JPS58136623A - Production of primary amino group-terminated polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having easily controllable microstructure and MW in good yields, by polymerizing an N-carboxylic anhydride of an amino acid by using a prim. amino group-terminated diene polymer as an initiator. CONSTITUTION:An N-carboxylic anhydride of an amino acid is polymerized in the presence of an initiator which is a prim. amino group-terminated diene polymer prepared by reacting (A) an anionic living diene polymer prepared by polymerization with the aid of an organoalkali metal compound as an initiator with (B) an aminating agent of formulaIor II (wherein X is a halogen, R<4> is a 1-12C alkylene, R<1>, R<2> and R<3> are each a 1-12C hydrocarbyl, R<5> and R<6> are each a 1-10C hydrocarbyl or H, and Y is a group of formulaIor II) and hydrolyzing the product. The anionic living diene polymer is one obtained by polymerizing at least one member selected from the group consisting of butadiene, isoprene and 1,3-pentadiene, with the aid of an anionic catalyst in an inert hydrocarbon and having a number-average MW of 500-1,000,000.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides α- Amino acid ■−
The present invention relates to a method for producing a block copolymer with a carboxylic acid anhydride (hereinafter referred to as island and ridge).

Polydiene with attractive physical properties as a functional polymer/
Several methods for producing polypeptide block copolymers have been reported. Namely, 1) After modifying the polybutadiene pasting polymer with ethylene oxide, phosgene, or carbon dioxide, a large amount of diamine is added to introduce the terminal primary amino group t- to form the NC of r-benzyl-L-glutamate.
A method for producing a block copolymer by reacting A (B,
Perry et al. MakromoL Cheml 77.2
569 (1976)) 2) Cybutadiene having a primary amino group is polymerized by radical polymerization in the presence of a chain transfer agent to introduce a terminal primary amino group, and then reacted with NCk of an amino acid to form a block copolymer. Method of manufacturing a coalescence [A.

Nakajima et al. Polymer Journal,
11.995 (1979)].

However, in the case of 1), there are drawbacks such as the necessity of a two-step reaction to introduce the amino groups of the anionic living polymer and the low amination rate. In addition, in the case of 2), it is difficult to control the microstructure and molecular distribution of the diene polymer due to radical polymerization, and it is difficult to control the microstructure and molecular distribution of the diene polymer. Butide block copolymer cannot be obtained in υ.

As a result of intensive study by the present inventors to eliminate the above drawbacks,
We have discovered a novel polydiene/polypeptide block copolymer using as a polymerization initiator an aminated polymer in which a terminal primary amine is introduced by reacting an anionic living polymer with a specific aminating agent, resulting in the present invention.

That is, the present invention F1' is an anionic living diene polymer (8) polymerized using an organic alkali metal as a polymerization initiator.
to the general formula xR4N(s utI R2R5)2 or R
5R6C=N-Y (where X is halogen, R4 is an alkylene group having 1 to 12 carbon atoms, R1, R2, and R3 are hydrocarbon groups having 1 to 12 carbon atoms, R5 and R6 are 1 to 1 O-
8iR' R2R3) Aminating agent I
A polydiene/polyR-butide characterized in that N-carboxylic acid anhydrides of amino acids are polymerized using a diene polymer containing a terminal primary amino group obtained by reacting and then hydrolyzing 'B) as a polymerization initiator. Manufacturing method of block copolymer
It provides:

The anionic living diene polymer (A) produced by polymerization using an organic alkali metal as a polymerization initiator according to the present invention refers to at least one of butadiene, inoprene, and 1,3-ntadiene, such as n-butyllithium, SθC-butyllithium. , 1-butyllithium, ethyllithium,
Polymerization using an anionic catalyst such as methyllithium, phenyllithium, 1,4-dilithiobutane, sodium naphthalene V, potassium naphthalene V, etc. in an inert hydrocarbon such as n-hexane, toluene, phosphorus, cyclohexane, tetrahydrofuran, dioxane, etc. The molecular weight (preferably a diene polymer using an L1 catalyst) is not particularly limited, but the number average molecular weight is 500 to 1.
,000,000 can be used.

One of the aminating agents as component (B) is a halogen of the general formula %, R4 is an alkylene group having 1 to 2 carbon atoms, and R1, R2, R5/d is a halogen having 1 to 12 carbon atoms. is a hydrocarbon group. ) such as N,N-bis-trimethylsilyl-2-bromoethylamine, N,N-histriphenylsilyl-3-bromopropylamine, N-triphenylsilyl-N-)
IJ methylsilyl-2-chloroethylamine, N, N
-His-trimethylsilyl-p-bromomethylaniline, N,N-his-triphenyl-m-chloromethylaniline, and the like.

On the other hand, the general formula R5R6C=N-Y (where Y is 18 or 18iRIR2R3, and R5 and R6 have 1 carbon number
~10 hydrocarbon groups or hydrogen. ), in which Y is -, C>, specific examples are as follows. Namely, N--1 tylidenebenzenesulfenamide, N-impropylidenebenzenesulfenamide, N-benzylidenebenzenesulfenamide, N-ethylidenebenzenesulfenamide,
Examples include N-(α-phenylbenzylitine)benzenesulfenamide and N-(α-methylbenzylidene)benzenesulfenamide.

When -Y is 18iR'R2R', specific examples are as follows. Namely, N-)limethylsilylbenzaldimine, N-triphenylbenzaldimine,
N-)limethylsilyru (1-phenyl silyl)
Amine, N-(1-phenylpropylidene)-1",
Examples include 1-silyl-1-phenylsilane amine and N-trimethylsilyl-ethylidene amine.

Preferably used aminating agents have the general formula R5R6
C=N-Y, and Y is 18iRIR2R5 and R
An aminating agent in which either 5 or R6 is hydrogen.

These aminating agents can be used in solid or liquid form, or can be used in the form of a solution dissolved in a solvent such as a hydrocarbon or ether.

The proportion of the above component (B) is preferably at least the chemical equivalent of the alkali metal of component (2).

The reaction temperature can be the same as the polymerization temperature, or can be at any temperature after heating or cooling, usually from -80°C to 150°C, preferably from -30°C to 80°C.

After the reaction between the above component (1) and component (B), water, acidic water, or alcohol can be added in an amount of at least twice the mole of the aminating agent to hydrolyze it and obtain a polymer containing terminal primary amino groups. Possible examples include r-benzyl-L-glutamine FIL r-methyl-L-glutamic acid, β-ethyl-L-asnograginic acid, β-benzyl-L-asnoragic acid, valine, phenylalanine, etc.rrr I can do that. The NCA to be polymerized is preferably a single component or a solution polymerized polymer using dioxane, benzene, or a dioxane/methylene dichloride mixed system as a solvent. Polymerization temperature is usually -20℃ to 10℃
00°C, preferably 0°C to 40°C.

The number average molecular weight of the resulting block copolymer is 1,000.
It is also possible to use a ratio between 1,500,000 and 1,500,000.

According to the present invention, it is easy to control the microstructure and block length of a part of the diene polymer, and moreover, it is possible to easily control the microstructure and block length of a part of the diene polymer, and to produce a polybutide block copolymer or a polypeptide/polydiene/polypeptide block copolymer with good yield. can be obtained, so it has great industrial value.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Reference Example 1 N-trimethylsilylbenzaldimibe (C=N-8iMe 3 ) as an aminating agent is used as an aminating agent (U,
(Chem, Bθr
, 96.2132 (1963)),
This was used as a TRF solution and 1.4 mmol was sealed in a glass tube with a breaker seal. n-butyllithium (
n-Bu-Li) Q, 5 mmol was a commercially available product as it was, isoprene (manufactured by Japan Synthetic Rubber Co., Ltd.) 7.3 t (
108 mmol) was dried with LiAffi4 and sealed in a tube as a cyclohexane solution.

Furthermore, 35 mmol of sodium stilbene Q as a scavenger for the aminating agent was sealed in a THF solution.

The above four reagents were connected to a 100-glass reaction tube, and after sufficiently drying, 20-cyclohexane was introduced by vacuum distillation, and the glass reaction tube was sealed.

Keep the glass reaction tube at 40°C and add isoprene and n-BuL.
The breaker seal of i was broken and inoprene was polymerized. After the polymerization was completed, a solution prepared by mixing N-trimethylsilylupenzaldimine and sodium stilbene was added to the polymerization solution at 30° C. to carry out an amination reaction. After 30 minutes, this solution was added to a large amount of methanol to precipitate the polymer. Further, reprecipitation purification was carefully repeated, and after confirming that there was no unreacted aminating agent by GPC for low molecules, lyophilization was performed to obtain 5.9 tons of polymer. The molecular weight of the polymer was determined by the universal calibration method using GPC for polymers and individual viscosity, and the number average molecular weight was 17,400 and the weight average molecular weight was 23,00.
It was 0.

Amine content was determined using crystal violet as an indicator.
It was determined by dropping an acetic acid solution of HClO4 into a benzene solution of the polymer, and 51.8XIQ-6 mol per gram of polymer.
Met. The amination rate was 90% based on the number average molecular weight and amine content.

The microstructure of the obtained polymer was a cis-1,4 structure73.
0chi, trans-1,4 structure 20.3%, 3.4 structure 6
．． 7ch, 1.2 structure 0ch. The glass transition temperature is −
The temperature was 76.5°C.

Reference Example 2 Tetrahydrofuraf (THF) was used instead of the solvent cyclohexane in Reference Example 1, and n-BuLi 0.37m
mol, isoprene 9.1 f (134 mmol)
Imprene was polymerized in the same manner as in Reference Example 1 except that the amount was changed to .

The obtained polymer had a number average molecular weight of 8.32, a number average molecular weight of 29,300, and a polymerization average molecular weight of 34,000. The amine content was 27.9 x 10''6 ml per gram of polymer and the reamination rate was 82. The microstructure of the polymer is cis-1,4 structure 4.5 B, trans-1,4 structure 1B,
El, 3.4 structure 62.9ch, 1.2 structure 13.8%
Met. The glass transition temperature was 0.5°C.

Reference example 3 Styrene 5,2f (50
Styrene was polymerized in the same manner as in Reference Example 1, except that the solvent was changed to 15 mmol of n-BuLiO using benzene instead of cyclohexane. The polymer yield is 5.
Of, the number, average, and average molecular capsule was 10,000°. The amination rate was 96%.

Example 1 Polyisoprene containing terminal primary amino groups produced according to Reference Example 1. Using Of as a polymerization initiator, 1.5 f of N-carboxylic anhydride of r-, benzyl-L-glutamic acid was placed in a 50-glass reaction tube, thoroughly dried under reduced pressure, and then 20 m of THF obtained by vacuum distillation was introduced into the glass tube. The reaction tube was sealed. This reaction tube was left stirring at 30° C. for 3 days, and after completion of polymerization, it was precipitated in methanol, washed several times with methanol, and dried under reduced pressure to obtain polymer 2.2f.

1.2 t of this polymer was dissolved in THF and precipitated with n-hexane. 0.7Of of the polymer precipitated from THF to n-hexane is determined by IH-NMR spectrometer.
A has a 35 molar implication. Furthermore, Tt(F/n−
The hexane-soluble polymer was precipitated in methanol, dried, and extracted with n-hexane.

The 0.03 f of polymer extracted with n-hexane contained 1 mole of NC.

Further, 0.259 mol of this n-hexane insoluble polymer contained 38 mol of N-carboxylic anhydride.

Therefore, the terminal primary aminated polyimprene prepared by Chemical Formula 5 in Reference Example 1 had the ability to initiate the polymerization of N-carboxylic acid anhydride of r-carbonyl-L-glutamate and produced a block copolymer.

Example 2 Similarly to Example 1, terminal primary aminated polyisoprene of Reference Example 2 was prepared. r as in Example 1 except that Of was used.
-1.52% of the N-carboxylic anhydride of benzyl-L-glutamate was polymerized.

The polymer yield was 1.9f. This polymer was also used in Example 1.
It was confirmed that it was a block copolymer by solvent fractionation in the same manner as above.

Example 3 N- of r-benzyl-glutamate was prepared in the same manner as in Example 1 except that the terminal primary aminated polystyrene i,ot produced in Reference Example 3 was used in the same manner as in Example 1.
1.52 ml of carboxylic anhydride was polymerized.

The obtained polymer was a block copolymer, and the yield was 2.1 tons.

Claims (1)

[Claims] Anionic living diene polymerized using an organic alkali metal as a polymerization initiator #? The general formula xR4N(s
R
5, R6 is a hydrocarbon group having 1 to 10 carbon atoms or hydrogen, Y
Using a diene polymer containing a terminal primary amino group obtained by reacting and hydrolyzing an aminating agent (representing keichi8no or 18iRI R2R') as a polymerization initiator, the N-carboxylic acid of an amino acid is A method for producing a polydiene/polyRzotide block polymer, which comprises polymerizing an acid anhydride.