl-group-containing copolymer or a novel polar-group-containing block copolymer (see Japanese Patent Application Laid-Open Nos. 2003-73412 and 2003-40953). However, the two published documents neither disclose any polymer having polar functional groups at both of its terminals nor any process for the production thereof.
A polymer degradation process is known as a process for producing a linear polyolefin having functional groups at both of its terminals. For example, it is reported that polypropylene is thermally decomposed under appropriate conditions, thereby yielding a polypropylene oligomer having vinylidene groups at both of its terminals (see, for example, WO2002042340, Macromolecules, 28, 7973 (1995), and Polymer Journal, 28, 817 (1996)). As another degradation process, there is also known a process of decomposing polybutadiene and the like with a metathesis catalyst in the presence of a functional-group-containing olefin such to synthesize telechelic polymer (see, for example, Macromolecules, 28, 1333 (1995)). However, such polymer degradation processes have a drawback that when the introduction ratio of the functional group is intended to be raised, only a product having a low molecular weight, which falls in an oligomer range, can be obtained. In the latter metathesis degradation process, it is impossible to synthesize a polyolefin having stereoregularity.
A telechelic polyolefin can be synthesized by conducting polymerization of a cycloollefin or diene (ROMP, ADMET) with a metathesis catalyst in the presence of a functional-group-containing olefin and then hydrogenating the resultant polymer (see, for example, US2002111447, and Macromolecules, 33, 6621 (2000)). According to this process, a telechelic polyolefin having a high molecular weight can be synthesized. It is however impossible to synthesize a stereoregular polyolefin.
In either of the polymer degradation process or the metathesis polymerization process, a molecular weight distribution (Mw/Mn) of about 2 or more is obtained and further it is impossible to synthesize a telechelic block copolymer or the like wherein length of block sequences is minutely controlled. There is also a drawback that a telechelic polyolefin of a hetero-telechelic type, wherein functional groups at both the terminals are different from each other, cannot be synthesized, either.
The Applicant has eagerly searched a telechelic polymer which has overcome the above-mentioned problems and is useful for various purposes, and has then made the present invention.
Accordingly, the present invention relates to a polyolefin which has polar functional groups at its both-terminal positions and is useful for various purposes.
The telechelic polyolefin (F) of the present invention is represented by the following general formula (I):
X—P—Y (1)
wherein X and Y are each a group containing at least one element selected from oxygen, sulfur, nitrogen, phosphorus and halogens, X and Y may be the same or different, P represents a polymer chain made mainly of an olefin composed only of carbon and hydrogen atoms, and X and Y are bonded to both terminals of P, wherein the molecular weight distribution (Mw/Mn) obtained by gel permeation chromatography (GPC) is from 1.0 to 1.5.
A preferred embodiment of the polymer chain (P) is a polymer chain made of units of at least one olefin selected from ethylene and olefins having 3 to 20 carbon atoms.
The invention also relates to the telechelic polyolefin (F) produced by a specific production process. Specifically, the telechelic polyolefin of the invention comprises a telechelic polyolefin obtained by: performing the following steps 1, 2 and 1 in this order in the presence of an olefin polymerizing catalyst containing a compound (A) which contains a transition metal in the groups IV to V; and subsequently performing the following step 3. if necessary:
[step 1] the step of bringing it into contact with a polar-group-containing olefin (C) represented by the following general formula (II):
CHA=C(R)-Q-Y′ (II)
wherein Y′ is a group containing at least one element from oxygen, sulfur, nitrogen, phosphorus and halogens, Q is an alkylene group which may have a substituent, a carbonyl group, or bivalent oxygen, A and R each represent a hydrogen atom or a hydrocarbon group which may have a substituent, and A or R may be bonded together to Q to form a ring,
[step 2] the step of bringing the resultant into contact with at least one olefin (D) selected from ethylene and olefins having 3 to 20 carbon atoms n times wherein n is an integer of 1 or more, so as to mix them (provided that when n is an integer of 2 or more, the olefins (D) used in the respective contact operations are different in kind or composition), and
[step 3] the step of chemical conversion.
The following will describe the telechelic polyolefin of the present invention, and the telechelic polyolefin produced by a specific production process in detail.
Telechelic Polyolefin
The telechelic polyolefin (F) of the invention is represented by the following general formula (I):
X—P—Y (I)
In the formula (I), X is a group containing at least one element selected from oxygen, sulfur, nitrogen, phosphorus and halogens, that is, a polar functional group. Specific examples thereof include an oxy group; a peroxy group; a hydroxyl group; a hydroperoxy group; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy, and phenylethoxy; an acetoxy group; a carbonyl group; groups wherein an element in the group XIII or XIV is bonded to an oxygen, such as silyloxy, boryloxy, and aluminoxy; an amino group; N-mono-substituted amino groups such as methylamino, N-benzylamino, and N-cyclohexylamino; N,N-di-substituted alkylamino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, dibenzylamino, piperidino, and morpholino; arylamino or alkylarylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; N,N-disilyl-substituted amino groups such as N,N-bis(trimethylsilyl)amino, N,N-bis(triethylsilyl)amino, and N,N-bis(t-butyldimethylsilyl)amino; nitrogen-containing groups such as imine, amide, imide, ammonium, nitrile and sulfonamide; sulfonate groups such as methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; sulfinate groups such as methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups; a sulfate group; a sulfide group; a polysufide group; and a thiolate group. Examples of the phosphorus-containing group include phosphines such as phenylphosphino, methylphosphino, ethylphosphino, diphenylphosphino, dimethylphosphino, diethylphosphino, methylphenylphosphino, and dibenzylphosphino; phosphine oxides; phosphine sulfides; and phosphinous acids. Examples of the halogens include fluorine, chlorine, bromine, and iodine. Y is a group containing at least one element selected from oxygen, sulfur, nitrogen, phosphorus and halogens. Examples of Y are the same as exemplified as X. Polymer chain P represents a polymer chain made mainly of an olefin composed only of carbon and hydrogen atoms. Such an olefin polymer chain is preferably a polyolefin polymer chain made of structural units derived from at least one selected from ethylene and α-olefins having 3 to 10 carbon atoms, as will be described later in the item of production process.
The molecular weight distribution (Mw/Mn) of the telechelic polyolefin of the invention represented by the general formula (I), the distribution being obtained by gel permeation chromatography (GPC), is from 1.0 to 1.5, preferably from 1.0 to 1.4. However, when the telechelic polyolefin of the invention is produced by a production process which will be described later (n=1 in the step 2), the molecular weight distribution (Mw/Mn) is usually 1.3 or less.
In the telechelic polyolefin of the invention, when X and Y are equal to each other and each contain an α-olefin chain having 3 to 20 carbon atoms, the α-olefin chain has a feature of exhibiting syndiotacticity. The fact that the α-olefin chain is syndiotactic can be identified by various spectral analyses. The following will describe the fact that the telechelic polyolefin of the invention is syndiotactic on the basis of analytic findings, giving a case in which the α-olefin is propylene as an example.
The 13C NMR spectrum of polypropylene is measured, and attention is paid to a range of methyl groups of side chains (19.5-21.7 ppm). The syndiotacticity [rr] of a triad can be obtained by substituting an integrated value of plural peaks (19.5-20.2 ppm) corresponding to an rr triad in this range and an integrated value of peaks (20.2-21.7 ppm) corresponding to a different mm or mr triad for I(rr)/{I(rr)+I(mr)+I(mm)} wherein I represents the integrated intensity of each chain in the 13C NMR. In the case that polypropylene has no regularity, a statistically-random distribution is generated; therefore, values close to the following are obtained: I(rr):I(mr):I(mm)=1:2:1 and [rr]=0.25. In the telechelic polyolefin of the invention, the [rr] can be controlled into any value from 0.25 to 1.0 by catalytic structure or other polymerizing conditions. In the case that the regularity is particularly high ([rr]>0.80), a sharp peak corresponding to an rrrr pentad makes its appearance at a higher intensity than peaks resulting from other peaks in the range of 20.0-20.1 ppm. Accordingly, the syndiotacticity can be more precisely evaluated by the [rrrr]. In a copolymer made from ethylene and propylene also, syndiotacticity is kept when chains of propylene are present therein. In this case, the value of the [rr] can be obtained from a value obtained by amending overlap of methyl groups which originates from chains of EPE and EPP wherein E and P represent an ethylene unit and a propylene unit, respectively, in each polymer.
Out of the telechelic polyolefins (F) satisfying such requirements, preferred are polyolefins wherein X and Y are each an oxygen-containing group or nitrogen-containing group, and polyolefins wherein X is an oxygen-containing group and Y is a nitrogen-containing group.
Telechelic Polyolefin Produced by a Specific Production Process
The telechelic polyolefin of the invention can be effectively obtained by carrying out steps which will be detailed below in the presence of an olefin polymerizing catalyst containing a compound (A) which contains a transition metal in the groups IV to V in the-periodic table.
As the group IV to V transition metal containing compound (A), transition metal compounds described in the above-mentioned Japanese Patent Application Laid-Open No. 2003-40953, which was filed by the Applicant, can be used without any limitation. Of these transition metal compounds, preferred transition metal compounds are illustrated below.
In the production process according to the invention, an organic aluminum oxy compound (B) can be used together with the group IV to V transition metal containing compound (A). The organic aluminum oxy compound (B) may be an aluminoxane known in the prior art, or an organic aluminum oxy compound insoluble in benzene, as exemplified in Japanese Patent Application Laid-Open No. 2-78687.
The known aluminoxane can be produced by, for example, a process as described below, and is usually obtained as a solution containing a solvent of a hydrocarbon.
(1) A process of adding an organic aluminum compound, such as trialkylaluminum, to a suspension of a compound containing absorbed water or a salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerium (I) chloride hydrate, in a hydrocarbon medium, so as to cause the absorbed water or crystal water to react with the organic aluminum compound.
(2) A process of causing water, ice or water vapor to act directly on an organic aluminum compound, such as trialkylaluminum, in a solvent such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A process of causing an organic tin oxide such as dimethyltin oxide or dibutyltin oxide to react with an organic aluminum compound, such as trialkylaluminum, in a solvent such as decane, benzene or toluene.
Specific examples of the organic aluminum compound used when the aluminoxane is prepared include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, and trioctylaluminum; branched-trialkyl aluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum, and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum, and tritolylaluminum; and trialkenylaluminums such as triisoprenylaluminum represented. by (i-C4H9)xAly(C5H10)z wherein x, y and z are each a positive number and z≧2x. Of these, trialkylaluminums and tricycloalkylaluminums are preferred and trimethylaluminum is particularly preferred. The above-mentioned organic aluminum compounds may be used alone or in combination of two or more thereof.
In the production process according to the invention, at least one selected from the following can be caused to be present together with the group IV to V transition metal containing compound (A) and the organic aluminum oxy compound (B): an organic metal compound, a compound which can react with the transition metal compound (A) to form an ion pair, a carrier, and an organic compound. About the four components used if necessary, ones described in the Japanese Patent Application Laid-Open No. 2003-40953 can be used without any limitation.
The telechelic polyolefin (F) of the invention is obtained by: performing the following steps 1, 2 and 1 in this order in the presence of an olefin polymerizing catalyst containing a compound (A) which contains a transition metal in the groups IV to V; and subsequently performing the following step 3 if necessary:
[step 1] the step of bringing it into contact with a polar-group-containing olefin (C) represented by the following general formula (II):
CHA=C(R)-Q-Y′ (II)
wherein Y′ is a group containing at least one element from oxygen, sulfur, nitrogen, phosphorus and halogens, Q is an alkylene group which may have a substituent, a carbonyl group, or bivalent oxygen, A and R each represent a hydrogen atom or a hydrocarbon group which may have a substituent, and A or R may be bonded together to Q to form a ring,
[step 2] the step of bringing the resultant into contact with at least one olefin (D) selected from ethylene and olefins having 3 to 20 carbon atoms n times wherein n is an integer of 1 or more, so as to mix them (provided that when n is an integer of 2 or more, the olefins (D) used in the respective contact operations are different in kind or composition), and
[step 3] the step of chemical conversion
Y′ in the general formula (II) used in the step 1 is a group containing at least one element from oxygen, sulfur, nitrogen, phosphorus and halogens. Examples of such a group include an oxy group; a peroxy group; a hydroxyl group; a hydroperoxy group; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy, and phenylethoxy; an acetoxy group; a carbonyl group; groups wherein an element in the group XIII or XIV is bonded to an oxygen, such as silyloxy, boryloxy, and aluminoxy; an amino group; N-mono-substituted amino groups such as methylamino, N-benzylamino, and N-cyclohexylamino; N,N-di-substituted alkylamino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, dibenzylamino, piperidino, and morpholino; arylamino or alkylarylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; N,N-disilyl-substituted amino groups such as N,N-bis(trimethylsilyl)amino, N,N-bis(triethylsilyl)amino, and N,N-bis(t-butyldimethylsilyl)amino; nitrogen-containing groups such as imine, amide, imide, ammonium, nitrile and sulfonamide; sulfonate groups such as methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; sulfinate groups such as methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups; a sulfate group; a sulfide group; a polysufide group; and a thiolate group. Examples of the phosphorus-containing group include phosphines such as phenylphosphino, methylphosphino, ethylphosphino, diphenylphosphino, dimethylphosphino, diethylphosphino, methylphenylphosphino, and dibenzylphosphino; phosphine oxides; phosphine sulfides; and phosphinous acids. Examples of the halogens include fluorine, chlorine, bromine, and iodine. Of these, preferred are silyloxy, aluminoxy, boryloxy, and N,N-disiyl-substituted amino groups, which do not poison the catalyst easily and which generate active hydrogen after hydrolysis after the end of the step 2.
In the general formula (II), Q is an alkylene group which may have a substituent, a carbonyl group, or bivalent oxygen. Q is usually an alkylene group which may have a substituent wherein the total number of carbon atoms is from 1 to 20. Of alkylene groups having such a requirement, an unsubstituted linear alkylene group represented by the following formula (III) is preferably used:
—[CH2]n— (III)
wherein n is a positive integer of 1 to 15.
In the general formula (II), A and R each represent a hydrogen atom or a hydrocarbon group which may have a substituent, and A or R may be bonded together to Q to form a ring. Of structures satisfying such requirements, a cycloolefin represented by the following formula (IV) or (IV′) is preferably used:
wherein p represents an integer of 1 to 10, and is bonded to Y at any position, q is an integer of 0 to 10, and when q is 0, the cycloolefin is a monocycloolefin.
Examples of the α-olefin having 3 to 20 carbon atoms, used in the step 2, include linear or branched α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene; and cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Other examples of the olefin having 3 to 20 carbon atoms include vinylcyclohexane, dienes and polyenes. Additional examples of the olefin include aromatic vinyl compounds styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene, and other mono- or poly-alkylstyrenes; and 3-phenylpropylene, 4-phenylbutene, and α-methylstyrene. These olefins may each contain in the molecule thereof a heteroatom such as an oxygen, nitrogen, or silicon atom. The olefins may be used alone or in combination of two or more thereof.
The process for producing the telechelic polyolefin (F) of the invention will be specifically described hereinafter.
The telechelic polyolefin (F) of the invention can be effectively produced by carrying out operations composed of the steps 1 to 2 and the optional step 3 in order of the steps 1, 2 and 1, and the optional step 3.
When kinds of the polar-group-containing olefin (C) used in the first and second [steps 1] are made different from each other in the production of the telechelic polyolefin (F) (for example, the polar-group-containing olefin (C) represented by the general formula (II) wherein Y′ is an oxygen atom and that wherein Y′ is a nitrogen atom are used), two groups X and Y in the resultant telechelic polyolefin can be made different from each other.
In the case that the above-mentioned production process, wherein the steps 1, 2 and 1 are successively carried out in this order and subsequently the step 3 may be optionally carried out, is schematically shown as illustrated in the following scheme (a):
1→2→1→3 (a)
a telechelic polyolefin wherein functional groups are introduced to both terminals of the polymer chain P and simultaneously one or more functional groups are introduced also to the side chain moiety of the polymer chain (P) is produced when the following scheme (b) is carried out:
ti 1−[→2→1−]n→3 (b)
wherein n is an integer of 2 or more. Attention should be paid to this matter. In other words, when n is 2, it is possible to produce a telechelic polyolefin wherein functional groups are introduced to both terminals thereof and further one functional group is introduced to the side chain moiety thereof; and when n is k wherein k is an integer of 2 or more, functional groups, the number of which is (k-1), are introduced to the side chain moiety of the polymer chain as well as functional groups are introduced to both the terminals. The telechelic polyolefin of the invention includes such polyfunctional polyolefins.
In the case that the olefins (D) used in the first and second contacts in the [step 2] are made different from each other in kind or composition in the production of the telechelic polyolefin (F), the polymer chain (P) in the telechelic polyolefin (F) represented by the general formula (I) can be rendered a block type chain composed of two kinds of olefin chains each having a controlled molecular weight (the wording “different in kind or composition” in the step 2 related to the invention means the following: “different in kind”; “different in composition”; and further “different in kind and composition”) For example, when the olefin (D) used in the first contact in the step 2 is ethylene and the olefin (D) used in the second contact in the step 2 is propylene, the resultant telechelic polyolefin is represented by the following formula (V):
X—PE-PP—Y (V)
wherein X and Y have the same meanings as in the formula (I), and PE and PP represent a polyethylene chain and a polypropylene chain, respectively.
When the olefin (D) used in the first contact in the step 2 is ethylene and olefins (D) used in the second step 2 are propylene and propylene, the resultant telechelic polyolefin is a telechelic polyolefin represented by the following formula (VI):
X—PE-EPR—Y (VI)
wherein X and Y have the same meanings as in the formula (I), and PE and EPR represent a polyethylene chain and an ethylene/polypropylene copolymer chain, respectively.
The step 3, which may be performed if necessary, is a step for converting the group (Y′) in the general formula (II) to a different group by a reaction such as hydrolysis, oxidization, reduction, or nucleophilic substitution. For example, in Example 1 in the present specification, hydrolysis reaction is used to convert a Y′ group: Me3SiO— to a different group (hydroxyl group). However, the conversion is not limited to this chemical conversion.
In the invention, the polymerization can be carried out by anyone of liquid-phase polymerizations, such as dissolution polymerization, suspension polymerization, and gas-phase polymerizations.
Specific examples of an inert hydrocarbon medium used in the liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof. The olefin itself can be used as the solvent.
When the telechelic polyolefin according to the invention is produced in the presence of the above-mentioned catalyst, the operations composed of the steps 1 and 2 are usually carried out without isolating any product in each of the steps. Usually, the catalyst is once charged when the initial step 1 is started. The group IV to V transition metal compound (A) is used in an amount ranging usually from 10−12to 1 mole, preferably from 10−10 to 10−1 mole per liter of the reaction volume. The organic aluminum oxy compound (B) is used in such an amount that the mole ratio of aluminum atoms in the component (B) to transition metal atoms (M) in the transition metal compound (A) (Al/M) will be a value ranging usually from 10 to 500, 000, preferably from 50 to 100,000.
When an organic metal compound, a compound which can react with the transition metal compound (A) to form an ion pair, a carrier and an organic compound, as other optional components, are used together, the used amounts thereof are amounts described in Japanese Patent Application Laid-Open No. 11-315109.
The step 1 can be finished by the contact usually at −20 to 50° C., preferably at 0 to 25° C. for 1 to 300 minutes, preferably for 20 to 200 minutes.
In the step 2, the polymerization reaction is advanced by the contact usually at −20 to 75° C., preferably at −10 to 50° C. for 1 to 600 minutes, preferably for 5 to 180 minutes. The pressure in the step 2 is usually from a normal pressure to 100 kg/cm2, preferably from a normal pressure to 50 kg/cm2. The polymerization reaction can be conducted by any one of batch type, semi-continuous type, and continuous type processes. The polymerization can be conducted at two or more separated stages wherein reaction conditions are different.
The telechelic polyolefin of the invention can be developed into various applications. The polyolefin can be applied to, for example, a high molecular weight additive; a compatibility accelerator; a diblock copolymer useful as a compatibility accelerator or modifier for polymer; a precursor of a triblock copolymer useful as thermoplastic elastomer or the above-mentioned articles; or a surface modifier for improving paintability, adhesive property and other properties of resin. The polyolefin can be used, in the form of a macromonomer, as raw material of a polymer having a specific structure such as a comb-shaped or star-shaped structure, and applied to a viscosity adjustor for oil, or some other article.
In the hydrolysis step of the step 3, which is an optional constituting requirement of the production process according to the invention, water or alcohol is usually used as a hydrolyzing agent, and the hydrolysis is conducted under an acidic or basic condition. The hydrolysis may be conducted in the presence of an organic solvent in a two-phase system, or conducted in a gas phase using steam. Usually, the following conditions are adopted: a temperature of 0 to 800° C. and a time of 1 minute to 24 hours.
The invention will be specifically described on the basis of examples hereinafter. However, the invention is not limited to these examples. The structures of polymers obtained in the examples were each decided by use of NMR (FT: 270 MHz, 1H; and 67.5 MHz, 13C), DSC, high-temperature GPC, and so on.
Into a glass reactor having an internal volume of 500 mL and purged sufficiently with nitrogen were charged 250 mL of toluene and 7.95 mmol of methylaluminoxane, the amount being an amount in terms of aluminum atoms therein. Thereto was added a solution of 20.9 mg (0.0862 mmol) of Me3SiO—(CH2)9CH═CH2 in toluene. Thereto was added a solution of 69.8 mg (containing diethyl ether,. 0.0795 mmol) of a titanium complex, bis [N-(3-t-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinat e]titaniumdichloride in toluene, and then the components were caused to react at 25° C. for 5 minutes. Thereafter, the reaction solution was cooled to 0° C. Thereafter, propylene (gas flow rate: 100 L/h), the pressure of which was a normal pressure, was blown from the bottom of the reactor to the inside thereof so as to cause the components to react at 0° C. for 90 minutes. Thereafter, the supply of propylene was stopped, and then the reaction solution was heated to room temperature while nitrogen (gas flow rate: 50 L/h) was caused to flow thereinto. Thereto was added a solution of 113.3 mg (0.4673 mmol) of Me3SiO—(CH2)9CH═CH2 in toluene, and then the components were caused to react for 1 hour. Thereafter, thereto was added methanol to terminate the polymerization. After the termination of the polymerization, the reactant was poured into 600 mL of methanol containing a small amount of hydrochloric acid to precipitate the entire amount of a polymer. The polymer was collected by filtration. The polymer was dried at 80° C. under a reduced pressure for 10 hours so as to be yielded in an amount of 0.317 g. The polymerization activity per mmol of titanium was 2.65 g, the weight-average molecular weight (Mw) of the polymer was 10,280, the ratio of the weight-average molecular weight to the number-average molecular weight (Mn) was 1.08, and the melting peak temperature based on DSC was 143.0° C. In the 1H NMR spectrum (FT, 270 MHz in C2D2Cl4, at 120° C.) of this polymer, a triplet corresponding to methylene groups adjacent to OH groups made its appearance near 3.64 ppm. The ratio between the triplet and the sum of main peaks of the polymer was 2:681. The number-average molecular weight (Mn) based on GPC was 9,560. From these matters, it is understood that two functional groups were introduced per polymer chain. In the 13CNMR spectrum (FT, 67.5 MHz, in C2D2Cl4, at 120° C.), a signal corresponding to methylene groups adjacent to OH groups made its appearance at 62.9 ppm. Peaks at 22.5-24.0 ppm corresponding to isopentyl and isobutyl groups, which were unreacted initiating and terminating ends, and a peak (near 14 ppm) originating from any n-propyl group hardly made their appearance. It is understood from the above that telechelic syndiotactic polypropylene was synthesized.
Into a glass reactor having an internal volume of 500 mL and purged sufficiently with nitrogen were charged 250 mL of toluene and 10.1 mmol of methylaluminoxane, the amount being an amount in terms of aluminum atoms therein. The reaction solution was cooled to 0° C., and then thereto was added a solution of 33.3 mg (0.106 mmol) of (Me3Si)2N—(CH2)9CH═CH2 in toluene. Thereto was added a solution of 88.5 mg (containing diethyl ether, 0.101 mmol) of a titanium complex, bis[N-(3-t-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinat e]titanium dichloride in toluene, and then the components were caused to react at 0° C. for 120 minutes. Thereafter, propylene (gas flow rate: 100 L/h), the pressure of which was a normal pressure, was blown from the bottom of the reactor to the inside thereof so as to cause the components to react at 0° C. for 120 minutes. Thereafter, the supply of propylene was stopped, and then the reaction solution was heated to room temperature while nitrogen (gas flow rate: 50 L/h) was caused to flow thereinto. Thereto was added a solution of 126.3 mg (0.521 mmol) of Me3SiO—(CH2)9CH═CH2 in toluene, and then the components were caused to react for 1 hour. Thereafter, thereto was added methanol to terminate the polymerization. After the termination of the polymerization, the reactant was poured into 600 mL of methanol containing a small amount of hydrochloric acid to precipitate the entire amount of a polymer. The polymer was collected by filtration. The polymer was dried at 80° C. under a reduced pressure for 10 hours so as to be yielded in an amount of 0.254 g. The polymerization activity per mmol of titanium was 1.59 g. In the 1H NMR spectrum (FT, 270 MHz, in C2D2Cl4, at 120° C.) of this polymer, a broad peak corresponding to a methylene group adjacent to a NH3Cl group and a triplet corresponding to a methylene group adjacent to an OH group made their appearance near 3 ppm and near 3.64 ppm, at an integration ratio of 2:2. From the above, a structure of a polymer of the following formula was identified.
The polyolefin having polar functional groups at its both terminal positions itself, or the polyolefin subjected to a further modifying treatment is useful for various purposes.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-302240 | Aug 2003 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP04/12792 | 8/27/2004 | WO | 2/24/2006 |
