JPH09143224A - Production of primary amino group-terminated polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and reliably introduce primary amino groups at polymer ends, by end-termination of an anionic living polymer with a nitrile such as acetonitrile and by treating under hydrogenation reaction condition. SOLUTION: The processes consist of those by reacting a polymer (A) having carbanion as end groups of the molecule with a nitrile (B) and then treating with a compound (C) having an active hydrogen atom, followed by treating the product under hydrogenation reaction condition. The polymer A can easily be synthesized by anionic living polymerization, and, e.g. an anionic living polymer having carbanions at the ends of the molecule is obtained through the anionic polymerization of a monomers such as an aromatic vinyl compound. It is preferable that the resultant polymer has primary amino groups bound to the secondary carbon atoms at the polymer ends and the ratio (Mw /Mn ) is 1.0-1.3 (where Mw is weight-average molecular weight and Mn is number- average molecular weight).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a polymer having a primary amino group (--NH ₂ ) at the molecular end, and a secondary carbon atom bonded to a secondary carbon atom which can be suitably produced by the method. The present invention relates to a polymer having a primary amino group at the molecular end and having a narrow molecular weight distribution.

[0002]

2. Description of the Related Art Plastics are used in all areas of life including electric / electronic parts, automobiles, transportation equipment parts, building materials and machine parts. At present, in order to further improve the performance of plastics, a study on mixing a plurality of polymers (polymer blend) is being actively conducted. However, in general, the combination of polymers that are compatible when mixed is limited to a small part,
In the majority of cases it causes phase separation, which results in elongation,
There arise problems that mechanical properties such as impact resistance are deteriorated and that a uniform molded product cannot be obtained.

In order to solve this problem, two kinds of polymers having mutually reactive functional groups are melt-kneaded, and at that time, a part of them is reacted and bonded to form a compatibilizer component. Attempts have been made to produce polymer compositions in which, by forming, both polymers are compatible or one polymer is finely dispersed in the matrix of the other polymer. According to this method, it becomes possible to obtain a polymer composition which prevents the above-mentioned deterioration of physical properties and makes the most of the characteristics of each polymer. As the polymer having a functional group having a reactivity suitable for use in this method, a polymer having a highly reactive primary amino group at a molecular terminal can be mentioned.

As a method of introducing a primary amino group into the molecular terminal of the polymer, the anion living polymer is reacted with a halogenoalkylamine protected with an alkylsilyl group or an imine protected with an alkylsilyl group to terminate the terminal. And then deprotecting the amino group by hydrolysis [Japanese Patent Laid-Open No. 58-136604, Makromolekulare Chemie, Vol. 184, No. 135].
Pp 5 to 1362 (1983), Macromourecules (Macromo
Lecules) 23, 939-945 (1990)], a method of reacting an anion living polymer synthesized from styrene with a reagent prepared from methoxyamine and methyllithium [Macromolecules 19
Vol., Pages 1291 to 1294 (1986)] and the like. As another method, there is known a method in which radical polymerization is performed using a chain transfer agent having a primary amino group.

[0005]

However, the method of reacting the above-mentioned anionic living polymer with a protected halogenoalkylamine, a protected imine, or a reagent prepared from methoxyamine and methyllithium is a Suitable for industrialization because the above-mentioned protected compound or the above-mentioned reagent to be used is not industrially versatile and requires the use of expensive raw materials and an extra step under cooling conditions for its preparation. It is hard to say that

In the above radical polymerization method, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer obtained is at most about 1.6 even if it can be reduced. Is. When such a polymer having a relatively large molecular weight distribution is used in the production of the above-mentioned polymer composition, the heterogeneity of the molecular weight and the like in the product by the reaction with other polymers becomes large, so that various desired physical properties and thermal properties are obtained. It is difficult to realize the above with good reproducibility.

The first object of the present invention is to reliably introduce a primary amino group at the molecular end of a polymer by using an industrially versatile compound without passing through extra steps such as protection. Another object of the present invention is to provide a novel method of producing a polymer having a primary amino group at the molecular end. A second object of the present invention is to provide a polymer having a highly reactive primary amino group at the molecular end and having a narrow molecular weight distribution, which can be produced by the method.

[0008]

Means for Solving the Problems As a result of earnest studies, the inventors of the present invention have found that an anionic living polymer end-capped with a nitrile such as acetonitrile is treated under a hydrogenation reaction condition to give a primary polymer at the polymer end. The present invention has been reached by finding that an amino group is easily and surely formed, and by further studies.

According to the present invention, the above-mentioned first object is to react a polymer having a carbanion at a molecular end with a nitrile, and then to treat the polymer with an active hydrogen atom-containing compound, and then to obtain the reaction product. It is achieved by providing a process for producing a polymer having a primary amino group at the molecular end, which is characterized by treating under hydrogenation reaction conditions.

Further, according to the present invention, the above second object is to have a primary amino group bonded to a secondary carbon atom at a molecular end, and to have a weight average molecular weight (Mw) and a number average molecular weight. It is achieved by providing a polymer characterized in that the ratio (Mw / Mn) of (Mn) is in the range of 1.0 to 1.3.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polymer having a carbanion at the molecular end used in the production method of the present invention may be linear or branched. Further, the carbanion may be present at the molecular end to which the primary amino group is to be introduced among the molecular ends of the polymer, and may be at the entire molecular end or at a part of the molecular end. .

The monomer constituting the above-mentioned polymer having a carbanion at the molecular end is not particularly limited, but for example, styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene,
Vinyl aromatic compounds such as 2-vinylnaphthalene; conjugated dienes such as isoprene and butadiene; methacrylates such as methyl methacrylate, ethyl methacrylate, t-butyl methacrylate and phenyl methacrylate; anionically polymerizable monomers such as alkylene oxides such as ethylene oxide and propylene oxide. 1 or 2 such as
More than species are available.

The manner of arrangement of the monomers in the polymer chain is not particularly limited, and can be appropriately selected from the manner of homopolymer, random copolymer, block copolymer and the like according to the purpose. In the case of the block copolymer type, the blocks constituting the block copolymer may be one of a random copolymer block, a homopolymer block or the like or two.
It is arbitrarily selected from more than one species.

There is no particular limitation on the molecular weight of the above-mentioned polymer having a carbanion at the molecular end, but it is suitable for forming processability in the finally obtained terminal amino group-containing polymer and a composition with other polymer. Considering the concentration of terminal amino groups, the number average molecular weight is 10
It is preferably in the range of 0 to 1,000,000,
More preferably, it is in the range of 3000 to 300,000.

The method for producing the above-mentioned polymer having a carbanion at the molecular end is not particularly limited, but it can be easily synthesized by the anion living polymerization method. That is, monomers such as vinyl aromatic compounds, conjugated dienes, and methacrylates as exemplified above produce anionic living polymers having carbanions at the molecular ends by anionic polymerization. In the anionic polymerization, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained anionic living polymer is 1.0 to 1.3 by appropriately selecting the conditions according to a conventional method.
Can be within the range of. Mw within this range
When a polymer having a carbanion having a value of / Mn is used at the molecular end, the resulting amino group-containing polymer also has Mw / Mn in the range of 1.0 to 1.3 (that is, a narrow molecular weight distribution). When used in the production of a polymer composition, the homogeneity of the molecular weight etc. in the product of the reaction with other polymers becomes high, so that the desired physical properties, thermal characteristics, etc. can be realized with good reproducibility. Is possible, which is preferable.

The anionic polymerization for obtaining the anionic living polymer can be carried out by a conventional method, for example, by polymerizing a monomer in an organic solvent using a polymerization initiator such as an organic alkali metal compound. When a monofunctional polymerization initiator such as n-butyllithium or s-butyllithium is used as the polymerization initiator,
It is possible to obtain a linear anionic living polymer having a carbanion at one terminal of the molecular chain, and to obtain an alkali metal such as lithium or sodium and an aromatic or unsaturated carbonization such as naphthalene, divinylbenzene or diisopropenylbenzene. When a bifunctional polymerization initiator combined with a hydrogen compound is used, a linear anion living polymer having carbanions at both molecular chain ends can be obtained. As the organic solvent, saturated aliphatic hydrocarbon compounds such as hexane, heptane, cyclohexane; aromatic hydrocarbon compounds such as benzene, toluene; ether compounds such as tetrahydrofuran can be used. Moreover, as the temperature of anionic polymerization, a temperature within a range of −100 ° C. to + 70 ° C. is generally used. A solution of an organic solvent containing an anionic living polymer prepared by performing anionic polymerization in this manner, without any particular operations such as concentration and dilution,
It can be used as it is for the reaction with nitrile.

The nitrile used in the production method of the present invention is an organic compound having a cyano group (--CN), and examples thereof include acetonitrile, propiononitrile, isobutyronitrile, isovaleronitrile and trimethylacetonitrile. Alkane nitriles such as acrylonitrile, methacrylonitrile, and allyl cyanide; cycloalkane nitriles such as cyclohexane nitrile; phenylacetonitrile, 3-
Arylalkane nitriles such as phenylpropiononitrile; Nitriles having substituents such as halogen atom, acyl group, alkoxyl group, acyloxyl group, alkoxycarbonyl group and the like such as 3-chloropropiononitrile;
Examples include dinitriles such as succinonitrile, 1,4-dicyanobutane, and 2-methylglutaronitrile. Among these nitriles, in terms of high uniformity of the terminal structure formed when introduced at the polymer end,
As described above, a hydrocarbon compound in a form substituted by one cyano group such as alkane nitrile, alkene nitrile, cycloalkane nitrile, aryl alkane nitrile is preferable, and further, it has high versatility and is introduced into a polymer terminal. Considering the high rate and the high reactivity of the formed primary amino group (high ionization degree, low steric hindrance), acetonitrile and propiononitrile are also taken into consideration. Lower alkane nitriles such as and the like are more preferable, and acetonitrile is particularly preferable.

When a nitrile having a substituent such as a halogen atom is used among the above-mentioned nitrites, the reaction with the polymer having a carbanion at the molecular end of a part of the nitrile causes the reaction inside or inside the substituent. Although it may occur at the substitution site, according to the method of the present invention, such a side reaction product also undergoes a hydrogenation reaction condition, so that a polymer having a primary amino group at the molecular end is added. Can be converted. Further, among the above-mentioned nitriles, when dinitrile is used, it is presumed that one cyano group is retained in an unreacted form in the reaction with a polymer having a carbanion at the molecular end. According to the method
It can then be converted to a polymer having two primary amino groups on at least one of the molecular ends for passing through hydrogenation reaction conditions.

The reaction of the polymer having the carbanion at the molecular end with the nitrile can be carried out at a temperature at which the polymer having the carbanion at the molecular end can stably exist, and is generally in the range of -100 ° C to + 70 ° C. The reaction temperature can be appropriately selected from the inside. The amount of nitrile used is preferably an amount of 1 mol or more, and preferably in the range of 1 to 10 mol, based on 1 mol of the carbanion contained in the polymer having a carbanion at the molecular end. More preferably, it is an amount. In this way, by setting the amount of nitrile used to be an excess mole number with respect to the carbanion, when dinitrile is used as the nitrile, it is possible to suppress the coupling reaction between polymers having carbanion at the molecular end. Is especially effective from.

The reaction between the polymer having a carbanion at the molecular end and the nitrile is preferably carried out in an organic solvent. Examples of preferred organic solvents include saturated aliphatic hydrocarbon compounds such as hexane, heptane, and cyclohexane; aromatic hydrocarbon compounds such as benzene and toluene; ether compounds such as tetrahydrofuran. The reaction time is not particularly limited, but is generally within the range of about 1 minute to 1 hour.

After the reaction of the above-mentioned polymer having a carbanion at the molecular end with nitrile, the obtained reaction mixture is treated with a compound containing an active hydrogen atom.

The above-mentioned active hydrogen atom-containing compound may be any one that can be used as a polymerization terminator in ordinary anionic polymerization, and suitable examples thereof include alcohols such as methanol and ethanol; carboxylic acids such as acetic acid. And so on. The reaction mixture obtained by the reaction of a polymer having a carbanion at the molecular end with a nitrile is treated with an active hydrogen atom-containing compound in the same manner as in the operation at the end of the reaction in the usual anionic polymerization. It can be easily performed by adding a hydrogen atom-containing compound. Generally, the reaction temperature can be appropriately selected from the range of -100 ° C to + 70 ° C. The amount of the active hydrogen atom-containing compound used is such that it is generally 1 mol or more per 1 mol of the carbanion contained in the polymer having the carbanion used at the molecular end, and is in the range of 1 to 10 mol. The amount is preferably such that The treatment time is not particularly limited, but is generally within the range of about 1 minute to 1 hour.

In the production method of the present invention, the reaction product obtained by the treatment using the above active hydrogen atom-containing compound is then treated under hydrogenation reaction conditions. As the reaction product, it is possible to use a product which is separated and obtained by a method such as distillation from the reaction mixture obtained by the treatment with the compound containing an active hydrogen atom. However, the desired reaction product may be hydrolyzed by water during the separation operation. In order to prevent this, the reaction product is used in the form of the reaction mixture obtained by the treatment with the compound containing an active hydrogen atom as it is, and is immediately subjected to hydrogenation reaction conditions. Is preferred.

When the reaction product is treated under hydrogenation reaction conditions, the conditions according to the usual conversion reaction of an imine or nitrile into an amine by hydrogenation can be adopted, and the treatment method is, for example, A method of performing reduction treatment using a hydrogen compound such as lithium aluminum hydride or sodium borohydride as a reducing agent; a method of contacting with hydrogen gas in the presence of a hydrogenation catalyst can be employed.

The reduction treatment using the above hydrogen compound as a reducing agent can be carried out, for example, as follows. That is, lithium aluminum hydride was used at a ratio within a range of about 3 to 20 times the molar ratio with respect to the carbanion in the polymer having the carbanion initially used, and this was dehydrated with anhydrous diethyl ether or the like. After adding concentrated sulfuric acid in the same weight as the lithium aluminum hydride to the suspension suspended in the organic solvent, the organic reaction product obtained by the treatment with the active hydrogen atom-containing compound is added to the suspension. A solvent solution (preferably a reaction mixture obtained by the treatment in an organic solvent) is gradually added and refluxed for about 1 to 10 hours. After finishing the treatment under the hydrogenation reaction condition in this way, the obtained reaction mixture is cooled to a temperature of about 0 ° C., water is added dropwise thereto with stirring, and then an aqueous sodium hydroxide solution is added dropwise. By removing the aqueous layer together with the precipitated aluminum hydroxide and distilling off the organic solvent, the desired polymer having a primary amino group at the molecular end can be obtained.

In the method of contacting with hydrogen gas in the presence of the hydrogenation catalyst, a homogeneous or heterogeneous hydrogenation catalyst can be used as the hydrogenation catalyst. As the homogeneous catalyst, an organic transition metal catalyst (for example,
It is possible to use a Ziegler catalyst or the like in which nickel acetylacetonate, cobalt acetylacetonate, nickel naphthenate, cobalt naphthenate, etc.) and an alkylated metal such as aluminum, an alkali metal or an alkaline earth metal are combined. Further, as a heterogeneous catalyst, it is possible to use a metal such as nickel, cobalt, palladium, rhodium, ruthenium, or platinum alone or in a form in which these are supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon. it can.

The method of contacting with hydrogen gas in the presence of a homogeneous hydrogenation catalyst can be carried out, for example, as follows. That is, the homogeneous hydrogenation catalyst was used at a ratio within the range of about 1 to 50 times mol of the carbanion in the polymer having the carbanion used at the end of the molecule, and this was used. A mixture solution obtained by adding the reaction product of the treatment with the compound to an organic solvent solution (preferably, the reaction mixture solution obtained by the treatment in the organic solvent) is heated at room temperature to 150 ° C.
It is contacted with hydrogen gas under conditions of hydrogen gas pressure within the range of atmospheric pressure to 50 kg / cm ² for about 1 to 50 hours. After finishing the treatment under the hydrogenation reaction condition in this manner, acidic water is added to the obtained reaction mixture, and the hydrogenation catalyst is dissolved in water by vigorous stirring. The aqueous phase is removed from the two phases that have been phase-separated, and the organic solvent is distilled off from the organic phase to obtain a target polymer having a primary amino group at the molecular end.

The method of contacting with hydrogen gas in the presence of a heterogeneous hydrogenation catalyst can be carried out, for example, as follows. That is, a heterogeneous hydrogenation catalyst,
It is used in a ratio within the range of about 0.5 to 10% by weight with respect to the polymer to be treated, and this is used as an organic solvent solution (preferably, an organic solvent) of the reaction product obtained by the treatment with the active hydrogen atom-containing compound. The mixture obtained by adding to the reaction mixture obtained by the above treatment under the conditions of a temperature in the range of normal temperature to 250 ° C. and a hydrogen gas pressure in the range of normal pressure to 200 kg / cm ² . Contact with hydrogen gas for about 1 to 50 hours. After finishing the treatment under the hydrogenation reaction condition in this way, the catalyst is filtered off from the obtained reaction mixture, and the organic solvent is distilled off from the obtained filtrate to obtain the desired first mixture.
A polymer having a primary amino group at the molecular end is obtained.

Although the treatment under hydrogenation reaction conditions can be carried out by various methods as described above, when the polymer to be treated has a carbon-carbon double bond, the conditions can be selected depending on the conditions. It is also possible to produce a polymer having a primary amino group at the molecular end in a form in which at least a part of carbon-carbon double bonds is hydrogenated.
In addition, when the polymer having a carbanion as a raw material in the method of the present invention at the molecular end is obtained by using a conjugated diene as at least a part of the constituent monomers, the polymer has carbon atoms in the molecule. Since it has a carbon double bond, the reaction product obtained by the reaction with the nitrile and the treatment with the active hydrogen atom-containing compound also becomes a polymer having a carbon-carbon double bond in the molecule.

When the reaction product subjected to the treatment under the hydrogenation reaction condition has a carbon-carbon double bond, the formation of the primary amino group is larger than that of the hydrogenation reaction of the carbon-carbon double bond portion. Since the treatment occurs preferentially, the treatment is carried out while confirming the chemical structure of the product present in the reaction system, and by terminating the treatment in a timely manner, the carbon-carbon dicarbonate in the obtained polymer having a primary amino group at the molecular end is obtained. The hydrogenation rate of the heavy bond can be arbitrarily adjusted within the range of 0 to 100%. For the purpose of obtaining a polymer having a primary amino group at the molecular end in the form in which at least a part of carbon-carbon double bonds is hydrogenated, the treatment under hydrogenation reaction conditions is carried out by the homogeneous system as described above or It is preferably carried out by a method of contacting with hydrogen gas in the presence of a heterogeneous hydrogenation catalyst. Depending on the type of hydrogenation catalyst used,
It is also possible to control the degree of hydrogenation of the carbon-carbon double bond depending on the amount of the catalyst used, since the primary amino group formed during the treatment deactivates it.

When the obtained polymer having a primary amino group at the molecular end has a carbon-carbon double bond in the molecule, the weather resistance may be insufficient. Therefore, in order to improve the weather resistance, the treatment under hydrogenation reaction conditions is preferably set so that the initial hydrogenation rate with respect to the carbon-carbon double bond is 50% or more, and 70% or more. More preferably,
It is particularly preferable that the content be 85% or more.

The polymer having a primary amino group at the molecular end, which is separated and obtained from the reaction mixture obtained by the treatment under the hydrogenation reaction condition as described above, when the purity is not sufficiently high, It can be appropriately subjected to purification treatment by a method such as reprecipitation purification.

The polymer having a primary amino group at the molecular end obtained by the production method of the present invention may have a structure in which the primary amino group is bonded to a secondary carbon atom. The primary amino group tends to have higher reactivity as the degree of ionization is higher and the steric hindrance is lower. Therefore, when it is desired to react a polymer having a primary amino group at the molecular end with another polymer, the carbon atom to which the primary amino group is bonded is secondary, that is, the carbon atom at the molecular end is Is the general formula

[0035]

Embedded image —CH (R ¹ ) —NH ₂

(In the formula, R ¹ represents a hydrocarbon group.)

It is advantageous to have a structure represented by:

[0038]

Embedded image —CH (R ² ) —NH ₂

(In the formula, R ² represents a lower alkyl group such as a methyl group, an ethyl group and a propyl group.)

It is more advantageous to have a structure represented by:

[0041]

Embedded image —CH (CH ₃ ) —NH ₂

It is particularly advantageous to have the structure shown by

As described above, according to the method of the present invention, by using an anion living polymer obtained by anion living polymerization as a polymer having a carbanion at a molecular end, high monodispersibility in the anion living polymer is obtained. Has a primary amino group bonded to a secondary carbon atom at the molecular end and has a ratio (Mw / Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
It is possible to produce polymers with Mn) in the range of 1.0 to 1.3. As a typical example of a polymer having a primary amino group bonded to such a secondary carbon atom at the molecular end and having Mw / Mn in the range of 1.0 to 1.3, a secondary polymer is used. Mention may be made of a methacrylate-based polymer having a primary amino group bonded to a carbon atom at the molecular end and having Mw / Mn in the range of 1.0 to 1.3, and as another example, , The molecular chain is mainly
(1) Olefin compound polymer block and (2)
It is composed of at least one polymer block selected from the group consisting of other olefin compound polymer blocks and vinyl aromatic compound polymer blocks, and has a primary amino group bonded to a secondary carbon atom at the molecular end. And M
A block polymer having w / Mn in the range of 1.0 to 1.3 can be mentioned. The methacrylate-based polymer is mainly composed of units whose molecular chains are derived from methacrylate. In addition, the above-mentioned two kinds of olefin compound polymer blocks are, for example, an unsaturated polymer block mainly composed of a unit derived from a conjugated diene and a carbon-block in the unsaturated polymer block.
Partially hydrogenated unsaturated polymer block in a form in which a part of the carbon double bond part is hydrogenated, and a form in which substantially all of the carbon-carbon double bond part in the unsaturated polymer block is hydrogenated Examples thereof include saturated polymer blocks. The vinyl aromatic compound polymer block is a polymer block mainly composed of units derived from a vinyl aromatic compound. Incidentally, when the above block polymer has an olefin compound polymer block and another olefin compound polymer block, the difference between the two blocks is, for example, the type of the monomer unit, the quantitative ratio of the comonomer unit, 1 in 1,2-bonding rate or 3,4-bonding rate in conjugated diene unit
There are more than points.

The reaction steps estimated for the production method of the present invention will be schematically shown below, citing an example thereof. In addition,
The present invention is not limited by this.

1. A step of producing an addition reaction product by reacting a polymer having a carbanion at a molecular end with a nitrile:

[0046]

Embedded image P−M + R−CN → P−C (R) = N−M

(In the formula, P represents a polymer chain, M represents a metal atom, and R represents an organic group.)

2. Step of producing a polymer having an imino group at the molecular end by treating the addition reaction product with an active hydrogen atom-containing compound:

[0049]

Embedded image P−C (R) = N−M + R′−H → P−
C (R) = NH + R'-M

(In the formula, R'represents a residue obtained by removing one active hydrogen atom from an active hydrogen atom-containing compound, and P, M and R are as defined above.)

3. Step of producing a polymer having a primary amino group at the molecular end by treating the polymer having an imino group at the molecular end under hydrogenation reaction conditions:

[0052]

Embedded image P—C (R) = NH + H ₂ → P—CH (R) —NH ₂

(In the formula, P and R are as defined above.)

[0054]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Synthesis of polymethylmethacrylate having a primary amino group at one end of the molecular chain) s-Butyl was placed in a vessel equipped with a stirrer containing 30 parts by weight of fully dehydrated cyclohexane. Lithium (0.2 parts by weight) and 1,1-diphenylethylene (0.57 parts by weight) were reacted for 1 hour and transferred to a pressure vessel equipped with a stirrer containing 1000 parts by weight of fully dehydrated tetrahydrofuran. After cooling the pressure vessel with a dry ice / methanol bath to bring the temperature of the solution in the vessel to −78 ° C., 100 parts by weight of methyl methacrylate was gradually added dropwise, and then the mixture was further stirred at that temperature for 1 hour. The anionic polymerization reaction was carried out.

To the tetrahydrofuran solution of the anionic living polymer of methyl methacrylate thus prepared, 0.13 parts by weight of acetonitrile was added at -78 ° C and stirring was continued for 30 minutes. The weight part was added and it stirred for 30 minutes. In this way, the reaction mixture (A) was obtained.

To a suspension of 4.0 parts by weight of lithium aluminum hydride in 100 parts by weight of anhydrous diethyl ether, 5.0 parts by weight of concentrated sulfuric acid was slowly added dropwise at 0 ° C., and then 1 part at room temperature. Stir for hours. While stirring this, the above reaction mixture (A) was added at room temperature and the temperature was gradually raised.
Refluxed for 3 hours. The obtained reaction mixture was cooled to 0 ° C., 500 parts by weight of water was added, and then 100 parts by weight of an aqueous solution containing 20 parts by weight of sodium hydroxide was added dropwise with stirring. The precipitated aluminum hydroxide was filtered off and the filtrate was poured into a large amount of methanol to reprecipitate the polymer. The precipitate was vacuum dried at 70 ° C. to obtain 97 parts by weight of a crude polymer.

The obtained crude product was dissolved in toluene and washed three times with distilled water until the pH of the aqueous phase reached 8. The obtained toluene phase was poured into a large amount of methanol to reprecipitate the polymer. After the obtained precipitate was vacuum dried at 70 ° C., a series of operations of dissolving in toluene, reprecipitating in methanol, and vacuum drying the precipitate was repeated twice more.
In this way, a purified product of the polymer was obtained.

The purified product of the above polymer shows a unimodal peak by gel permeation chromatography (GPC) measurement, and has a number average molecular weight of 30,000, a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) ( Mw / M
n) was found to be 1.08.

Further, a quinhydrin reagent was added dropwise to a saturated solution of the purified product in acetone, and dark brown to purple coloration was confirmed. Further, 300 mg of the purified product was dissolved in 20 ml of a saturated solution of methyl orange in acetone and titrated with a 0.01 mol / l acetic acid solution of perchloric acid. From these results,
It was confirmed that primary amino groups were introduced into the polymer molecule at a ratio of 0.88 / molecule.

10 g of the purified product was completely incinerated,
As a result of elemental analysis of the ash, only 1 ppm of aluminum was detected as a metal component.

Example 2 (Synthesis of Linear Polystyrene-Hydrogenated Polyisoprene-Polystyrene Triblock Copolymer Having Primary Amino Group at One End of Molecular Chain) Sufficiently in a pressure vessel equipped with a stirrer. 1000 parts by weight of cyclohexane, 15 parts by weight of styrene and n
-Butyllithium (0.2 parts by weight) was added and polymerized at 40 ° C for 1 hour, then isoprene (70 parts by weight) was added and polymerized at the same temperature for 1 hour, and styrene (15 parts by weight) was further added and polymerized at the same temperature for 1 hour. .

At 40 ° C., 0.13 parts by weight of acetonitrile was added to the cyclohexane solution of the anion living polymer thus prepared in the form of polystyrene-polyisoprene-polystyrene triblock copolymer, and stirring was continued for 30 minutes. Then, 0.1 part by weight of methanol was added at the same temperature and stirred for 30 minutes.

10 parts by weight of a diatomaceous earth-supported nickel catalyst was added to the obtained reaction mixture in a hydrogen gas atmosphere to give 15
The hydrogenation reaction was carried out at 150 ° C. for 5 hours at a hydrogen gas pressure of kg / cm ² . The obtained reaction mixture was diluted with cyclohexane, the catalyst was filtered off, and the filtrate was concentrated and dried under reduced pressure to obtain 89 parts by weight of a crude polymer.

The crude product obtained was dissolved in toluene and dissolved in 5%.
The residual metal components were removed by washing with dilute hydrochloric acid, followed by washing with a 5% aqueous sodium hydroxide solution, and further with distilled water seven times until the pH of the aqueous phase reached 8. The obtained toluene phase was poured into a large amount of methanol to reprecipitate the polymer. After the obtained precipitate was vacuum dried at 70 ° C., a series of operations of dissolving in toluene, reprecipitating in methanol, and vacuum drying the precipitate was repeated twice more.
In this way, a purified product of the polymer was obtained.

The purified product of the above polymer shows a unimodal peak by GPC measurement and has a number average molecular weight of 82,000.
(Polystyrene conversion value), the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) was found to be 1.10.

As a result of NMR analysis of the purified product, it was found that almost all carbon-carbon double bonds in the polyisoprene block were hydrogenated.

Further, 1 part of a saturated solution of the purified product in toluene was added.
After adding 0% by volume of methanol, a quinhydrin reagent was added dropwise, and dark brown to purple coloration was confirmed. In addition, 300 mg of the purified product was added to a saturated solution of methyl orange in toluene 2
It was dissolved in 0 ml and titrated with a 0.01 mol / l perchloric acid acetic acid solution. From these results, it was confirmed that primary amino groups were introduced into the polymer molecule at a ratio of 0.91 / molecule.

It should be noted that 10 g of the purified product was completely incinerated,
As a result of elemental analysis of ash, nickel is 3 as a metal component.
Only ppm was detected.

[0070]

EFFECTS OF THE INVENTION According to the production method of the present invention, industrially versatile nitrile is used without passing through an extra step such as protection to ensure that a primary amino group is present at the molecular end of the polymer. Since it can be introduced, a polymer having a primary amino group at the molecular end can be industrially advantageously produced. Further, according to the production method, it is possible to produce a polymer having a highly reactive primary amino group bonded to a secondary carbon atom at the molecular end and having a narrow molecular weight distribution.

Claims (5)

[Claims] 1. A method comprising reacting a polymer having a carbanion at a molecular end with a nitrile, treating the compound with an active hydrogen atom-containing compound, and then treating the resulting reaction product under hydrogenation reaction conditions. A method for producing a polymer having a primary amino group at the molecular end. 2. The production method according to claim 1, wherein the polymer having a carbanion at a molecular end is an anion living polymer obtained by anion living polymerization. 3. A primary amino group bonded to a secondary carbon atom is present at the molecular end, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0. ~ 1.
A polymer having a range of 3. 4. A primary amino group bonded to a secondary carbon atom is present at the molecular end, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0. ~ 1.
Methacrylate-based polymer characterized by being in the range of 3. 5. A polymer chain having at least one polymer selected from the group consisting of (1) olefin compound polymer block and (2) other olefin compound polymer block and vinyl aromatic compound polymer block. The first, consisting of a united block, bound to a secondary carbon atom
Having a primary amino group at the molecular end and having a weight average molecular weight (M
w) and number average molecular weight (Mn) ratio (Mw / Mn) is 1.
A block polymer having a range of 0 to 1.3.