JPH0144203B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer having a terminal primary amino group introduced therein by the reaction of component A, an anionic living polymer, with component B, an aminating agent. Polymers with a primary amino group (-NH ₂ ) at the end can be used not only as an important component of polyurethane and polyamide, but can also be used as block and graft polymers by taking advantage of their reactivity. . Synthesis methods known to date for this polymer include (1) a method in which it is obtained by radical polymerization in the presence of a chain transfer agent containing NH ₂ groups (for example, A.
Nakajima, Polymer Journal 11 995
(1979)) (2) A method (DN
Schulz et al. J. Polymer Sci, Polym Chem. Ed.,
15 2401 (1977)) (3) A method of obtaining a cationic living polymer by ammonia treatment. (4) A method of reacting a polymer terminal carboxylic acid with a large excess of diamine. However, in method (1), two or more NH ₂ groups are introduced per polymer or only low molecular weight polymers can be obtained, and in method (2), the cis-1.4 structure of the polydiene accounts for 20 to 40% of the polymer. It is extremely difficult to control the microstructure to a large extent, and methods (3) and (4) can only be applied to special systems; There are some drawbacks, such as the need for a reaction. As a result of intensive studies to solve the above-mentioned drawbacks, the present inventors found that it is possible to easily introduce a terminal primary amino group in a one-step reaction, and that a high amination rate and molecular weight control are possible.
Possibility of amination at one end and both ends;
We have discovered a method for introducing primary amino groups that has many excellent features, such as being able to control the microstructure of dienes, and have arrived at the present invention. That is, the present invention provides at least one monomer of a conjugated diene and/or α-olefin represented by the general formula RM or MRM (where R is a hydrocarbon group having 1 to 12 carbon atoms and M is an alkali metal). Anionic living polymer A polymerized using an organic alkali metal as a polymerization initiator and general formula XR ⁴ N
(SiR ¹ R ² R ³ ) ₂ or R ⁵ R ⁶ C=N—Y (where X is a halogen, R ¹ , R ² , and R ³ are hydrocarbon groups having 1 to 12 carbon atoms, and R ⁴ is a carbon number 1 to 12 alkylene groups, R ⁵ R ⁶
is a hydrocarbon group having 1 to 10 carbon atoms or hydrogen, Y is [formula] or -SiR ¹ R ² R ³ ), and then hydrolyzed to form terminal primary This is a method for producing a polymer having a terminal primary amino group, which is characterized by introducing an amino group. The present invention will be explained in detail below. Conjugated dienes and/or α-olefins in the present invention are monomers capable of anionic living polymerization, such as conjugated dienes such as butadiene, isoprene, 1,3-pentadiene, styrene, α-methyl-styrene, methyl methacrylate, These are α-olefins such as ethyl acrylate, 2-vinylpyridine, 4-vinylpyridine, and acrylonitrile. As a polymerization initiator, the general formula RM or MRM
(Here, R is a hydrocarbon group having 1 to 12 carbon atoms, M is Li,
Organic alkali metals such as Na, K, etc., such as n-butyllithium, sec-
Butyllithium, t-butyllithium, ethyllithium, methyllithium, phenyllithium,
1,4-dilithiobutane, lithium naphthalide,
Examples include sodium naphthalide and potassium naphthalide, but Li compounds are preferred in order to obtain an efficient amination rate. The number average molecular weight of the anionic living polymer A to be produced is not particularly limited as long as it is from 500 to 1,000,000. The manufacturing method of anion living polymer is n-hexane, toluene, heptane,
Cyclohexane, tetrahydrofuran (THF),
A solution polymerization method using an inert hydrocarbon such as dioxane as a solvent is preferred, and a bulk polymerization method using no solvent is also possible. Further, the polymerization method may be a continuous method or a batch method. Polymerization temperature is usually -80℃ to 150℃
℃, preferably from -78℃ to 80℃. One of the aminating agents for component B is the general formula
XR ⁴ N(SiR ¹ R ² R ³ ) ₂ (where X is a halogen such as Br, I, Cl, R ⁴ is an alkylene group having 1 to 12 carbon atoms, and R ¹ , R ² , R ³ is a hydrocarbon group having 1 to 12 carbon atoms);
For example, N,N-bis-trimethylsilyl-2-
Bromoethylamine, N,N-bis-triphenylsilyl-3-bromopropylamine, N-triphenylsilyl-N-trimethylsilyl-2-chloroethylamine, N,N-bis-trimethylsilyl-P-bromomethylaniline, N, Examples include N-bis-triphenyl-m-chloromethylaniline. On the other hand, the general formula R ⁵ R ⁶ C=N-Y (where Y is [formula] or -SiR ¹ R ² R ³ , and R ⁵ and R ⁶ are a hydrocarbon group having 1 to 10 carbon atoms or hydrogen When Y is [Formula], specific examples are as follows. Namely, N-butylidenebenzenesulfenamide, N-isopropylidenebenzenesulfenamide, N-benzylidenebenzenesulfenamide, N-ethylidenebenzenesulfenamide, N-(α-phenylbenzylidene)benzenesulfenamide, N- -(α-methylbenzylidene)benzenesulfenamide and the like. When Y is -SiR ¹ R ² R ³ , specific examples are as follows. Namely, N-trimethylsilyl-benzaldimine, N-triphenyl-benzaldimine, N-trimethylsilyl-(1-phenylpentylidene)amine, N-(1-phenylpropylidene)-1,1-dimethyl-1-phenyl-silane amine. , N-trimethylsilyl-ethylideneamine, and the like. A preferred aminating agent is a compound having the general formula R ⁵ R ⁶ C=N-Y, and in which Y is -SiR ¹ R ² R ³ , R ⁵ or R ⁶ 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. It is preferable that the B component is reacted in a proportion equal to or higher than the chemical equivalent of the alkali metal of the A component. In addition, the reaction temperature can be the same as the polymerization temperature, or any temperature after heating or cooling, usually -80 to 150℃,
Preferably it is -30 to 80°C. After the reaction between component A and component B, water, acid, water, or alcohol can be added in an amount of twice the mole or more of the aminating agent to cause hydrolysis, thereby obtaining a polymer containing terminal primary amino groups. can. According to the method of the present invention, it is possible to control the molecular weight with a higher amination rate by reacting the living polymer with a specific aminating agent, and it is also possible to aminate one and both ends. The first terminal allows control of the microstructure of the diene.
The present invention is an extremely useful method industrially because a polymer containing a grade amine can be easily produced. 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. Example 1 N-trimethylsilylbenzaldimine [formula] as an aminating agent was prepared by the method of U. Wannagats et al. [Chem. Ber., 96 ,
2132 (1963)], and 1.4 mmol of this was prepared as a THF solution and sealed in a glass tube with a breakable seal. n-Butyllithium (n-BuLi)
0.5 mmol was a commercially available product as it was, and 7.3 g (108 mmol) of isoprene (manufactured by Nippon Gosei Rubber Co., Ltd.) was dried with LiAlH ₄ and sealed in a tube as a cyclohexane solution. Furthermore, as a scavenger for an aminating agent, 0.35 mmol of sodium stilbene was sealed in a THF solution. Connect the above four reagents to a 100ml glass reaction tube,
After thorough drying, 20 ml of cyclohexane was introduced by vacuum distillation, and the glass reaction tube was sealed. Keep the glass reaction tube at 40℃ and add isoprene and n-
The breakable seal of BuLi was broken and isoprene was polymerized. After the polymerization was completed, a solution prepared by mixing N-trimethylsilyl-benzaldimine 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 for hydrolysis, and the polymer was precipitated. After carefully repeating the reprecipitation purification, it was confirmed that there was no unreacted aminating agent by GPC for small molecules, and the polymer was lyophilized.
I got g. The molecular weight of the polymer was determined by the universal calibration method using GPC for polymers and intrinsic viscosity, and the number average molecular weight was 17,400 and the weight average molecular weight was 23,000. The amine content was determined by dropping an acetic acid solution of HClO ₄ into a benzene solution of the polymer using crystal violet as an indicator, and found it to be 51.8×10 ^-6 mol per gram of polymer. The amination rate was 90% based on the number average molecular weight and amine content. The microstructure of the obtained polymer is a cis-1.4 structure.
73.0%, trans-1.4 structure 20.3%, 3.4 structure 6.7%,
1.2 structure was 0%. Glass transition temperature is −76.5
It was warm at ℃. Example 2 Using tetrahydrofuran (THF) instead of the solvent cyclohexane in Example 1, n-
BuLi0.37mmol, isoprene 9.1g (134mmol)
Isoprene was polymerized in the same manner as in Example 1, except that the amount was changed to . The obtained polymer weighed 8.3g and had a number average molecular weight of 29300.
The polymerization average molecular weight was 34,000. The amine content is 27.9 x 10 ^-6 mol per gram of polymer;
The amination rate was 82%. The microstructure of the polymer is 4.5% cis-1.4 structure and 18.8% trans-1.4 structure.
%, 3.4 structure 52.9%, 1.2 structure 13.8%. The glass transition temperature was 0.5°C. Example 3 22.0g (324mmol) of isoprene from Example 1,
Example 1 except that n-BuLi was varied to 0.37 mmol
Isoprene was polymerized in the same manner. The polymer yield was 20.3g, and the number average molecular weight was
It was 100,000. The amine content was 9.18 x 10 ^-6 mol per gram of polymer, and the amination rate was 92%. The microstructure of the polymer is cis-1.4 structure81.4
%, trans-1.4 structure 12.3%, 3.4 structure 6.3%, 1.2
The structure was 0%. Example 4 Butadiene was polymerized in the same manner as in Example 1 except that butadiene was used instead of isoprene. The polymer yield was 6.8 g and the number average molecular weight was 18,000. The amination rate was 93%. Example 5 Styrene 5.2g instead of isoprene in Example 1
(50 mmol), styrene was polymerized in the same manner as in Example 1, except that benzene was used instead of cyclohexane as the solvent, and n-BuLi was changed to 0.5 mmol. The polymer yield was 5.0 g, and the number average molecular weight was
It was 10,000. The amination rate was 96%. Example 6 N-trimethylsilyl-α-butylbenzaldimine [formula] was used instead of N-trimethylsilyl-benzaldimine in Example 1, and 5.2 g of styrene was used instead of isoprene.
(50mmol), instead of cyclohexane as solvent
Styrene was polymerized in the same manner as in Example 1 except that THF was used and n-BuLi was varied to 0.3 mmol. The polymer yield was 4.9 g and the number average molecular weight was 35,000. The amination rate was 41%. Example 7 N-butylidenebenzenesulfenamide [Formula] was substituted for N-trimethylsilylbenzaldimine in Example 1 according to the method of FA Davis et al. [J.Org.Chem., 38 , 2809]
(1973)], Example 1 except that 1.8 mmol was sealed in a glass tube with a breakable seal.
Similarly, 6.6g of isoprene with 0.6mmol of n-BuLi
(97 mmol) was polymerized. After the polymer was precipitated, it was sufficiently hydrolyzed with benzene/6N hydrochloric acid, washed with NaHCO ₃ and water, and then freeze-dried. The polymer yield was 6.4 g and the number average molecular weight was 6100. The amination rate was 32%. The microstructure of the polymer was 75.1% cis-1.4 structure, 18.3% trans-1.4 structure, 6.6% 3.4 structure, and 0% 1.2 structure.
The glass transition temperature was -75.5°C. Examples 8-11 Butadiene instead of isoprene in Example 7,
Example 7 except that 1.3-pentadiene, styrene, and α-methylstyrene were used and the solvent was shown in Table 1.
It was polymerized in the same way. [Table] Examples 12 to 17 N,N-bis-trimethylsilyl-2-bromoethylamine [BrCH ₂ CH ₂ N
(SiMe ₃ ) ₂ ] was synthesized by the following method and sealed in a glass tube with a breakable seal. Polymerization was carried out in the same manner as in Example 1 except that the above aminating agent was used and the solvent and monomer were shown in Table 2. [Table] [Table] Examples 18 to 23 Examples except that sodium naphthalide and potassium naphthalide were used in place of n-BuLi in Example 1, and the monomers and aminating agents shown in Table 3 were used in THF. Polymerization was carried out in the same manner as in Example 1 or Example 7. 【table】

Claims (1)

[Scope of Claims] 1 At least one monomer of a conjugated diene and/or α-olefin has the general formula RM or
MRM (where R is a hydrocarbon group having 1 to 12 carbon atoms,
Anion living polymer A polymerized using an organic alkali metal represented by the formula (M represents an alkali metal) as a polymerization initiator and the general formula XR ⁴ N (SiR ¹ R ² R ³ ) ₂ or R ⁵ R ⁶ C=N-
Y (here, X is halogen, R ¹ , R ² , R ³ are 1 carbon number
~12 hydrocarbon group, R ⁴ is an alkylene group having 1 to 12 carbon atoms, R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms or hydrogen, Y is [formula] or - SiR ¹ R ² R ³ Aminating agent B represented by
and then hydrolyzed to form the terminal first
The first terminal is characterized by introducing a class amino group.
A method for producing a polymer having a class amino group.