JPH06322013A - Polymerization initiator, polymerization method, and polymer - Google Patents

Abstract

(57) [Summary] [Structure] A polymerization initiator comprising an alkenyllithium compound represented by the general formula: CH ₂ = CH (CH ₂ ) nLi (wherein n represents an integer of 3 or more), and the polymerization initiation. And a general formula: CH ₂ ═CH (CH ₂ ) n- (wherein n is 3 or more, characterized in that anionic polymerization is performed using an agent. A polymer having a double bond-containing group represented by. [Effect] A desired double bond is quantitatively introduced into at least one terminal of the polymer by anionically polymerizing an anionically polymerizable monomer using the polymerization initiator comprising the alkenyllithium compound of the present invention. It is possible to produce polymers of molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel anionic polymerization initiator comprising an alkenyllithium compound, a method for producing a polymer having a double bond at at least one end using the polymerization initiator, and a diamine at at least one end. It relates to a polymer having a heavy bond.

[0002]

2. Description of the Related Art In recent years, polymer reactions such as block polymerization, graft polymerization and reactive blending have been studied for the purpose of improving the performance of polymer materials, and various functional groups are introduced at the ends of the polymer. Things have been done. Among the polymers having a functional group introduced at the end, particularly a polymer having a reactive double bond at the end should form a graft copolymer or a block copolymer directly with another polymer. It is also possible to use it for a wider range of applications by converting the terminal double bond into another functional group by a chemical reaction, which is very useful industrially. As a conventional method for producing such a polymer having a reactive double bond at the terminal, a method of performing radical polymerization in the presence of a chain transfer agent and a method of anionic polymerization are known.

[0003]

In the production method by radical polymerization, a chain transfer agent is used to obtain a polymer having an arbitrary functional group at the terminal, and then a compound having a double bond with the functional group is coupled. It is complicated because it requires a two-step manufacturing process. Further, in radical polymerization, it is difficult to control the molecular weight of the obtained polymer, and since the molecular weight distribution of the obtained polymer is wide, the polymer obtained by such radical polymerization is subjected to graft polymerization or block polymerization. When applied, there is a problem that a polymer having desired physical properties is difficult to obtain. In radical polymerization,
Since the chain transfer reaction and the termination reaction proceed in parallel, there is a problem that it is difficult to quantitatively introduce a functional group into the polymer terminal. There is also a method of polymerizing using a thiol compound having a large chain transfer constant in order to increase the introduction rate of the functional group at the polymer terminal, but the resulting polymer is sulfur-
Since it has a carbon bond, it is susceptible to an oxidation reaction and is unstable.

As a production method by anionic polymerization, vinyllithium, propenyllithium ["Macromonomer Chemistry and Industry", edited by Yuya Yamashita, p.43 (1989)] or butenyllithium ["Polymer" Vol.28, p. 881 (1987)]
Although an anionic polymerization using a polymerization initiator has been reported,
When these polymerization initiators are used, the polymerization rate is very slow, and the living polymerizability is low, so that a copolymer having a narrow molecular weight distribution and at least a double bond quantitatively introduced at one end is obtained. It was difficult to get.

A first object of the present invention is to provide a polymerization initiator capable of quantitatively introducing a double bond into at least one terminal of a polymer. A second object of the present invention is to provide a method for producing a polymer having a double bond at least at one end. A third object of the present invention is to provide a polymer having excellent stability, a narrow molecular weight distribution, and a double bond at least at one end.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies in order to solve the problems of the above-mentioned prior art, and as a result, an alkenyllithium compound having a double bond at the 1-position was used as a polymerization initiator. It was found that a polymer having a double bond at least at one end can be quantitatively obtained by anionically polymerizing a polymerizable monomer,
The present invention has been completed based on the findings.

According to the present invention, the first object mentioned above is achieved by providing a polymerization initiator comprising an alkenyllithium compound represented by the following general formula (I).

[0008] _{CH 2 = CH (CH 2)} nLi (I) ( wherein, n represents an integer of 3 or more.)

A second object of the present invention is to carry out anionic polymerization of an anionically polymerizable monomer using a polymerization initiator comprising an alkenyllithium compound represented by the above general formula (I). It is achieved by providing a method for producing a polymer having a double bond.

The third object of the present invention is to provide the following general formula (I
It has a double bond-containing group represented by I) at the terminal and has a ratio (Mw / Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
This is achieved by providing a polymer having a Mn) of 1.0 to 1.3.

CH ₂ ═CH (CH ₂ ) n- (II) (In the formula, n represents an integer of 3 or more.)

The polymerization initiator of the present invention is an alkenyllithium compound represented by the above general formula (I), for example, 4-pentenyllithium, 5-hexenyllithium, 6-heptenyllithium, 7-octenyl. Examples thereof include lithium and 8-nonenyllithium. Among them, the alkenyllithium compound in which n is 3 to 6 in the above-mentioned general formula (I) is preferable.

Examples of the polymerization initiator of the present invention include alkenyl halides such as 5-bromo-1-pentene, 6-bromo-1-hexene and 7-bromo-1-heptene, and an inert solvent such as n-heptane. It is obtained by reacting with metallic lithium in.

By anionically polymerizing an anionically polymerizable monomer using the above-mentioned polymerization initiator, a polymer having a double bond at least at one end can be obtained.

Examples of anionically polymerizable monomers include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, methoxystyrene, 3,5-diethylstyrene, 4-n-propyl. Styrene, 2,4,6-trimethylstyrene, 4
-Phenyl styrene, 4-p-tolyl styrene, 3,5
-Diphenylstyrene, 1-vinylnaphthalene, 3-ethyl-1-biphenylnaphthalene, 3-phenyl-1-
Aromatic compounds such as biphenylnaphthalene and p-N, N-dimethylaminostyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( (Meth) acrylates such as (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentenyl (meth) acrylate, heptenyl (meth) acrylate; 1,3-butadiene, 1,3 -Pentadiene, 2,3-dimethyl-1,3-butadiene,
Examples thereof include conjugated dienes such as 2,4-hexadiene, 2-phenyl-1,3-butadiene and isoprene; and nitriles such as acrylonitrile and methacrylonitrile. These monomers are used alone or in combination of two or more.

The anionic polymerization can be carried out in the absence of a solvent, but it can also be carried out in the presence of a suitable organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; propane,
Aliphatic hydrocarbon solvents such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, isooctane, decane, hexadecane, isopentene, n-hexene; methylcyclopentane, cyclohexane, cyclooctane, etc. Alicyclic hydrocarbon solvent; ethers such as tetrahydrofuran (THF), dioxane, diethyl ether, dibutyl ether and ethylene glycol diethyl ether. Among these organic solvents, benzene, toluene and THF are preferably used. These organic solvents are used alone or in combination of two or more.

As the polymerization conditions, it is possible to use the polymerization conditions adopted in ordinary anionic polymerization. However, in order to not deactivate the polymerization initiator and the living site at the end of the polymer, it is possible to use oxygen and dioxide in the polymerization system. It is preferable to carry out under the condition that carbon or water is not mixed. For example, under high vacuum (10 ⁻³ Pa or less) or in a nitrogen atmosphere containing almost no water, a polymerization initiator is added to a degassed / dehydrated solvent, and then the above-mentioned monomer is added to carry out anionic polymerization.
The order of adding the polymerization initiator and the monomer may be changed depending on the reactivity of the monomer. Further, the monomers may be polymerized while being gradually added, instead of adding all of the monomers at once.

A copolymer having an arbitrary monomer composition can be obtained by polymerizing the above anionically polymerizable monomers in a combination of two or more kinds. In addition, after the polymerization of one kind of monomer is completed, it is successively polymerized with another kind of monomer to obtain a block copolymer (diblock copolymer, triblock copolymer) having an arbitrary monomer composition and structure. , A multi-block copolymer, etc.) can be obtained. Further, it is also possible to impart a branched structure to the polymer or expand the molecular weight distribution by a method of adding a polyfunctional monomer such as divinylbenzene to the polymerization system during or after the polymerization of the monomer.

The polymerization temperature will vary depending on the type of polymerization initiator, monomer, solvent, etc. used, but is usually from -80 ° C to
The temperature is preferably in the range of 150 ° C, more preferably in the range of -78 ° C to 80 ° C. The polymerization time depends on the polymerization initiator used,
Usually 10 depending on the monomer, solvent, reaction temperature, etc.
Within the range of 10 minutes from 10 minutes. The polymerization reaction can be performed by either a batch method or a continuous method.

When the polymerization is terminated, a compound having active hydrogen is added as a polymerization terminator to the polymerization system to obtain a polymer having inactive termination terminals. Further, by using a polymerization terminator having a specific functional group, it is possible to obtain a polymer (telechelic polymer) in which a specific functional group is introduced at the terminal end of the polymer. Examples of the functional group that can be introduced into the terminating end by this method include a vinyl group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and a halogen. These functional groups can be further converted into a dicarboxyl group, a diol group or the like, if necessary.

Examples of the polymerization terminator include water, methanol, ethanol, propanol, isopropanol,
In addition to compounds having active hydrogen such as butanol, ethylamine, propylamine, butylamine, diethylamine, dipropylamine, dibutylamine, carbon dioxide,
Ethylene oxide, propylene oxide, bromine, chlorine,
Examples thereof include phosgene, allyl chloride, allyl bromide, glycidyl chloride, vinyldimethylsilyl chloride, vinyldiethylsilyl chloride, vinylbenzyl bromide, vinylbenzyl chloride, (meth) acrylic acid halide, and silane coupling agent.

The molecular weight of the polymer obtained by the present invention is almost uniquely determined by the molar ratio of the monomer and the polymerization initiator. Therefore, by changing the ratio of the amounts of the monomer and the polymerization initiator to be used, It is possible to easily control the molecular weight over a wide range. The controllable molecular weight range is 500 to 500000 in terms of number average molecular weight.
It is a degree. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained from the standard polystyrene calibration curve by the gel permeation chromatography (GPC) method of the obtained polymer is usually 1 .
It is within the range of 0 to 1.3.

The polymer having a double bond-containing group represented by the general formula CH ₂ ═CH (CH ₂ ) n- (wherein n represents an integer of 3 or more) at the terminal of the present invention is Examples thereof include poly (meth) acrylic acid ester-based polymers, poly (meth) acrylonitrile-based polymers, polystyrene-based polymers, polybutadiene-based polymers, polyisoprene-based polymers, and copolymers thereof. . The number average molecular weight of the polymer is 500 to 500,000, preferably 1,000.
Within the range of 100,000. Molecular weight distribution (Mw / M
n) is usually 1.0 to 1.3, preferably 1.0 to
It is within the range of 1.1.

The polymer having a reactive double bond at least at one end, which is obtained by the present invention, can form a graft copolymer or a block copolymer with another polymer, It is a polymer useful for enhancing the functionality of polymer materials. It can also be suitably used as a compatibilizing agent for different polymers. Furthermore, it is also possible to appropriately convert the reactive double bond at the terminal into another functional group by a chemical reaction, and the polymer thus converted into another functional group is suitable for reactive blending and the like. Used. Further, a known coupling agent, for example, an ester compound, a polyepoxy compound, a halogenated hydrocarbon compound, a silicon halide compound, a tin halide compound or the like is used to form a polymer having a reactive double bond at least at one end. It is also possible to modify and use it.

[0025]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. In addition, all reactions were carried out under high vacuum (10 ⁻³ Pa or less) using a glass apparatus equipped with a break seal.

Example 1 5 g of metallic lithium and 6 g of 5-bromo-1-pentene
Was added to 120 ml of n-heptane and reacted at room temperature for 3 days. Next, 40 ml of diethyl ether was added to the reaction solution, the mixture was stirred at 0 ° C. for 24 hours and then filtered, and the solvent of the filtrate was distilled off. By proton NMR analysis, peaks derived from a vinyl group and a methyl anion were observed, and it was confirmed that 4-pentenyllithium was obtained. Yield 70
%Met. Obtained 4-pentenyllithium 0.24
g was diluted with 9.3 ml of n-heptane, and this was added dropwise to a benzene solution of styrene (15-fold mole with respect to 4-pentenyllithium), and the mixture was polymerized at room temperature for 2 hours. Stopped. All the styrene charged was consumed. The number average molecular weight of the obtained polymer determined by the GPC method was 1900, which was in good agreement with the number average molecular weight of the polymer theoretically determined from the molar ratio of the monomer and the polymerization initiator. Molecular weight distribution (Mw / Mn)
Was 1.07. Proton NMR of the obtained polymer
In the spectrum, the number average molecular weight obtained from the ratio of the peak intensity derived from the polystyrene main chain and the peak intensity derived from the terminal vinyl group is 2000, which is in good agreement with the number average molecular weight obtained by the GPC method. It was confirmed that a vinyl group was quantitatively introduced at one end of the united body.

Comparative Example 1 3-Bromo-1-in place of 5-bromo-1-pentene
2-Propenyllithium was synthesized under the same conditions as in Example 1 except that propene was used. The yield was 20%.
The obtained 2-propenyllithium (0.24 g) was diluted with n-heptane (9.3 ml), and this was added dropwise to a benzene solution of styrene (15-fold mol based on 2-propenyllithium), and the mixture was reacted at room temperature for 24 hours. After that, methanol was added to terminate the polymerization, but only 75% of the charged styrene was consumed. The number average molecular weight of the obtained polymer determined by the GPC method was 2000, which did not match the number average molecular weight (1500) of the polymer theoretically determined from the molar ratio of the consumed monomer and the polymerization initiator. . The molecular weight distribution (Mw / Mn) was as wide as 1.4. The number average molecular weight obtained from the ratio of the peak intensity derived from the polystyrene main chain and the peak intensity derived from the terminal vinyl group in the proton NMR spectrum of the obtained polymer was 3000, and the number average molecular weight obtained by the GPC method. It was confirmed that the homopolymer and the polymer in which a vinyl group was not introduced at one end coexisted.

Example 2 4-pentenyllithium 0.24 synthesized in Example 1
g was diluted with 9.3 ml of n-heptane, this was added dropwise to a benzene solution of methyl methacrylate (20-fold mole with respect to 4-pentenyllithium), polymerized at -78 ° C for 2 hours, and then 2 ml of methanol was added. To stop the polymerization. All of the charged methyl methacrylate was consumed. The number average molecular weight of the obtained polymer determined by the GPC method was 2000, which was in good agreement with the number average molecular weight of the polymer theoretically determined from the molar ratio of the monomer and the polymerization initiator. The molecular weight distribution (Mw / Mn) was 1.09. The number average molecular weight determined from the ratio of the peak intensity derived from the polymethylmethacrylate main chain to the peak intensity derived from the terminal vinyl group in the proton NMR spectrum of the obtained polymer was 2000, which was the number obtained by the GPC method. It was in good agreement with the average molecular weight, and it was confirmed that a vinyl group was quantitatively introduced at one end of the polymer.

Example 3 4-pentenyllithium 0.24 synthesized in Example 1
g was diluted with 9.3 ml of n-heptane, and this was added dropwise to a benzene solution of isoprene (50-molar with respect to 4-pentenyllithium) and polymerized at room temperature for 1 hour. Stopped. All of the charged isoprene was consumed. GPC of the obtained polymer
The number average molecular weight determined by the method was 2000, which was in good agreement with the number average molecular weight of the polymer theoretically determined from the molar ratio of the monomer and the polymerization initiator. The molecular weight distribution (Mw / M
n) was 1.08. Proton N of the obtained polymer
The number average molecular weight obtained from the ratio of the peak intensity derived from the polyisoprene main chain and the peak intensity derived from the terminal vinyl group in the MR spectrum was 2000, which is in good agreement with the number average molecular weight obtained by the GPC method. It was confirmed that a vinyl group was quantitatively introduced at one end of the polymer.

Example 4 4-pentenyllithium synthesized in Example 1 0.05
g was diluted with 5 ml of n-heptane, and this was added to styrene (4
-A 270-fold mole of pentenyllithium) was added dropwise to 500 ml of a benzene solution, polymerization was carried out at room temperature for 8 hours, and then carbon dioxide was bubbled through the polymerization solution for 5 minutes to stop the reaction. All the styrene charged was consumed. The number average molecular weight of the obtained polymer was 31,000, which was in good agreement with the number average molecular weight of the polymer theoretically determined from the molar ratio of the monomer to the polymerization initiator. The molecular weight distribution (Mw / Mn) is 1.0.
It was 7. In the proton NMR spectrum of the obtained polymer, the number average molecular weight obtained from the ratio of the peak intensity derived from the polystyrene main chain and the peak intensity derived from the terminal vinyl group, and the peak intensity derived from the polystyrene main chain and the termination end The number average molecular weight obtained from the ratio of the peak intensity derived from the carboxyl group is in good agreement with the number average molecular weight obtained by the GPC method, and a vinyl group is present at one end of the polymer and a carboxyl group is present at the other end. It was confirmed that was introduced quantitatively.

Example 5 5-Bromo-1-instead of 5-Bromo-1-pentene
5-Hexenyllithium was synthesized under the same conditions as in Example 1 except that hexene was used. The yield was 75%.
0.24 g of the obtained 5-hexenyllithium was diluted with 9.3 ml of n-heptane, and this was added dropwise to a benzene solution of styrene (15 moles with respect to 5-hexenyllithium), and polymerized at room temperature for 2 hours. Then, 2 ml of methanol was added to stop the polymerization. All the styrene charged was consumed. The number average molecular weight of the obtained polymer determined by the GPC method was 1950, which was in good agreement with the number average molecular weight of the polymer theoretically determined from the molar ratio of the monomer and the polymerization initiator. The molecular weight distribution (Mw / Mn) was 1.08. The number average molecular weight obtained from the ratio of the peak intensity derived from the polystyrene main chain and the peak intensity derived from the terminal vinyl group in the proton NMR spectrum of the obtained polymer was 2000, and the number average molecular weight obtained by the GPC method. It was confirmed that the vinyl group was quantitatively introduced at one end of the polymer.

[0032]

EFFECTS OF THE INVENTION By using the polymerization initiator comprising the alkenyllithium compound of the present invention, anionic polymerization of an anionically polymerizable monomer is carried out, whereby a double bond is quantitatively introduced into at least one terminal of the polymer. It is possible to produce a polymer having a desired molecular weight in high yield.

Claims (3)

[Claims] 1. A polymerization initiator comprising an alkenyllithium compound represented by the following general formula (I). CH ₂ = CH (CH ₂ ) nLi (I) (In the formula, n represents an integer of 3 or more.) 2. A monomer capable of being anionically polymerized.
A method for producing a polymer having a double bond at a terminal, which comprises performing anionic polymerization using the described polymerization initiator. 3. A compound having a double bond-containing group represented by the following general formula (II) at the terminal and having a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1. 0-1.3
Polymer. _{CH 2 = CH (CH 2)} n- (II) ( wherein, n represents an integer of 3 or more.)