JPH07304829A - Production of polymer - Google Patents

Abstract

PURPOSE:To obtain a high-melting point cyclopolymer with small amounts of catalyst residue without the need for using any catalyst such as an organoaluminum compound in high yield, by catalytically polymerizing a specific hexadiene in the presence of a catalyst containing a specific metallocene compound. CONSTITUTION:This polymer of formula III is obtained by catalytically polymerizing 1,5-hexadiene in the presence of a catalyst containing a metallocene compound of formula I or II (R is H, a 1-5C hydrocarbon or a Si-contg. hydrocarbon; when R is not H, two of the Rs may be mutually bound at the respective omega- terminals into a ring condensed with the cyclopentadiene ring; M is a group IIIA element with an atomic number of 21-71; X is H, a 1-10C hydrocarbon or a Si-contg. hydrocarbon; (m) is 0 or 1; Z is a 1-3C alkylene or alkylsilylene; D is a solvent molecule; (n) is 0-3). It is preferable that the metallocene compound be e.g. biscyclopentadienylsamarium.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-yield cyclopolymer having a high melting point and having a small amount of catalyst residue.

[0002]

2. Description of the Related Art As described in J. Am. Chem. Soc., 80, 1740 (1958), a method for producing a 1,5-hexadiene cyclopolymer using a Ziegler-Natta catalyst is used. Are various ratios of TiCl ₄ / Al
It is known to be a (C ₄ H ₉ ) ₃ mixture.

However, the data described in the above-mentioned literature show that for 1,5-hexadiene cyclopolymers obtained by the method, the ring-closing polymerization is not complete (5-8% of the monomer units contained in the chain are It retains double bonds) and has a low melting point (85-90 ° C). Further, long-term polymerization (50 to 70 hours) is required to obtain a high monomer conversion rate.

On the other hand, J. Polym. Sci. Part A, 2, 1549
(1964) contains TiCl ₄ / Al (C ₂ H ₅ ) ₃ , Ti
Cl ₃ · 0.22AlCl ₃ / Al (C ₂ H ₅ ) ₃ and TiCl ₂ · 0.5AlCl ₃ / Al (C ₂ H ₅ ) ₃
Although a polymerization method of 1,5-hexadiene using a catalyst system is described, the cyclization rate is low regardless of which catalyst system is used.
And seems to have low activity.

Cyclopolymers of this kind (TiCl ₃ / A
l (C 2 _{H 5)} Study on the detailed structure of the 2 _Cl use of a catalyst system obtainable by 1,5-hexadiene polymerization) is, J.Appl. Polymer. Sci., described in 35, 825 (1988) The NMR analysis shows that the units generated in the polymer chain are mainly

[0006]

[Chemical 3] However, it is shown that the cyclopentane rings are groups having a cis- or trans-configuration. The data described in the above-referenced documents showed that the polymers obtained with the catalyst system described above contained cyclopentane rings in the cis- and trans-configurations in a ratio of about 1/1.

J. Am. Chem. Soc., 112, 4953 (1990) and JP-A-6-25319 disclose a mixture of zirconocene and methylaluminoxane or triisobutyldialumoxane in the ring-closing polymerization of 1,5-hexadiene. Although the method to be used is shown, in this method also, since a large amount of organoaluminum compound is used as a cocatalyst, it seems that there are many problems in post-treatment and physical properties of the polymer. [Outline of Invention]

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a polymer in a high yield and without using a cocatalyst such as an organoaluminum compound while maintaining a high cyclization rate in the ring-closing polymerization of 1,5-hexadiene. A method of manufacturing is provided.

[0009]

[Means for Solving the Problems]

<Summary> The method for producing a cyclopolymer having a structure represented by the following formula (III) as the main component of the present invention comprises a catalyst containing a compound represented by the following formula (I) or (II)
-Hexadiene is contacted and polymerized.

[0010]

[Chemical 4] [In formula, R is respectively independently a hydrogen atom, a C1-C5 hydrocarbon group, or a silicon-containing hydrocarbon group. However, when R is other than a hydrogen atom, two of them may bond at each ω-end to form a ring condensed with the cyclopentadiene ring. M is the Periodic Table II
It is an element of atomic number 21 to 71 of IA group. X is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group containing silicon, and m is 0 or 1. Z is an alkylene group having 1 to 3 carbon atoms or an alkylsilylene group. D is a solvent molecule, and n = 0 to 3. ]

[0011]

[Chemical 5] <Effect> According to the present invention, a cyclopolymer having a high melting point and a small amount of catalyst residue can be produced in a high yield. [Detailed Description of the Invention] [Catalyst] The catalyst used in the present invention comprises a metallocene compound represented by the formula (I) or the formula (II). <Metallocene Compound> The definition of each symbol in formula (I) or (II) is as described above. The substituent R on the cyclopentadiene ring is on the same ring and / or
Both rings may be the same or different. Further, R is basically a monovalent group, but when it is a hydrocarbon group or a silicon-containing hydrocarbon group, a plurality thereof, normally two, preferably two adjacent are the ω. -End, that is, a ring fused with the cyclopentadiene ring may be bonded to each other at opposite ends of the fused position with the cyclopentadiene ring.

A specific example of the case where R is a hydrocarbon is C ₁
Straight or branched chain alkyl or alkenyl -C _5,
For example, methyl, ethyl, n- or i-propyl, n
-, I- or t-butyl, and its corresponding alkenyl groups. Lower alkyl, especially methyl or t-butyl, is preferred. It has been mentioned above that these groups may be bonded to each other at their ω-ends to form a condensed ring with cyclopentadiene.

When R is a C _{1 to} C ₅ silicon-containing hydrocarbon group, it is preferable that all the valences of the silicon atom are satisfied by the bond with the carbon atom. The number of silicon atoms is usually 1 to 2, preferably 1. Accordingly, preferred embodiments of this silicon-containing hydrocarbon group, trialkyl _{(C 1 to 10)} a silyl group, preferably a trialkyl _{(C 1 to 4)} silyl group, more trimethylsilyl group, dimethyl -t- butylsilyl Group etc.

The metallocene compound of formula (I) has a structure bridged by Z. The bridging group Z is an alkylene group having 1 to 3 carbon atoms or an alkylsilylene group having 1 to 3 carbon atoms. The alkylsilylene group in this case also preferably has all the valences of silicon satisfied by a bond with a carbon atom. The number of silicon atoms is usually 1-2, preferably 1. The bridging group Z has a "bridge length" of 1
It is preferably an atom or two atoms. Thus, specific examples of Z are methylene, ethylene, isoprene (bridge length is 1 atom) and dimethylsilylene.

M is atomic number 21 of Group IIIA of the periodic table
~ 71 elements, namely Sc, Y, La, Ce, Pr,
Nd, Pm, Sm, Eu, Ga, Tb, Dy, Ho, E
r, Tm, Yb or Lu. Of these, preferred is Y, Sm, Yb or Lu, especially Y or Sm.

X is a group bonded to satisfy the free valence of a given metal M, and is a hydrogen atom or a carbon number of 1
-10, preferably 1-4, hydrocarbon groups or silicon-containing hydrocarbon groups. Except for the large number of carbons,
The same applies to R for X (including bonding to each other at the ω-end). Therefore, specific examples of X include, for example, hydrogen, methyl group, ethyl group and the like. The number m of X is 0 if the metal M is divalent, and 1 if M is trivalent.

D is a solvent atom. This solvent is usually the solvent used in the preparation of the metallocene compound, and specifically, for example, oxygen-containing aprotic compounds such as ethers, that is, tetrahydrofuran, diethyl ether, etc., aliphatic or aromatic compounds. Hydrocarbons such as benzene and toluene are exemplified.

Specific examples of the metatocene compound represented by the formula (I) or (II) are as follows.

Biscyclopentadienyl samarium, dimethylsilylene biscyclopentadienyl samarium,
Dimethylsilylenebis (2,4-ditrimethylsilylcyclopentadienyl) samarium, dimethylsilylenebis (2-trimethylsilyl-4-t-butylcyclopentadienyl) samarium, biscyclopentadienyl lutetium hydride, biscyclopentadienyl Lutetium methyl, biscyclopentadienyl lutetium ethyl, biscyclopentadienyl lutetium bistrimethylsilylmethyl, bispentamethylcyclopentadienyl lutetium hydride, bispentamethylcyclopentadienyl lutetium methyl, bispentamethylcyclopentadienyl lutetium bis Trimethylsilylmethyl, biscyclopentadienyl ytterbium hydride, biscyclopentadienyl ytterbium methyl, bispentame Lecyclopentadienyl ytterbium hydride, bispentamethylcyclopentadienyl ytterbium methyl, bispentamethylcyclopentadienyl ytterbium bistrimethylsilylmethyl, biscyclopentadienyl samarium hydride, biscyclopentadienyl samarium methyl, bispentamethylcyclo Pentadienyl samarium hydride, bispentamethylcyclopentadienyl samarium methyl, bispentamethylcyclopentadienyl samarium bistrimethylsilylmethyl, biscyclopentadienyl europium hydride, biscyclopentadienyl europium methyl, bispentamethylcyclo Pentadienyl europium hydride, bispentamethylcyclopentadienyl europium Mumechiru, bis pentamethylcyclopentadienyl neodymium methyl,
Bispentamethylcyclopentadienylcerium hydride, bispentamethylcyclopentadienyl yttrium methyl, bispentamethylcyclopentadienyl scandium hydride, bispentamethylcyclopentadienyl scandium methyl, bisindenyl lutetium methyl, ethylene bisindenyl Lutetium methyl, ethylene biscyclopentadienyl lutetium methyl, biscyclopentadienyl yttrium hydride, biscyclopentadienyl yttrium methyl, dimethylsilylene biscyclopentadienyl yttrium hydride, dimethylsilylene biscyclopentadienyl yttrium methyl, dimethylsilylene Screw (2-
Trimethylsilyl-4-trimethylsilylcyclopentadienyl) yttrium hydride, dimethylsilylenebis (2-trimethylsilyl-4-trimethylsilylcyclopentadienyl) yttrium methyl, dimethylsilylenebis (2-trimethylsilyl-4-dimethylt)
-Butylsilylcyclopentadienyl) yttrium hydride, dimethylsilylene bis (2-trimethylsilyl-4-dimethyl t-butylsilylcyclopentadienyl) yttrium methyl.

In these examples, the solvent molecule D (eg, tetrahydrofuran, THF, diethyl ether, benzene, toluene, etc.) is omitted.

These compounds can be prepared by known methods, for example,
Tobin J. Marks, J. Am. Chem. Soc. 107, 8091, 1985.
: William. J. Evans. J. Am. Chem. Soc .: 105, 140
1, 1983.:PL Watson, ACS Symp., 495, 1983.
: Tobin J. Marks, WO 8605788.

In the above formulas (I) and (II), M is 3
Valence is preferable, and hydride (X = H) is more preferable. When X is not hydrogen, it is preferable that the catalyst compound is hydrotreated and used for polymerization.

The method for obtaining the hydride of the organic rare earth compound is not particularly limited, but it is usually preferable to introduce hydrogen into the solution of the organic rare earth compound and react it. The temperature of the reaction is -10 to 100 ° C, preferably 0 to 50.
C, and the reaction time is 1 minute to 10 hours, preferably 1
0 minutes to 5 hours. The solvent used may preferably be the same as the polymerization solvent. <Catalyst> The catalyst according to the present invention comprises a compound represented by the above formula (I) or (II).

Here, it should be understood that the term "compound represented by the formula (I) or (II)" does not exclude the combined use of both compounds, and "comprising" is purposeful. Does not exclude the presence of specific auxiliary ingredients. One specific example of such an auxiliary component is an organoaluminum compound (including alumoxane) having the formula (I) or (I
The metallocene compound of I) has catalytic activity without the combined use of an organoaluminum compound, and this is a preferable aspect of the present invention. [Polymerization] Polymerization is performed by using an inert gas (for example, nitrogen, argon,
(Such as helium) atmosphere, in the presence or absence of a solvent,
-100 ° C to + 200 ° C, preferably -100 ° C to +1
It is usually carried out by contacting 1,5-hexadiene with the above catalyst at a temperature of 50 ° C., particularly preferably −50 ° C. to + 100 ° C. The polymerization time depends on the polymerization activity, but is usually 10 seconds to 1000 hours,
It is preferably 30 seconds to 500 hours, more preferably 1 minute to 100 hours.

The amount of the organic rare earth compound used as a catalyst depends on the desired molecular weight of the polymer, but is usually 5 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol, preferably 3 ×, relative to 1 mol of all the monomers. It is in the range of 10 ^{−5 to} 2 × 10 ⁻¹ mol.

When a solvent is used, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as hexane, etc. Aliphatic hydrocarbons such as heptane, such as cyclohexane, bicyclo-2,2,1-heptane, etc., ethers such as tetrahydrofuran, diethyl ether, etc. can be used, but aromatic hydrocarbons are preferred. Used.

[0027]

【Example】

<Production Example-1> Synthesis of dimethylsilylene bis (2-trimethylsilyl-4-dimethyl t-butylsilylcyclopentadienyl) yttrium ditrimethylsilylmethyl A bis (2-
Trimethylsilyl-4-dimethyl t-butylsilylcyclopentadienyl) dimethylsilane (7.89 mmol) and sufficiently dried tetrahydrofuran (25 ml) were added, and after cooling to 0 ° C, n-butyllithium was added to a hexane solution at 17.4 mm.
ol, and then 10.2 mmol of trichloroyttrium, and then 12 under reflux of tetrahydrofuran (THF).
Reacted for hours. Then, the solvent was distilled off under reduced pressure, and
120 ml of sufficiently dried hexane was added, the precipitated solid was removed by centrifugal sedimentation, and the compound of the formula (V) was recrystallized from the solution, that is, bis (tetrahydrofuran) lithium dimethylsilanediylbis (2-trimethylsilyl- 2.39 mmol of 4-dimethyl t-butylsilylcyclopentadienyl) dichloroytrate were obtained.

[0028]

[Chemical 6] In a flask that had been sufficiently dried and purged with nitrogen, 2.3 mmol of the compound of formula (V) and 60 ml of sufficiently dried toluene were charged, and after cooling to 0 ° C., lithium bis (trimethylsilyl)
3.5 mmol of methane was added as an ether solution, and the mixture was reacted at room temperature for 12 hours with stirring. Then, the solvent was distilled off under reduced pressure, 80 ml of sufficiently dried hexane was added and stirred, the precipitated salt was removed by centrifugal sedimentation, and dimethylsilylenebis (2-trimethylsilyl-4- Dimethyl t-butylsilyl cyclopentadienyl) yttrium ditrimethylsilylmethyl (Compound A) 0.83
Obtained mmol. The structure of Compound A was identified by ¹ H-NMR using a solvent C ₆ D ₆ . Compound A ¹ H-NMR (C ₆ D ₆ ), δ (ppm) 7.64 (m, 1H, Cp-H), 6.96 (d, 1)
H, Cp-H), 6.77 (d, 1H, Cp-H),
6.62 (d, 1H, Cp-H), 0.96, 0.9
4, 0.53, 0.48, 0.42, 0.26 (s, 3
H × 6, Me-Si × 6), 0.78, 0.76 (s,
9H × 2, t-Bu), 0.46, 0.38, 0.3
3,0,20 (s, 9H × 4, Me ₃ Si × 4) <Production Example-2> Synthesis of bis (tetrahydrofuran) dimethylsilylenebis (2-trimethylsilyl-4-t-butylcyclopentadienyl) samarate Sufficient Then, 6.77 mmol of bis (2-trimethylsilyl-4-t-butylcyclopentadienyl) dimethylsilane and 80 ml of well-dried tetrahydrofuran were added to a flask which had been dried and completely purged with argon, and after cooling to 0 ° C, n-butyllithium was added. A hexane solution (13.5 mmol) was added, and the mixture was stirred at room temperature for 6 hours.
13.6 mmol of potassium t-butoxide was added thereto in a tetrahydrofuran solution, and the mixture was reacted for 12 hours under reflux of tetrahydrofuran. Then, the tetrahydrofuran was distilled off and washed with sufficiently dried hexane to obtain lithium t-butoxide.
The butoxide was removed to give a white solid.

Next, in a flask that had been sufficiently dried and purged with argon, 10 mmol of diiodosamarium, 5.64 g of the above white solid and 8 ml of sufficiently dried tetrahydrofuran were placed.
After adding 0 ml and reacting for 12 hours under reflux of tetrahydrofuran, solids were removed by centrifugal sedimentation, tetrahydrofuran was further distilled off, and 110 ml of sufficiently dried toluene was added to the resulting residue and stirred for 12 hours. Then, the toluene-soluble part was removed by centrifugal sedimentation, and the insoluble part was recrystallized from a sufficiently dried tetrahydrofuran / hexane solution to give bis (tetrahydrofuran) dimethylsilylenebis (2-trimethylsilyl-4-t-butylcyclolopenta). Dienyl) samarate (compound B) was obtained.

The ¹ H-NMR of compound B was as follows. Compound _{^{B 1 H-NMR (C 6}} D 6), δ (ppm) -10.41 (s, 2H, Cp-H), - 2.34
_{(S, 6H, Me 2 Si} ), - 0.83 (s, 8H, t
_{hf), 3.26 (s, 18H} , Me 3 Si), 3.7
9 (s, 8H, thf), 10.00 (s, 18H, M
e ₃ C), 44.46 (s, 2H, Cp-H) <Example-1> Compound A 6.1 obtained in Catalyst Preparation Example-1 in a 50 ml Schlenk tube thoroughly dried and purged with argon.
Add 9 × 10 ^-3 mmol and 4 ml of well dried toluene,
Hydrogen was added thereto at 1 atm and reacted at room temperature for 1 hour to synthesize dimethylsilylenebis (2-trimethylsilyl-4-dimethylt-butylsilylcyclopentadienyl) yttrium hydride. After sufficiently replacing the Schlenk tube with argon, the mixture was cooled to 0 ° C., and 16.8 mmol of sufficiently dried 1,5-hexadiene was added, and the mixture was added at 12 ° C. at 12 ° C.
Polymerization was carried out for a time. Then, the polymerization solution was added into a large excess of methanol, and the precipitated polymer was separated by filtration and dried to obtain 0.86 g of a polymer.

As a result of analyzing this polymer by gel permeation chromatography, the number average molecular weight (Mn)
Is 137,000, and the weight average molecular weight (Mw) is 334.
000, and the cyclization rate was 100% because no double bond was detected in the polymer by ¹ H-NMR.
On the other hand, the presence of a cyclopentane ring was confirmed by ¹³ C-NMR.

The ratio of the cis configuration and the trans configuration of the cyclopentane ring was found to be 46/54 by the ¹ H-NMR measurement. -5 with a differential calorimeter
As a result of measurement from 0 ° C. to 250 ° C. at a temperature rising rate of 10 ° C./minute, the glass transition point was 8.2 ° C. and the melting point was 118.8 ° C. <Example-2> Example-2, except that the polymerization temperature was 20 ° C.
Polymerization was performed in exactly the same manner as in 1 to obtain 1.38 g of a polymer. This polymerization was carried out almost quantitatively.

The Mn of this polymer was 17,600, Mw
Is 44,000, the cyclization rate is 100%, the cis / trans ratio is 44/56, the glass transition point is -0.5 ° C, and the melting point is 10%.
It was 8.4 ° C. Example 3 A compound B 0.0 obtained in Catalyst Preparation Example-2 was placed in a 50 ml Schlenk tube thoroughly dried and purged with argon.
1 mmol and 2 ml of sufficiently dried toluene were added, and 25.1 mmol of sufficiently dried 1,5-hexadiene was added thereto, and after polymerization was carried out at room temperature for 36 hours, the polymerization solution was added into a large excess of methanol, The precipitated polymer was separated by filtration and dried to obtain 34 mg of polymer.

The Mn of this polymer was 28,500, Mw
Was 53,600, the cyclization rate was 100%, and the cis / trans ratio was 49/51. Comparative Example-1 4 ml of sufficiently dried toluene, 7.0 × 10 ⁻³ mmol of bis (tetramethylcyclopentadienyl) zirconium dichloride, and 50 × 10 ⁻³ mmol of Tosoh Akzo Co., Ltd. were placed in a 50 ml Schlenk tube thoroughly dried and replaced with argon. Add 6.3 mmol of aluminoxane, bring the temperature to 20 ° C.,
16.8 mmol of sufficiently dried 1,5-hexadiene was added, and polymerization was carried out at 20 ° C. for 12 hours. Then, the polymerization solution was added to a large excess of methanol, and the precipitated polymer was separated by filtration and dried to obtain 1.35 g of a polymer. From this result, the polymerization was carried out almost quantitatively.

This polymer has Mn of 950 and Mw of 2,
100, cyclization rate is 100%, cis / trans ratio is 71 /
It was 29.

Further, when Al remaining in the polymer was analyzed by fluorescent X-ray, 1.5% by weight remained.

[0037]

Industrial Applicability According to the present invention, a cyclopolymer having a high melting point with a small amount of catalyst residue can be produced in a high yield, as described above in the "Summary of the Invention".

Claims (5)

[Claims] 1. A compound represented by the following formula (III), which is characterized in that 1,5-hexadiene is brought into contact with a catalyst containing a compound represented by the following formula (I) or (II) to polymerize the catalyst. A method for producing a cyclopolymer whose main structure is. [Chemical 1] [In formula, R is respectively independently a hydrogen atom, a C1-C5 hydrocarbon group, or a silicon-containing hydrocarbon group. However, when R is other than a hydrogen atom, two of them may bond at each ω-end to form a ring condensed with the cyclopentadiene ring. M is the Periodic Table II
It is an element of atomic number 21 to 71 of IA group. X is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group containing silicon, and m is 0 or 1. Z is an alkylene group having 1 to 3 carbon atoms or an alkylsilylene group. D is a solvent molecule, and n = 0 to 3. ] [Chemical 2] 2. The compound of formula (I) or (II), wherein R is hydrogen atom, methyl group, t-butyl group or trialkyl (C _1-10 ) silyl group, respectively. Method for producing cyclopolymer of. 3. The method for producing a cyclopolymer according to claim 1, wherein Z in the compound of formula (I) is dimethylsilylene. 4. The process for producing a cyclopolymer according to claim 1, wherein X in the compound of formula (I) or (II) is hydrogen. 5. A compound of formula (I) or (II) wherein M is S
c, Y, La, Ce, Pr, Nd, Pm, Sm, Eu,
Ga, Tb, Dy, Ho, Er, Tm, Yb or Lu
The method for producing a cyclopolymer according to any one of claims 1 to 4, wherein