JPH10226708A - Process for producing polymetallized composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a polymetallized composition, a method for using the same as a polymerization catalyst and a process for producing a hydrocarbon-soluble polymetallized composition. SOLUTION: This invention provides a process for producing a polymetallized composition, comprising reacting an allene compound of the formula: R<2> -CH=C =CH2 [wherein R<2> is H or a 1-10C aliphatic group] with an organometallic compound R<0> M [wherein R<0> is a hydrocarbyl group, and M is an alkali metal] in a molar ratio of about 1:2 to about 1:6 and a process for producing a hydrocarbon-soluble polymetallized composition, comprising reacting the aliphatic allene compound of the formula with an organometallic compound R<0> M in a molar ratio of about 1:2 to about 1:6 to produce an intermediate and reacting this intermediate with a 1,3-conjugated diene in an amount to give a molar ratio of about 2:1 to the allene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Technical Field of the Invention The present invention relates to a novel process for preparing arene (Allenic) Multi metallization from compound (is) (polymetalated) composition. More particularly, the present invention relates to such compositions comprising 2, 3 or 4 alkali metal substituents per molecule. These compositions are useful as catalysts in anionic polymerization.

BACKGROUND Multi-metallized 1- alkyne compositions of the invention are U.S. Patent No. 5,080,
835, these multi-metallated 1-alkyne compositions comprise 1-alkynes, organometallic compounds (R
⁰ M, wherein R ⁰ is a hydrocarbyl group and M is an alkali metal), and a reaction product of a 1,3-conjugated diene. The molar ratio of conjugated diene to 1-alkyne is at least about 2: 1. The composition described in the '835 patent has the formula

[0003]

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Wherein R is hydrogen, a hydrocarbyl group or R ¹ M, M is an alkali metal and R ¹ is a divalent moiety comprising moieties derived from a conjugated diene. An oligomeric hydrocarbyl group,
And the total number of sites derived from conjugated dienes in all R ¹ groups in Formula I is from about 2 to about 30].

[0005] Other alkali metal acetylides have also been described in the literature, and various methods for making such acetylides from alkyne compounds have been suggested. Among the publications describing such reactions are U.S. Pat. No. 3,303,225; Eberly and Ad.
ams, J.A. Organometal. Chem. , 3
(1965) 165-167; E. FIG. Adams et al.
Kautschukund Gummi, Kunsto
ffe 18. Jahrgang , pp. 709-716,
Nr, 11/1965; Makowski et al . Ma
cromol. Sci. -Chem. , E2 (4) 68
3-700 pages, July 1968; Masuda et al., Ma.
cromolecules , volume 20, no. 7, (19
87) pages 1467-1487.

US Pat. No. 3,410,918 describes the production of sodium propynyl and lithium propynyl. This method involves mixing a gaseous mixture of propyne and allene with a slurry of sodium or lithium metal in a 1: 1 ratio.
Contacting in an inert ether type solvent or in certain aromatic and aliphatic hydrocarbon solvents in a weight ratio of ４4: 1.

[0007] US Patent No. 3,975,453 discloses 1,
Fine powder obtained by dispersing 2-butadiene or an unsaturated hydrocarbon selected from the group consisting of a mixture of 1,2-butadiene, 1,3-butadiene, 1-butyne and 2-butyne in a strongly coordinated ethereal solvent A method for producing butynyl lithium by passing through a slurry of lithium metal is described.

US Pat. No. 4,339,397 discloses a process for preparing the sodium salt of a 1-alkyne of the general formula R ¹ R ² C (H) C≡CNa, which comprises the corresponding 1,2
-Describes a method of reacting alkadiene with sodium metal in an inert organic solvent.

[0009] describe the use of multiple metallization composition as catalyst in the process and polymerization reaction to produce a summary polymetalated compositions of the invention. This method uses the following formula (A-1): R ² —CH ＝ C 2CH ₂ [wherein R ²
Is hydrogen or an aliphatic group containing from 1 to about 10 carbon atoms.] (A-2) an organometallic compound R ⁰ M, wherein R ⁰ is a hydrocarbyl group; M
Is an alkali metal] with a molar ratio of about 1: 2 to about 1: 6.

[0010] A method for producing a hydrocarbon-soluble multimetallized composition will be briefly described. The method comprises the steps of (A) (A-1) wherein R ² -CH = C = CH _{2 wherein} R ² is , Hydrogen, or 1
The allene compounds of a is] aliphatic group (A-2) an organometallic compound R ⁰ M [wherein containing about 10 carbon atoms, R ⁰
Is a hydrocarbyl group, and M is an alkali metal] to produce an intermediate by a molar ratio of about 1: 2 to about 1: 6; and (B) converting the intermediate to 1,3 Reacting such that the molar ratio of the conjugated diene and the 1,3-conjugated diene to the allene compound is at least about 2: 1.

[0011] The hydrocarbon soluble polymetallated compositions prepared by the process of the present invention are useful as catalysts in anionic polymerization.

[0012] The first embodiment of DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention, (A-1) formula R ² -CH
ＣCＣＨCH ₂ wherein R ² is hydrogen or an aliphatic group containing from 1 to about 10 carbon atoms, and (A-2) an organometallic compound R ⁰ M [formula Wherein R ⁰ is a hydrocarbyl group, and M is an alkali metal] with a molar ratio of about 1: 2 to about 1: 6 for producing a multimetallated composition. Is the way.
The multi-metalated composition of the first embodiment is described herein as
Sometimes called "intermediates". This is because they can be further reacted with 1,3-diene compounds.

The second embodiment of the present invention relates to (A) (A-
1) Formula R ² —CH ＝ C ＝ CH ₂ wherein R ² is hydrogen,
Or (A-2) an organometallic compound R ⁰ M, wherein R ⁰ is a hydrocarbyl group, and M is an alkali metal compound, which is an aliphatic group containing 1 to about 10 carbon atoms. To produce an intermediate by reacting the intermediate with a molar ratio of about 1: 2 to about 1: 6, and (B) reacting the intermediate with a 1,3-conjugated diene and a 1,3-conjugated diene. The molar ratio of the allene compound to at least about 2:
1. A method for producing a hydrocarbon soluble multimetallized composition comprising the step of reacting as described in 1. The composition produced by the method of the second embodiment is sometimes referred to herein as a "diene modified" multimetallized composition.

The allene compound used in the method of the present invention has the formula R ² —CH ＝ C ＝ CH ₂ wherein R ² is hydrogen or an aliphatic group containing from 1 to about 10 carbon atoms. Is]. More often, R ² is an aliphatic group containing from 1 to about 4 carbon atoms. Representative examples of such allene compounds include allene (1,2-propadiene), 1,2-butadiene,
1,2-pentadiene, 1,2-hexadiene, 1,2
-Heptadiene, 1,2-octadiene and the like.

The organometallic compound is represented by the formula R ⁰ M, wherein R ⁰ is a hydrocarbyl group which may be a saturated aliphatic group, a saturated alicyclic group, or an aromatic group.
Generally, R ⁰ will contain up to about 20 carbon atoms. M is an alkali metal such as lithium, sodium,
Potassium, rubidium, cesium and francium. Representative examples of the organometallic compound R ⁰ M are sodium methyl, ethyl lithium, propyl lithium, potassium isopropyl, n- butyl lithium, s- butyl lithium, t- butyl potassium, t- butyl lithium, pentyl lithium, n- Amyl rubidium, tert. -Including octyl cesium, phenyl lithium, naphthyl lithium and the like.

The molar ratio of R ⁰ M to the allene compound is from about 2: 1 to about 6: 1, more often from about 3: 1 to about 5: 1.

The reaction of the allene compound with the organometallic compound (followed by the reaction with the 1,3-conjugated diene) is carried out in the presence of an inert diluent and, in particular, of a hydrocarbon such as an aliphatic, cycloaliphatic or It can be carried out in the presence of an aromatic hydrocarbon. Representative examples of suitable hydrocarbon diluents include n-butane, n-hexane, isooctane, decane, dodecane,
Includes cyclohexane, methylcyclohexane, benzene and the like. Preferred hydrocarbons are aliphatic hydrocarbons containing from 4 to about 10 carbon atoms per molecule. Mixtures of multiple hydrocarbons can also be utilized.

The number of metal substituents introduced into the composition of the present invention depends mainly on the type of the allene compound and the relative amounts of the allene compound and the organometallic compound present in the initial reactant. Will depend. While not wishing to be bound by any theory, it is believed that when the organometallic compound reacts with the allenic compound on an equimolar basis, one or both of the following reactions will occur.

(1) R ² -CH = C = CH ₂ + R ⁰ M → R ² CH ₂ C≡CM + R ⁰ H (2) R ² CH = C = CH ₂ + R ⁰ M → R ² CH = CH = CHM + R ⁰ H In the first reaction, the allene compound is rearranged to 1-alkyne. It is currently believed that reaction (1) is the predominant reaction.

When two moles of R ⁰ M are reacted with one mole of an allene compound, the resulting intermediate has the formula R ²
CH (M) C≡CM and / or R ² CH = C = C (M) ₂
And when 3 moles are reacted, the resulting intermediate has the formula R ² -C (M) ₂ C≡
CM or R ² C (M) = C = C (M) ₂ . When R ² is hydrogen, 4 moles of R ⁰ M can be reacted, and the structure of the intermediate is M ₂ C =
C = CM ₂ and / or M ₃ C−C≡CM. 1 mole of intermediates produced when the allene compound is reacted with greater R ⁰ CM than 2 moles, comprise together with unreacted R ⁰ M, the mixture of multi-metallization 1- alkynes and polymetallic arene It is now believed to consist of

The reaction between the allenic compound and the organometallic compound to form an intermediate can be carried out at a temperature of from 20 to 80 ° C., and this reaction is generally carried out in an inert atmosphere, for example with nitrogen. Do it below. This reaction is generally performed at atmospheric pressure. The intermediate resulting from this reaction is believed to be a mixture of multimetallated alkynes and / or multimetallated allenes that are either insoluble or only slightly soluble in hydrocarbons. It is believed that the presence of unreacted R ⁰ M increases the solubility of the mixture of polymetallated compounds.

The multimetallated composition (first embodiment) produced by the above method of the present invention comprises a mixture of at least one multimetallated 1-alkyne and at least one multimetallated allene. Can be characterized as Multimetalated 1-alkynes have the formula

[0023]

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Wherein R ² is hydrogen, a hydrocarbyl group or M; R ¹ is hydrogen or M;
Is an alkali metal]. The allene compound in the mixture has the formula

[0025]

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Wherein R ² is hydrogen, a hydrocarbyl group or M, and R ¹ is hydrogen or M, and M is an alkali metal. The amounts of the various polymetalated compounds in the composition of the first embodiment of the present invention are currently unknown.

In a second embodiment of the present invention, the above described intermediate is reacted with a 1,3-conjugated diene. The reaction between the intermediate and the 1,3-conjugated diene produces a hydrocarbon soluble diene reformed product, and the reaction is generally carried out at temperatures above 50 ° C. and more usually at about 7 ° C.
It is carried out at a temperature between 0 ° C and about 150 ° C. The reaction is generally complete in less than about 5 hours. At about 80 ° C., the reaction is completed in about 2 hours. At higher temperatures, the reaction is completed in less than 2 hours. If the reaction mixture is heated for too long a period, the resulting product may have reduced catalytic activity. The product of this reaction is a hydrocarbon-soluble multimetallized composition believed to comprise one or more multimetalated 1-alkynes and one or more multimetalated allene-based compounds, and wherein these alkynes are And allenes contain one or more divalent oligomeric hydrocarbyl groups comprising sites derived from 1,3-conjugated dienes.
The molar ratio of the 1,3-conjugated diene to the allene compound reacted with the intermediate is at least about 2: 1 and 30:
It may be as high as one. In one preferred embodiment, the molar ratio of the conjugated diene to the allene compound is about 8: 1.
~ 20: 1.

The 1,3-conjugated diene can be any of a variety of 1,3-conjugated dienes, such as those containing from 4 to 12 carbon atoms and preferably from 4 to 8 carbon atoms per molecule. A specific example of a 1,3-conjugated diene is 1,3-
Butadiene, isoprene, 2,3-dimethyl-1,3-
Butadiene, 1,3-pentadiene (piperylene), 2
-Methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2
-Methyl-1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene and the like. In one preferred embodiment, the 1,3-conjugated diene is 1,3-butadiene, isoprene or 1,3-pentadiene.

In a second embodiment of the present invention, the multimetallated (modified) diene modified (modified) composition of the present invention comprises:
It can be characterized as comprising at least one multimetallated 1-alkyne and at least one multimetallated allene. The hydrocarbon soluble multimetalated 1-alkyne is
formula

[0030]

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Wherein R ² is hydrogen, a hydrocarbyl group or R ³ M; R ⁴ is hydrogen or R ³ M;
Is an alkali metal, and R ³ is a divalent oligomeric hydrocarbyl group comprising a site derived from a conjugated diene. The hydrocarbon soluble allene has the formula

[0032]

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Wherein R ² is hydrogen, a hydrocarbyl group or R ³ M; R ⁴ is hydrogen or R ³ M;
Is an alkali metal, and each R ³ is independently a divalent oligomeric hydrocarbyl group comprising a site derived from a conjugated diene.

As noted above, R ² can be hydrogen or a hydrocarbyl group, which can be a saturated aliphatic, saturated cycloaliphatic or aromatic group, generally containing up to about 10 carbon atoms. In one embodiment, R ² is an alkyl group containing 1-5 carbon atoms. In a further embodiment, R ² is a methyl group. M is an alkali metal such as lithium, sodium, potassium, rubidium, cesium and francium. Lithium, sodium and potassium are the preferred alkali metals, and lithium is the most preferred alkali metal, especially when the polymetallated composition is to be used as a polymerization catalyst.

The substituent R ³ in formulas III and IV is a divalent oligomeric hydrocarbyl group comprising a site derived from a 1,3-conjugated diene as described above. The number of moieties derived from a conjugated diene in the R ³ groups of the composition of formula III and IV can vary over a 2 to about 30 range. Generally, Formulas III and IV
The total number of moieties derived from a conjugated diene in all the R ³ groups in the composition of from about 2 to about 30. In one preferred embodiment, the total number of conjugated diene induction sites in all R ³ groups in the compositions of Formulas III and IV is:
From about 8 to about 20. The number of moieties derived from a conjugated diene oligomeric in radical R ³ is from about 200 to about 3000
Can be varied to give a composition having a weight average molecular weight of In one preferred embodiment, the composition has a weight average molecular weight in the range of about 500 to about 1500.

The polymetallated compounds prepared by the process of the present invention include active as well as inert metals. The presence of at least two different types of carbon metal bonds in the compositions of the present invention can be indicated by both chemical and physical evidence. Gilman titration with allyl bromide distinguishes between a metal acetylide that is inactive (—C≡CM) and another active lithium carbon bond (—CCM). Titration of the composition made by the method of the present invention shows that 50%, 67% and 75% of the total carbon-metal bonds are "active" corresponding to di-, tri-, and tetra-metallated alkynes. Indicates that Ultraviolet and visible spectral studies correspond to inert and active metal bonds, respectively.
300-340 NM and 400 for compositions of the invention
The peak absorption at -450 NM is shown.

An important property of these compositions reacted with 1,3-dienes is that they are soluble in hydrocarbon solvents and that these solutions can be used at room temperature for extended periods of time.
It is stable. As used herein and in the claims, the term "soluble in hydrocarbon solvents" or "hydrocarbon-soluble" refers to the fact that a substance is at least about 25 grams per 100 grams of solvent, especially an aliphatic solvent such as hexane. It is soluble in hydrocarbons up to about 5 g. The composition of the present invention is useful as a catalyst in anionic polymerization and copolymerization of various hydrocarbon monomers.

The following examples illustrate the process of the present invention for making multimetallized intermediates and the method for making hydrocarbon soluble multimetallated compositions. In these examples and elsewhere in the specification and claims, all parts and percentages are by weight, temperatures are in degrees Celsius and pressures are at or near atmospheric unless otherwise specified. .

In each of the following embodiments, 1,2-
Butadiene source is a mixture of 1,2-butadiene and cis-butene-2. Cis-butene-2 is not reactive with n-butyllithium.

[0040]

EXAMPLES Preparation of Intermediates Example A 96 of a 1.6 M solution of n-butyllithium in hexane
ml, and 43% of 1,2-butadiene and 55.2.
% Of the mixture containing cis-butene-2 at 28 oz. With a rubber liner, a three-hole cap and a magnetic stirrer. Produced at room temperature in a drinking bottle under a nitrogen atmosphere. The molar ratio of n-butyllithium to 1,2-butadiene is 3.06: 1. This mixture is brought to 65 ° C.
In a constant temperature bath for 3.0 hours. A small sample of the red clear solution is removed and analyzed for n-butyllithium. In one test, the analysis of the gas chromatograph about BuSiMe ₃ after reaction with ClSiMe ₃ shows that the 71% n-butyl lithium had reacted. Gilm on another little sample
An titration shows 67.9% active carbon-lithium bonds.

EXAMPLES BF The procedure of Example A was carried out at 65 ° C. for a period of about 0.5 to about 7 hours.
And at 80 ° C. The amount of n-butyllithium remaining at the end of each reaction was measured and summarized in the table below.

Example 65 % BuLi Residual at 65 ° C. B 5.0 23-25 C 7.0 21-23 Example 80 % BuLi Residual at 80 ° C. D 0.531 E 1.0 26-27F 2.0 Preparation of 21 Diene Modified Multimetallized Compositions Example 1 28 oz. 96 ml (153.6 mM) of a 1.6 M solution of n-butyllithium in hexane, and 43.0% of 1,3
6.3 grams of a mixture of 2-butadiene and 55.2% cis-butene-2 are added. The mixture is rolled in a constant temperature bath at 50 ° C. for 45 minutes and at 65 ° C. for 5 hours.
Analysis of the intermediate thus obtained showed 75% n-
Butyl lithium had reacted and the intermediate was 66.
Contains 7% active carbon-lithium bonds (Gilm
an titration).

To the above mixture (intermediate) is added 120.8 g of a blend of 1,3-butadiene in hexane containing 23.5% 1,3-butadiene. The molar ratio of 1,3-butadiene to 1,2-butadiene is 10.5: 1.
It is. The mixture is left at 65 ° C for 25 minutes and at 80 ° C.
Roll for 2 hours to produce the desired product, which is cooled to room temperature and stored.

Example 2 In a 10 gallon nitrogen-filled stainless steel reactor, about 3200 g of hexane, 694.8 g of 45.7 were added.
% 1,2-butadiene and 54% cis-butene-2.
As well as about 7.67 kg of a 15% solution of n-butyllithium in hexane. The mixture is stirred at room temperature for 30 minutes. Next, about 9.6 kg of a blend of 1,3-butadiene (33%) in hexane (the molar ratio of 1,3-butadiene to 1,2-butadiene is 10: 1) is added and the mixture is added. Jacket temperature about 8
Heat by raising to 5 ° C (185 ° F) and maintain this temperature for 2 hours. The desired product is obtained, which is cooled to room temperature.

Example 3 In a 10 gallon nitrogen filled stainless steel reactor, 3.2 kg of hexane, 694.8 g of 45.7%
Of 1,2-butadiene and 54% of cis-butene-2, and 7.67 kg of a 15% solution of n-butyllithium in hexane. About 65 of this mixture
Stir at 3 ° C. for 3 hours and then cool to about 32 ° C.
Blend of 1,3-butadiene (33% in hexane
(9.62 kg)) (the molar ratio of 1,3-butadiene to 1,2-butadiene is 10: 1) and the mixture is stirred at about 160 ° F. for about 2 hours. . Cool the product to room temperature.

The hydrocarbon-soluble diene-modified polymetallated composition produced by the process of the present invention is stable at room temperature for an extended period of time. For example, the multimetallized compositions can be stored at room temperature for up to 6 months or more under a nitrogen atmosphere without significant loss of their activity as a catalyst for anionic polymerization reactions.

The polymetalated diene-modified compositions of the present invention can be prepared from various hydrocarbon monomers such as olefins such as ethylene, styrene, α-methylstyrene, divinylbenzene and alkyl-substituted styrenes; and dienes such as butadiene, isoprene and piperylene. And a catalyst for anionic polymerization of 2,3-dimethylbutadiene. These catalysts can also be utilized to produce copolymers or mixtures comprising two or more of the above olefins, dienes, or mixtures thereof. The polymers and copolymers obtained in this manner contain alkali metals, and these types of polymers have been termed "living polymers". The "active terminus" (i.e., carbon-alkali metal bond) of these polymers can be used to attach the polymer, or by attaching terminal functional groups such as silane, hydroxyl, carboxyl, mercapto, Can be used to introduce amino, substituted tin, and the like.

The multimetalated diene modified compositions prepared by the process of the present invention are particularly useful as catalysts for the preparation of copolymers of 1,3-conjugated diene monomers and aromatic vinyl monomers. The relative amounts of conjugated diene and aromatic vinyl monomer contained in these copolymers can vary over a wide range depending on the desired copolymer properties. Thus, the amount of conjugated diene in the copolymer can vary from about 10 to about 90% by weight, and the amount of aromatic vinyl compound can be from about 10 to about 90%.
It can vary in weight percent. More generally, the copolymer comprises from about 50 to about 90%, preferably from about 50 to about 80%, by weight of the conjugated diene and from about 10 to about 50%, more preferably from about 20 to about 50% by weight of the fragrance. Would consist of an aromatic vinyl compound. The copolymer has at least about 30
It may have a weight average molecular weight of 000.

In one embodiment, the copolymers that can be made with the catalyst made according to the method of the present invention are of the type commonly referred to as ultrahigh molecular weight copolymer compositions. The ultra-high molecular weight copolymer composition comprises:
It is essentially gel-free and is further characterized as having a weight average molecular weight greater than about 500,000 and even more than about 1,000,000.
High molecular weight copolymer compositions having a weight average molecular weight greater than 1,100,000 can be produced with the catalysts described herein. Other characteristic features of ultrahigh molecular weight polymers made with the catalyst of the present invention include intrinsic viscosity, dilute solution viscosity, and percent relaxation measured using a Mooney viscometer. In one embodiment, the copolymer composition made with the catalysts described herein is characterized as having an intrinsic viscosity in tetrahydrofuran of at least 4.0, and in another embodiment, The copolymer has an intrinsic viscosity in tetrahydrofuran of at least about 4.5.

[0050] Copolymer compositions made with the catalysts described herein can also be characterized in terms of percent relaxation as measured by the procedure discussed more fully below. In one embodiment, the composition is characterized by a percent relaxation value of at least about 30% to about 100%, and more specifically, about 30% to about 70% relaxation.

[0051] The high molecular weight copolymer composition can also be characterized as having a dilute solution viscosity in toluene of at least about 3.5 dl / g, and in one embodiment, the copolymer is at least about 4.0 dl / g.
g of dilute solution viscosity. Copolymers will also generally be characterized by a M _w / M _n ratio of at least about 1.3.

A copolymer of a conjugated diene and an aromatic vinyl compound is prepared by polymerizing the mixture in a hydrocarbon solvent in the presence of the above-described polymetallated 1-alkyne catalyst composition. Polymerization temperatures can range from about 0 ° C to about 160 ° C or higher, but generally range from about 75 ° C to 1 ° C.
At a temperature of 50 ° C. for a period of about 10 minutes to about 2 or 3 hours,
Perform the polymerization. In a preferred embodiment, about 10
The polymerization is carried out at a temperature near 0 ° C. for about 15 minutes to 1 hour.

The amount of catalyst (polymetallated diene modified composition described above) used in the preparation of the copolymer is determined by the desired molecular weight of the copolymer. In one embodiment, the number of moles of catalyst charged to the reactor is 10
It is determined based on 0 g of monomer and can be calculated by dividing 100 by the desired molecular weight. For example, if a molecular weight of 500,000 is desired, 0.0
002 moles (100 divided by 500,000), ie 0.2
0 mmol of catalyst is charged to the reactor for every 100 g of monomer in the reactor.

Periodically, samples may be removed from the reactor during the polymerization reaction to determine the percent conversion (by measuring total solids), color and properties of the reactants. The reaction time of the polymerization depends on several factors, such as the polymerization temperature, the amount of the polar modifier (eg, 2,2′-di (tetrahydrofuryl) propane) and the catalyst concentration. Generally, complete conversion to the polymer can be obtained at a temperature of about 100 ° C. in about 15 minutes to 1 hour.

When the polymerization reaction has proceeded to the desired extent,
The product can be withdrawn from the reactor or combined with an alcohol such as methanol or isopropanol or other liquid medium which deactivates the initiator and pseudo-solidifies and precipitates the polymer product. Generally, an amount of isopropanol by weight equal to the amount of diluent (eg, hexane) used is sufficient to cause pseudo-solidification and precipitation. An antioxidant such as about 1% di-tert. It is also conventional and advantageous to include -butyl p-cresol. The copolymer product is recovered and dried to remove the solvent.

Unless otherwise stated, the molecular weights for the copolymers described herein are 34 Maple Street
et, Milford, Massachusetts,
01575 U.S. S. A. Measurements are made by gel permeation chromatography (GPC) according to techniques well known to those skilled in the art, using equipment, software and procedures supplied by Millipore's Waters Chromatography Division, Inc. The measurement is
It is performed using a preparative grade PL gel (crosslinked polystyrene) column. A sample of the polymer was dissolved in tetrahydrofuran (THF) stabilized by an antioxidant such as dibutyl p-cresol and four metallizations (cl)
ad) Inject into a GPC device equipped with a column. Especially,
GPC molecular weight measurements for the copolymers of the present invention are based on Wa
Performed using a model 200 Waters gel permeation chromatograph modified with a ters 510 pump, R-410 differential refractometer, and Waters Wisp injector system. Four Polymer Labs P
L gel column is used, but all have 7.5mm diameter x 3
00 mm in length, and sequentially 10 ⁶ , 10 ⁵ , 1
0 ⁴ and having a nominal pore size of 10 ³ Å, bridged polystyrene / divinylbenzene is filled. Polymer sample (0.005g)
Is placed in a flask containing 10 ml of stabilized THF, stoppered and allowed to stand overnight to complete the polymer solution. The sample is then filtered through a 0.45 micron pore size syringe filter.
Select a 200 μl sample of the THF-polymer solution,
Then, an operation time of 33 minutes is used. The flow rate of THF through the chromatograph is set at 1.5 ml per minute and, after equilibrium has been achieved, the copolymer sample solution is injected. The sample is chromatographed at room temperature and the detection of the eluted polymer fraction is carried out by means of a refractometer measurement performed at 32 ° C. Using overlapping injections at two hour intervals, this is achieved using two data acquisition interfaces. The resulting molecular weight separation is measured by the differential refractometer, and calculation of molecular weight parameters is performed using a computer program. The software used in these measurements is Waters M
It is an illennium multi-system software. Universal calibration is available from Pressure Chemical
Performed with a narrow distribution of polystyrene standards obtained from al.

The dilute solution viscosity (DSV) of the copolymer in toluene is measured as follows. A weighed sample of the copolymer is placed in a 4 oz bottle and the exact weight (W ₁ ) is determined. Add toluene (100 ml) using a pipette and cap the bottle tightly. The resulting solution was left at room temperature for about 18 hours, after which the mixture was shaken vigorously and
2 Filter through filter paper. A portion (10 ml) of the filtrate is pipetted into a tared aluminum pan,
The solvent is then evaporated on a hot plate and subsequently dried for 10 minutes in an oven maintained at 105 ° C.
The dry sample is weighed and drying is continued until the residue (liquid copolymer) shows a constant weight (W ₂ ).
The effluent time of the solvent (toluene) and of the filtered solution (residue) was determined by using
10 / I Schott Gerate Ubello
It is measured using an hde microviscometer. The viscometer is placed in a constant temperature bath (25 ° C.) for measurement of the outflow time. The programmed computer calculates the following formula: DSV = [Ln (solution outflow time / solvent outflow time)] /
(W ₂ x10) percent gel _{= 1- (W 2 x10 / W} 1) automatically calculates x100 based on to the DSV and the percent gel of the filtered solution.

The intrinsic viscosity (η) of the copolymer is determined by the general procedure used for DSV, except that the intrinsic viscosity is the average of four data points obtained for four different concentrations.

The glass transition temperature (Tg) of the copolymer
DuPont with 910 differential scanning colorimeter system
Measure using a 1090 thermal analyzer and according to the manufacturer's recommended procedure. Start, midway (infection)
And the end temperature are calculated according to the Interactive DSC Data Analysis Program V2D. The relaxation properties of the copolymer were measured using a Bendix Scott STI
/ 200 Mooney viscometer and a modification of the conventional method for measuring the "shear viscosity" of rubber and rubber-like substances such as SBR. In this procedure, the samples are placed between the platens and then they are closed.
Warm the sample at 100 ° C. for 1 minute and spin the rotor. After 4 minutes, measure the Mooney value (ML _{1 + 4} ) and stop the rotor. Begin measuring relaxation and record the relaxation time (AL ₈₀ ) when the torque reaches 20% of the Mooney value ML _{1 + 4} (T ₈₀ ). After a total of 10 minutes, the torque is again observed and recorded as Al _{1 + 4 + 5} and the platen is opened. The percent relaxation is calculated as follows: Percent relaxation = (AL _{1 + 4 + 5} / ML _{1 + 4} ) _× 100 The following examples are used as catalysts in making copolymers of styrene and 1,3-butadiene. 2 illustrates the use of the catalyst composition produced by the method of the present invention.

Example P-1 In a 100 gallon nitrogen filled stainless steel reactor:
115.7 kg of dry hexane, 29.8 kg of 33% styrene in hexane and 36.4 kg of a 33% solution of 1,3-butadiene in hexane are charged. The mixture was stirred and the reactor jacket temperature was raised to 50 ° C.
Heat by raising to (122 ° F). When the temperature of the mixture reaches about 43 ° C. (110 ° F.), the modifier (76.2 g of 2,2′-di (tetrahydrofuryl))
Propane) and 155.3 g of the product of Example 1 are added. The mixture is exothermic to about 168 ° F (75 ° C) and the jacket temperature is maintained at 60 ° C for 1 hour.
The mixture was cooled to room temperature and 225 g of water and 318
g antioxidant (Santoflex 13) is added. The copolymer is isolated by steam desolvation and oven drying. The analysis of the resulting polymer is as follows:

[0061]

[Table 1]

The analysis by gas chromatography is as follows.
It shows 00% styrene and 97.4% butadiene conversion.

Example P-2 1241.4 kg of dry hexane, 258.9 k in a 1000 gallon nitrogen filled stainless steel reactor
g of 33% styrene in hexane and 450.4 kg
Is charged with a 33% solution of 1,3-butadiene in hexane. The mixture is agitated and heated by raising the reactor jacket temperature to 63 ° C (145 ° F). When the temperature of the reactor mixture reached about 43 ° C. (110 ° F.), 161.2 g of 2,2′-di (tetrahydrofuryl) propane) and 1.69 kg of catalyst formation obtained in Example 2 Add things. The reaction mixture is 1
An exotherm to 217 ° F (03 ° C) and the jacket temperature was raised to 49 ° C (120 ° C) 30 minutes after the peak temperature was reached.
° F). The reaction product was cooled to room temperature and 2.4 kg of water and 3.5 kg of antioxidant (Sant
offlex 13) is added. The polymer is isolated by steam desolvation and oven drying. The resulting copolymer is analyzed as follows:

[0064]

[Table 2]

In this polymerization, a conversion of 99.8% butadiene and 100% styrene to polymer is achieved.

Example P-3 A 10 gallon nitrogen filled stainless steel reactor was charged with 1
2.4 kg dry hexane, 33% styrene in 2.6 kg hexane, and 33% in 2.5 kg hexane
% Of 1,3-butadiene. The mixture is stirred and heated by increasing the reactor jacket temperature to 63 ° C. At about 43 ° C., 1.55 g of 2,2 ′
-Di (tetrahydrofuryl) propane) and 16.5 g
The catalyst product described in Example 3 is added. The reaction mixture exotherms to about 75 ° C., and the jacket temperature is reduced to 49 ° C. 30 minutes after the peak temperature is reached. The reaction product is cooled to room temperature, water and antioxidants are added, and the polymer is isolated by drum drying. The resulting copolymer (conversion higher than 99%) is analyzed as follows:

[0067]

[Table 3]

While the invention has been described in terms of a preferred embodiment thereof, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it should be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

The main features and aspects of the present invention are as follows.

1. (A-1) Formula R ² -CH = C = C
H ₂ wherein R ² is hydrogen or an aliphatic group containing from 1 to about 10 carbon atoms.
Reacting with an organometallic compound R ⁰ M, wherein R ⁰ is a hydrocarbyl group and M is an alkali metal, in a molar ratio of about 1: 2 to about 1: 6, comprising: For producing an activated composition.

2. R ² is an aliphatic group containing from 1 to about 4 carbon atoms, the method of claim 1, wherein the.

3. The method of claim 1, wherein R ² is methyl.

4. The method of claim 1, wherein the alkali metal is lithium.

5. The method of claim 1 wherein R ⁰ is an alkyl group containing 1 to about 10 carbon atoms.

6. The method of claim 1, wherein R ⁰ is n-butyl.

7. (A) (A-1) Formula R ² —CH =
C = CH ₂ wherein R ² is hydrogen or an aliphatic group containing 1 to about 10 carbon atoms
-2) organometallic compound R ⁰ M [in the formula, R ⁰ is an hydrocarbyl group and M is an alkali metal] and about 1:
Preparing an intermediate by reacting in a molar ratio of 2 to about 1: 6; and (B) converting said intermediate to 1,3
-A process for producing a hydrocarbon soluble polymetallated composition comprising the step of reacting such that the molar ratio of the conjugated diene and the 1,3-conjugated diene to the allene compound is at least about 2: 1. .

8. R ² is an aliphatic group containing from 1 to about 4 carbon atoms, the method of claim 7, wherein.

9. The method of claim 7, wherein R ² is methyl.

10. The alkali metal is lithium,
The method according to the above 7,

11. The method of claim 7, wherein R ⁰ is an alkyl group containing 1 to about 10 carbon atoms.

12. 1,3-conjugated diene is aliphatic 1,
8. The method according to the above 7, which is a 3-diene.

13. 8. The method according to the above 7, wherein the 1,3-conjugated diene is 1,3-butadiene, isoprene or piperylene.

14. The method of claim 7, wherein the molar ratio of the 1,3-conjugated diene to the allene compound is from about 8: 1 to about 20: 1.

15. The method of claim 7, wherein the 1,3-conjugated diene is 1,3-butadiene.

16. (A) (A-1) Formula R ² —CH
= C = CH ₂ [wherein R ² is hydrogen or an aliphatic hydrocarbyl group containing 1 to about 4 carbon atoms] (A-2) an organolithium compound R ⁰ Li [ Wherein R ⁰ is an aliphatic group containing from 1 to about 5 carbon atoms] and a molar ratio of from about 1: 2 to about 1: 6 to produce an intermediate; and (B C.) Reacting the intermediate such that the molar ratio of 1,3-conjugated diene to 1,3-conjugated diene to the allene compound is at least about 2: 1. A method for producing a metallized composition.

17. 17. The method according to the above item 16, wherein the allene compound is 1,2-butadiene.

18. 1 above, wherein R ⁰ is n-butyl.
6. The method according to 6.

19. 16. The above-mentioned item 16, wherein the 1,3-conjugated diene is 1,3-butadiene, isoprene or piperylene.
The described method.

20. 17. The method of claim 16, wherein the molar ratio of the conjugated diene to the allene compound is from about 8: 1 to about 20: 1.

21. (A) (A-1) 1,2-butadiene is converted to (A-2) an organolithium compound R ⁰ Li [wherein:
R ⁰ is an aliphatic group containing from 1 to about 4 carbon atoms] and a molar ratio of from about 1: 3 to about 1: 4 to produce an intermediate; and (B) 1 mole of Reacting the above intermediate with from about 8 to about 20 moles of 1,3-butadiene.

22. 22. The method according to 21 above, wherein the reaction in step (A) is performed in a hydrocarbon solvent.

23. A composition comprising a mixture of one or more multimetalated 1-alkynes and one or more multimetallated allene compounds, wherein the 1-alkyne has the formula

[0093]

Embedded image

Wherein R ² is hydrogen, a hydrocarbyl group or M, and R ¹ is hydrogen or M, and M is an alkali metal.
And the allene compound has the formula

[0095]

Embedded image

Wherein R ² is hydrogen, a hydrocarbyl group or M; R ¹ is hydrogen or M;
Is an alkali metal].

24. In the above formula 23, R ² is a hydrocarbyl group and R ¹ is hydrogen or M.
A composition as described.

25. In the formula II, R ² is a hydrocarbyl group and R ¹ is hydrogen or M.
3. The composition according to 3.

26. 24. The composition according to the above 23, wherein M is lithium.

27. The composition according to claim 23, wherein in formula I, R ² is methyl and R ¹ is hydrogen or M.

28. A hydrocarbon-soluble composition comprising a mixture of one or more multimetalated 1-alkynes and one or more multimetalated allenes, wherein the alkyne has the formula

[0102]

Embedded image

Wherein R ² is hydrogen, a hydrocarbyl group or R ³ M; R ⁴ is hydrogen or R ³ M;
Is an alkali metal and R ³ is a divalent oligomeric hydrocarbyl group comprising a site derived from a conjugated diene.

[0104]

Embedded image

Wherein R ² is hydrogen, a hydrocarbyl group or R ³ M; R ⁴ is hydrogen or R ³ M;
Is an alkali metal, and each R ³ is independently a divalent oligomeric hydrocarbyl group comprising a site derived from a conjugated diene.

29. 28. The composition according to claim 28, wherein the composition comprises a mixture of a plurality of multimetalated 1-alkynes represented by formula III wherein R ⁴ is hydrogen or R ³ M and R is a hydrocarbyl group. Composition.

30. A hydrocarbyl group R ² contains from 1 to about 5 carbon atoms and M is lithium,
29. The composition according to the above item 28.

31. A copolymer composition of a 1,3-conjugated diene and a vinyl aromatic compound comprising polymerizing a 1,3-conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent in the presence of the composition of 28 above. Method for manufacturing.

32. 32. The method according to 31 above, wherein M is lithium.

33. R ³ is derived from an alkadiene containing from 4 to about 12 carbon atoms, the method of the 31 described.

34. The total number of conjugated diene derived sites in all R ³ groups is about 8 to about 20, and the conjugated diene is 1,3-butadiene, the method of the 31 described.

Claims (7)

[Claims] (A-1) Formula R ² -CH = C = CH
₂ wherein R ² is hydrogen or an aliphatic group containing 1 to about 10 carbon atoms, and (A-2) an organometallic compound R ⁰ M [wherein R ⁰ Is a hydrocarbyl group and M is an alkali metal] with a molar ratio of about 1: 2 to about 1: 6. (A) (A-1) Formula R ² —CH = C =
An allene compound of CH ₂ [wherein R ² is hydrogen or an aliphatic group containing 1 to about 10 carbon atoms] is represented by (A-
2) about 1: 2 with the organometallic compound R ⁰ M, where R ⁰ is a hydrocarbyl group and M is an alkali metal.
Preparing an intermediate by reacting at a molar ratio of about 1: 6, and (B) converting the intermediate to 1,3-
A method of making a hydrocarbon soluble polymetallated composition, comprising the step of reacting such that the molar ratio of the conjugated diene and the 1,3-conjugated diene to the allenic compound is at least about 2: 1. (A) (A-1) Formula R ² —CH = C =
Wherein the allene-based compound of CH ₂ [wherein R ² is hydrogen or an aliphatic hydrocarbyl group containing 1 to about 4 carbon atoms] is (A-2) an organolithium compound R ⁰ Li R ⁰
Is an aliphatic group containing 1 to about 5 carbon atoms] to produce an intermediate by a molar ratio of about 1: 2 to about 1: 6; and (B) reacting the intermediate Reacting the 1,3-conjugated diene and the 1,3-conjugated diene to the allene-based compound in a molar ratio of at least about 2: 1. How to make. (A) (A-1) 1,2-butadiene is converted to (A-2) an organolithium compound R ⁰ Li [where R ⁰ is 1
About 4 carbon atoms] and about 1: 3
Preparing the intermediate by reacting in a molar ratio of about 1: 4, and (B) reacting 1 mole of the intermediate with about 8 to about 20 moles of 1,3-butadiene. A method for producing a hydrocarbon soluble polylithiated composition comprising: 5. A composition comprising a mixture of one or more multimetalated 1-alkynes and one or more multimetallated allene compounds, wherein the 1-alkyne has the formula: Wherein R ² is hydrogen, a hydrocarbyl group or M, and R ¹ is hydrogen or M, and M is an alkali metal, and the allene compound is represented by the formula: ] Wherein R ² is hydrogen, a hydrocarbyl group or M, R ¹ is hydrogen or M, and M is an alkali metal. 6. A hydrocarbon-soluble composition comprising a mixture of one or more multi-metalated 1-alkynes and one or more multi-metalated allenes, wherein said alkyne has the formula: Wherein R ² is hydrogen, a hydrocarbyl group or R ³ M, R ⁴ is hydrogen or R ³ M, M is an alkali metal, and R ³ is derived from a conjugated diene Is a divalent oligomeric hydrocarbyl group comprising moieties, and wherein the allene is of the formula Wherein R ² is hydrogen, a hydrocarbyl group or R ³ M, R ⁴ is hydrogen or R ³ M, M is an alkali metal, and each R ³ is independently conjugated A divalent oligomeric hydrocarbyl group comprising a site derived from a diene]. 7. A 1,3-conjugated diene and a vinyl aromatic, comprising polymerizing a 1,3-conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent in the presence of the composition of claim 6. A method for producing a copolymer composition of a compound.