JPH07196728A - Production of polymer having terminal amino group - Google Patents

Abstract

PURPOSE:To obtain a polymer having a terminal amino group, excellent in heat resistance, ozone resistance and rubber elasticity and useful for medical materials, etc., by introducing a primary amino group into a specific living polymer terminal and hydrogenating. CONSTITUTION:To a chain end of a living polymer consisting of a conjugated diene such as 1,3-butadiene or one consisting of monomers of a conjugated diene and an alpha-olefin such as styrene, a primary and/or a secondary amino group is introduced and then hydrogenated to obtain the objective polymer having a terminal amino group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is directed to the end of primary and / or
Further, the present invention relates to a method for producing a polymer having a secondary amino group, more specifically, as a constituent component of polyurethane or polyamide, and as a block material or a graft polymer by utilizing the reactivity of the terminal, development as a medical material. The present invention relates to a method for producing a polymer having a terminal primary and / or secondary amino group, which is useful as a polymer that can be expected.

[0002]

2. Description of the Related Art The following method is known as a method for producing a polymer having a primary and / or secondary amino group at the terminal. (1) A method of radical polymerization in the presence of a chain transfer agent containing an amino group (for example, A. Nakajima, Po.
Lymer Journal, 11, 995 (197)
9)). (2) an organolithium and a protective group and primary amino group (e.g., _{[(CH 3) 3 Si]} 2 N-C 6 H 4 -Li) polymerizing the conjugated dienes as an anionic polymerization initiator, accordingly Method of performing hydrolysis later (D.N. Schultz
Et al., J. Poly-mer Sci. , Polym. C
hem. Ed. , 15, 2401 (1977)). (3) A method for producing a cationic living polymer by treating with ammonia. (4) At least one monomer of a conjugated diene and / or α-olefin is represented by the general formula RM or MRM (wherein R represents a hydrocarbon group having 1 to 12 carbon atoms and M represents an alkali metal). With an anionic living polymer prepared by polymerizing an organic alkali metal as a polymerization initiator with the general formula XR ₄ N
(SiR ₁ R ₂ R ₃ ) ₂ or R ₅ R ₆ C = NY (where X is
Is a halogen atom, R ₁ , R ₂ and R ₃ have 1 to 12 carbon atoms
Hydrocarbon group, R ₄ is an alkylene group having 1 to 12 carbon atoms,
R ₅ and R ₆ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y is a hydrocarbon group having 1 to 12 carbon atoms, SiR ₇ R ₈
R ₉ (wherein R ₇ , R ₈ and R ₉ represent a hydrocarbon group having 1 to 12 carbon atoms) or S-C ₆ H ₅ is reacted with an aminating agent to form a terminal A method of introducing a primary or secondary amino group (see Japanese Patent Publication No. 1-44203). (5) A chlorine gas is blown into the living polymer obtained in (4) above to chlorinate the polymer terminal and then react with ammonia or amine to introduce a primary or secondary amino group into the terminal. Method (Tokuhei 1-260
1 gazette, Japanese Patent Publication No. 1-49368 gazette).

[0003]

However, the polymers obtained by introducing a primary or secondary amino group at the terminal obtained by these methods have low heat resistance and ozone resistance,
Further, a polymer obtained by binding another monomer to the polymer has a problem that rubber elasticity is low. Therefore, the present invention provides a polymer having a primary and / or secondary amino group at the terminal, which is excellent in heat resistance and ozone resistance and has good rubber elasticity.

[0004]

Means for Solving the Problems The above-mentioned problems are solved by introducing a primary and / or secondary amino group into a terminal of a living polymer of a conjugated diene or a monomer composed of a conjugated diene and an α-olefin, and then introducing a hydrogen atom. And a method for producing a polymer having a primary and / or secondary amino group at the terminal, which is characterized in that it is added.

The present invention will be described in detail below. In the present invention, first, a conjugated diene or a monomer of a conjugated diene and an α-olefin is polymerized usually at −80 to 150 ° C., preferably −78 to 100 ° C. in the presence of an anionic polymerization initiator. Synthesize living polymer.

The above-mentioned conjugated diene and α-olefin are
A monomer that is capable of anionic polymerization and forms a living polymer, such as butadiene, isoprene, 1,
Conjugated dienes such as 3-pentadiene; styrene, α-methylstyrene, α-olefins such as methyl (meth) acrylate, and 2-vinylpyridine. The amount of the α-olefin copolymerized is preferably 50 mol% or less. α
-When the copolymerization amount of olefin exceeds 50%, the polymer finally obtained tends not to exhibit good rubber elasticity.

The anionic polymerization initiator is represented by the general formula RM or MRM (wherein R is a hydrocarbon group having 1 to 12 carbon atoms,
M represents an alkali metal such as lithium, sodium or potassium), and specific examples thereof include n-butyllithium, sec-butyllithium, t-butyllithium, ethyllithium,
Methyllithium, phenyllithium, 1,4-dilithiobutane, lithium naphthalide, sodium naphthalide,
Potassium naphthalide; a reaction product of diisopropenylbenzene or 1,3-bis (1-phenylethynyl) benzene and butyllithium, and the like can be mentioned. An organolithium compound is reacted for the introduction of an amino group provided below. It is preferable in terms of efficiency.

The amount of these anionic polymerization initiators used is 0.001 of the total molar amount of the conjugated diene and the α-olefin.
˜20 mol%, preferably 0.002 to 10 mol%.

Although the polymerization proceeds in the absence of a solvent, it is preferable to use a solvent such as n-pentane or n.
It is preferable to use an inert solvent such as -hexane, n-heptane, cyclohexane, toluene, tetrahydrofuran or dioxane. When these solvents are used, the amount used is 1 of the total amount of the conjugated diene and the α-olefin.
~ 50% by weight. The polymerization method is not limited to the continuous polymerization method or the batch method.

The content of 1,2-vinyl bond in the conjugated diene copolymerized with the obtained living polymer is 10%.
It is above, preferably 20% or more. When the content of 1,2-vinyl bonds is 10% or less, the polymer finally obtained tends not to exhibit good rubber elasticity. In order to control the 1,2-vinyl bond content of the living polymer, a method of adding an aprotic polar solvent such as tetrahydrofuran or dioxane to an inert hydrocarbon solvent such as n-hexane or toluene among the above solvents is used. It is convenient. At this time, the amount of the aprotic polar solvent used is usually 500 to 100,000 ppm of the total amount of the solvent,
It is preferably 1,000 to 50,000 ppm.

Next, primary and / or secondary amino groups are introduced into the ends of the living polymer obtained. As the method, a living polymer and a general formula XR ¹³ N (S
iR ¹⁰ R ¹¹ R ¹²⁾ ₂ or ^{R 14 R 15 = N-Y} ( wherein X
Is a halogen atom, and R ¹⁰ , R ¹¹ and R ¹² have 1 to 1 carbon atoms.
2 hydrocarbon group, R ¹³ is a C 1-12 alkylene group, R ¹⁴ and R ¹⁵ are hydrogen atoms or a C 1-10 hydrocarbon group, Y is a C 1-12 hydrocarbon group or S
Preferred is a method of reacting with an aminating agent represented by iR ¹⁰ R ¹¹ R ¹² or S—C ₆ H ₅ .

Here, the general formula XR ¹³ N (SiR ¹⁰ R
^{As the} aminating agent represented by ¹¹ R ¹² ) ₂ , N, N-bistrimethylsilyl-2-bromoethylamine, N, N
-Bistriphenylsilyl-3-bromopropylamine, N-triphenylsilyl-N-trimethylsilyl-
2-chloroethylamine, N, N-bistrimethylsilyl-P-bromomethylaniline, N, N-bistriphenyl-m-chloromethylaniline and the like can be mentioned. As the aminating agent represented by the general formula R ¹⁴ R ¹⁵ C = NY, N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, N
-Benzylideneaniline, N-benzylidenebenzylamine, N-benzylidenetoluidine, N- (α-phenylbenzylidene) benzylamine, N- (α-phenylbenzylidene) aniline, N- (α-methylbenzylidene) aniline, N-butylidene Benzenesulfenamide, N-isopropylidenebenzenesulfenamide,
N-benzylidenebenzenesulfenamide, N- (α
-Phenylbenzylidene) benzenesulfenamide,
N-trimethylsilylbenzaldoimine, N-triphenylsilylbenzaldoimine, N-trimethylsilyl-
Examples include (1-phenylpentylidene) amine and N-trimethylsilylethylideneamine. The preferred aminating agent represented by the general formula ^{R 14 R 15 C = N-} Y as the aminating agent, yet is the aminating agent is any of hydrogen R ¹⁴ or R ^15. These aminating agents can be used as a solid or liquid as they are, or in the form of a solution dissolved in the above-mentioned polymerization solvent.

The aminating agent preferably reacts with the alkali metal compound derived from the anionic polymerization initiator present at the end of the living polymer in a proportion equal to or more than the chemical equivalent.
The reaction temperature may be the same as the polymerization temperature or may be any temperature after heating or cooling, and is usually -80 to
It is 150 ° C, preferably -30 to 100 ° C.

After the reaction between the living polymer and the aminating agent, a polymer having a primary and / or secondary amino group introduced at the terminal by adding water or alcohol in an amount at least twice the molar amount of the aminating agent. Can be obtained.

Here, the rate of introduction of primary and / or secondary amino groups at the ends of the living polymer (hereinafter referred to as "amination rate") is preferably 75% or more, more preferably 90% or more. Is. If the amination ratio is less than 75%, the desired effects of the present invention may not be achieved. The resulting solution containing a living polymer having a primary and / or secondary amino group at its end (hereinafter, referred to as
It is called "terminal aminated polymer". It is preferable to purify () by repeating the procedure of putting it in methanol or the like, and performing precipitation and filtration.

Subsequently, the terminally aminated polymer is hydrogenated. As the method, it is preferable to perform heating in a solution state in the presence of a hydrogenation catalyst to 0 to 200 ° C., preferably 20 to 150 ° C., and under a hydrogen pressure of 1 to 300 kg / cm ² .

As the solvent used for hydrogenation,
n-pentane, n-hexane, n-heptane, cyclohexane, toluene, tetrahydrofuran, dioxane,
Examples thereof include dimethylformamide. It is preferable to dissolve the terminal aminated polymer in these solvents and hydrogenate it as a 1 to 30 wt% solution, preferably a 2.5 to 20 wt% solution.

Examples of the hydrogenation catalyst include the following compounds. (1) A catalyst in which a metal of Group 8 of the periodic table is supported on a carrier such as carbon, silica, or alumina. Here, the Group 8 metal is preferably cobalt, nickel, ruthenium, platinum, palladium, or rhodium. The preferred solvents when using these catalysts are dioxane, ether and toluene. (2) Organic fatty acid salts, chlorides of metals of Group 8 of the periodic table,
Compounds such as nitrates, sulfates and carbonates. Specifically, nickel naphthenate, cobalt naphthenate, nickel octenoate, cobalt octenoate, ruthenium trichloride, rhodium trichloride, palladium chloride, platinum chloride, palladium nitrate, platinum nitrate, palladium carbonate and the like and organic aluminum compounds are preferable. . Preferred examples of the organic aluminum compound include triethylaluminum, triisobutylaluminum, diethylaluminum chloride and the like.
In addition, when using these compounds, a preferable solvent is n
-Hexane and toluene. (3) Organometallic complexes of Group 4B and Group 8 metals of the periodic table. A phosphine complex is preferable as the complex. Specific examples thereof include chlorotristriphenylphosphine rhodium and dichlorotristriphenylphosphine rubidium. The preferred solvent when using these complexes is toluene.

The amount of these hydrogenation catalysts used is 0.01 to 20% by weight of the terminal aminated polymer, preferably 0.1%.
It is 1 to 10% by weight.

In order to obtain a polymer having the desired effects of the present invention, 90% or more, and more preferably 95% or more of all unsaturated bonds in the living polymer used are preferably hydrogenated. .

The polystyrene-reduced number average molecular weight (hereinafter referred to as "Mn") of the polymer of the present invention obtained above is usually 500 to 2,000,000,
It is preferably 1,000 to 1,000,000. Moreover, the ratio of polystyrene-reduced weight average molecular weight to Mn (hereinafter referred to as “Mw / Mn”) is preferably 1.01 to 5. If Mw / Mn is less than 1.01, rubber elasticity may be insufficient.

[0022]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Amination rate; with crystal violet as an indicator,
An acetic acid solution of perchloric acid was added dropwise to the chloroform solution of the polymer, and the calculation was performed using the following formula. Amination rate (%) = {Titrate of acetic acid solution of perchloric acid (ml) × Normality of perchloric acid (N)} / {Amount of polymer used (mg) / Mn of polymer} × 100

Example 1 Cyclohexane 100 was placed in a dry 500 ml pressure bottle.
ml, butadiene 20 g and tetrahydrofuran 4.
After adding 0 mmol, n-butyllithium 2.87 m
mol was added, and the mixture was polymerized at 25 ° C. for 60 minutes. After completion of the polymerization, 1.5 times the molar amount of N- with respect to n-butyllithium.
A cyclohexane solution of benzylidenebenzylamine was added and sufficiently stirred to obtain a terminal aminated polymer solution.
Pour this terminal aminated polymer solution into methanol,
The procedure of precipitating, filtering and redissolving the terminal aminated polymer was repeated to purify the terminal aminated polymer and dried to obtain 18 g of the terminal aminated polymer. When this terminal aminated polymer was measured by GPC, Mn was 5,30.
0, Mw / Mn was 1.09, the content of 1,2-vinyl bond determined by infrared absorption spectrum (Morero method) was 31%, and the amination ratio was 97%. To 5 g of this terminal aminated polymer, 40 ml of toluene was completely dissolved and placed in an autoclave having an internal volume of 100 ml which had been replaced with nitrogen, and 0.58 mmol of nickel naphthenate and 1.74 mmol of triethylaluminum were added.
Then, the inside of the system was replaced with hydrogen, the temperature of the content liquid was raised to 90 ° C., the hydrogen pressure was kept at 8 kg / cm ² , and the reaction was carried out for 10 hours to obtain a hydrogenated polymer. The hydrogenation rate of the obtained polymer was 98%, and it had good rubber elasticity.

Example 2 Cyclohexane 40 m in a dry 100 ml flask
1, diisopropenylbenzene 12.8 mmol, se
25.6 mmol of c-butyllithium and 25.6 mmol of triethylamine were added and reacted at 60 ° C. for 30 minutes to obtain an anionic polymerization initiator solution. 8 ml of this solution
Is used instead of N-benzylidenebenzylamine.
-A terminal aminated polymer was obtained in the same manner as in Example 1 except that benzylidene toluidine was used. The result of the analysis,
The Mn of this terminal aminated polymer is 9,480,
Mw / Mn was 1.19, the content of 1,2-vinyl bonds was 37%, and the amination ratio was 90%. This terminal aminated polymer was hydrogenated in the same manner as in Example 1 to obtain 4.7 g of a polymer. The hydrogenation rate of the obtained polymer was 97%, and it had good rubber elasticity.

Example 3 A terminal aminated polymer was prepared in the same manner as in Example 1 except that 17 ml of the anionic polymerization initiator solution obtained in Example 2 was used and N-benzylidenetoluidine was used instead of N-benzylidenebenzylamine. Got As a result of analysis, Mn of this terminal aminated polymer was 4,370, and Mw
/ Mn was 1.18, the content of 1,2-vinyl bonds was 35%, and the amination ratio was 92%. This terminal aminated polymer was hydrogenated in the same manner as in Example 1 to obtain 4.5 g of a polymer. The hydrogenation rate of the obtained polymer was 98%, and it had good rubber elasticity.

Example 4 In the same manner as in Example 1 except that 40 ml of the anionic polymerization initiator solution obtained in Example 2 was used and N-benzylidenetrimethyltrimethylamine was used in place of N-benzylidenebenzylamine, terminal amination was carried out. A polymer was obtained. As a result of the analysis, the Mn of this terminal aminated polymer was 2,050.
The Mw / Mn was 1.15, the content of 1,2-vinyl bonds was 39%, and the amination ratio was 93%. This terminal aminated polymer was hydrogenated in the same manner as in Example 1 to obtain 3.8 g of a polymer. The hydrogenation rate of the obtained polymer was 97%, and it had good rubber elasticity.

Example 5 In Example 1, butadiene 15 was used instead of butadiene.
g and 5 g of styrene, 40 ml of the anionic polymerization initiator solution obtained in Example 2 instead of n-butyllithium,
18 g of aminated terminal polymer was obtained in the same manner as in Example 1 except that N-benzylidene toluidine was used instead of N-benzylidene benzylamine. As a result of analysis, Mn of this terminal aminated polymer was 2,530, and Mw
/ Mn is 1.15, 1,2-vinyl bond content is 30%, styrene content is 25%, amination rate is 90%.
Met. This terminal aminated polymer was hydrogenated in the same manner as in Example 1 to obtain 3.8 g of a polymer. The hydrogenation rate of the obtained polymer was 98%, and it had good rubber elasticity.

[0028]

The polymer having a primary and / or secondary amino group at the terminal obtained by the present invention is excellent in heat resistance and ozone resistance, and also has good rubber elasticity. Further, the polymer having a primary and / or secondary amino group at the terminal obtained by the present invention is used as a constituent component of polyurethane or polyamide, and is made into a block polymer or a graft polymer by utilizing the reactivity of the terminal. Therefore, it is useful as a polymer that can be expected to be developed as a medical material.

Claims (1)

[Claims] 1. A first polymer at the end of a living polymer of a conjugated diene or a monomer composed of a conjugated diene and an α-olefin.
A method for producing a polymer having a primary and / or secondary amino group at a terminal, which comprises hydrogenating after introducing a primary and / or secondary amino group.