JPH0529643B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing polyalkenyl ethers. It has been found that when an alkenyl ether is polymerized using the initiator of the present invention, the polymerization proceeds with living chains at both ends, and therefore, by adding a functional group at the end of the polymerization, a telechelic polyalkenyl ether can be produced. A telechelic polymer is a polymer that has a functional group at the end of the polymer chain.Because there are functional groups at both ends, it can be used for chemical reactions, and can be used to add new functional groups or functional groups, extend the chain, or block. Copolymers can be produced and are widely used in thermoplastic elastomers, urethane elastic threads, antithrombotic materials, artificial leather, etc. There are various methods to obtain telechelic polymers, one of which is to proceed with living polymerization using a bifunctional initiator and then add a compound with a functional group at the end of the polymerization. . By the way, alkenyl ethers can only be polymerized by cationic polymerization. Living cationic polymerization of alkenyl ethers was recently discovered by the present inventors, but living polymerization of alkenyl ethers using a bifunctional initiator had not been previously known. The present inventors have arrived at the present invention as a result of intensive studies on a living polymerization method for alkenyl ethers using a bifunctional initiator. The gist of the present invention is that CHR ¹ = CH-O-(CH ₂ ) _o -O
−CH=CHR ² () and HI and I ₂ and/or and I ₂ as initiators, alkenyl ether
It consists in a method for producing polyalkenyl ether by polymerizing CHR ⁵ =CH(OR ⁶ ) (). To explain the present invention in more detail, the monomer alkenyl ether CHR ⁵ =CH(OR ⁶ )()
, R ⁵ represents -H or -CH ₃ group, R ⁶ represents an alkyl group or a cycloalkyl group, the number of carbon atoms is 1 to 24, and the bond is linear, branched, or cyclic. Alternatively, it may be substituted with halogen. One type of monomer or two or more types of monomers may be used together. Alternatively, after polymerizing one or more alkenyl ethers, another alkenyl ether (one or more) may be added to polymerize the alkenyl ether to form a block copolymer. Specific examples of alkenyl ethers include R ⁵ R ⁶ methyl vinyl ether H CH ₃ ethyl ether H C ₂ H ₅ isopropyl ether H CH (CH ₃ ) ₂ n-butyl ether H (CH ₂ ) ₃ CH ₃ isobutyl ether H CH ₂ CH (CH ₃ ) ₂ cyclohexyl ether H

[Formula] n-hexadecyl ether
H (CH ₂ ) ₁₅ CH ₃ 2-chloroethyl ether
H CH ₂ CH ₂ Cl Methyl propenyl ether
CH ₃ CH ₃ Ethyl ether CH ₃ C ₂ H ₅ Isopropyl ether CH ₃ CH (CH ₃ ) ₂ n-Butyl ether CH ₃ (CH ₂ ) ₃ CH ₃ Isobutyl ether CH ₃ CH ₂ CH (CH ₃ ) ₂ Cyclohexyl ether
CH ₃

[Formula] Hexadecyl propenyl ether
CH ₃ (CH ₂ ) ₁₅ CH ₃ 2-chloroethyl ether
Examples include CH ₃ CH ₂ CH ₂ Cl. The degree of polymerization of the polyalkenyl ether may be any degree as long as it is 2 or more. As an initiator, CHR ¹ =CH-O-(CH ₂ ) _o -
O−CH=CHR ² () and HI and I ₂ and/or and I ₂ . Here, R ¹ , R ² , R ³ , and R ⁴ of () and () are −
H, _-CH3 group is shown, and n is a natural number. Specifically, () 1,4-divinyloxybutane (R ¹ = R ²
=H), ()bis(1-iodoethoxy)butane ( ^R3 = ^R4 =H), and the like. CHR ¹ = CH−O−(CH ₂ ) _o −O−CH=CHR ²
() and HI and I When using ₂ initiators () and HI
The molar ratio of is preferably 2:1 to 1:10, especially ()
It is desirable that HI be more excessive. The amount of I ₂ is
The molar ratio with HI is preferably 2:1 to 1:10.
It is desirable that HI and I ₂ be around equivalents. When using and I ₂ , the molar ratio between the amount of I ₂ and () is
A ratio of 10:1 to 1:2 is desirable. The initiator ( ), HI and I ₂ , and ( ) and I ₂ may be mixed in advance, or may be added separately at the start of polymerization. Since the ratio of monomer to initiator corresponds to the degree of polymerization, it may be determined according to the molecular weight (degree of polymerization) of the produced polymer. When carrying out a polymerization reaction, a solvent is usually used, although it may be carried out in bulk. Desirable solvents include aliphatic hydrocarbons such as normal hexane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride and chloroform. The weight ratio of solvent and monomer is usually 1:1~
100:1 is preferred. Particularly preferred is 10:1 to 30:1. The polymerization temperature is preferably below room temperature, especially -5°C
The following are preferred. The polyalkenyl ether produced here has a very narrow molecular weight distribution of 1.2 (weight average molecular weight, number average molecular weight). Here / ratio is GPC (JASCO Corporation "TRIROTAR" chromatograph, column: Showa Denko Corporation polystyrene gel A802,
A803, A804; inner diameter 8 mm, length 500 mm). A telechelic polymer can be obtained by adding a compound having a functional group to the living polymer chains at both ends obtained as described above. -NH ₂ , -OR, -CN, depending on the compound added.
It is possible to use terminals such as -SR, _-NR2 , and -NHR (R represents an alkyl group). Examples of compounds to be added include ammonia, primary monoamines, secondary monoamines, primary diamines, alcohols, cyanide compounds, thiols, etc.
Specifically, nBuNH ₂ ,

[Formula] H ₂ N−(CH ₂ ) ₆ NH ₂ ,

Examples include [Formula]. The amount of these compounds added is in excess or equivalent (preferably in the case of chain extension) with respect to the active site concentration of the living polymer. 1.2 Mw: weight average molecular weight,
Mn: represents number average molecular weight. ), and by having an ether bonding group in the side chain, effects not seen in conventional telechelic polymers can be expected. For example, it can be used as a new surfactant. Furthermore, by extending the chain, the advantage of narrow molecular weight distribution can be utilized. That is, since the microphase-separated structure becomes clear, physical properties such as low-temperature recovery strain are expected to improve when used in thermoplastic elastomers, and because the molecular weight distribution is narrow, it is expected that mechanical strength etc. will be excellent. Furthermore, when it is made into a terminal amino group, it has an aminoether structure and can be used as a new chemical reactant. In addition to the above, it can also be used for antithrombotic materials, artificial leather, etc. The present invention will be explained in more detail below using Examples. Example 1 Living polymerization of ethyl vinyl ether with a difunctional initiator (): ([M] ₀ = 0.38M, [BIOEB] = 5.0mM, [I ₂ ] = 10
mM, toluene, -40℃) [[M] ₀ above means the initial concentration of monomer,
M in 0.38M stands for mole/liter. Also
BIOEB is 1,4-bis(1-iodoethoxy)
It is an abbreviation for butane. The same shall apply hereinafter. ] In the following examples, the reaction was carried out in a glass container that had been thoroughly dried, the interior was replaced with dry nitrogen, and a three-way stopcock was attached, and the reagent was injected through the three-way stopcock.
Perform under a stream of dry nitrogen using a syringe. 0.18 ml (1.9 mmol) of ethyl vinyl ether was dissolved in 2 ml of toluene and cooled to -40°C.
First, 1,4-bis(1-iodoethoxy)
1 ml of a 25 mmol/n-hexane solution of butane was added, followed by 2 ml of a 25 mmol/toluene solution of iodine, and the mixture was polymerized for 30 minutes. At 100% polymerization rate, Mn = 4600 (theoretical molecular weight 5480), w/n = 1.15
A telescopic living polymer is obtained. BIOEB is 0.1422g (1 mmol) of 1,
It can be obtained quantitatively by dissolving 4-divinyloxybutane in 10 ml of n-hexane and reacting it with 2 equivalents of hydrogen iodide (2.5 ml of 800 mmol/n-hexane solution) at -30°C. Hydrogen iodide can be prepared using well-known methods (for example, J. Polym. Sci., C, Vol. 16,
3797 (1968)). Application example 1 Synthesis of a telechelic polymer with amino groups at both ends ([nBuNH ₂ ] = 25 mM): Add 18.3 mg (0.25 mmol) to 5 ml of the living poly(ethyl vinyl ether) solution obtained in Example 1 at -40°C. ) of n-butylamine dissolved in 5 ml of toluene is added. A telechelic polymer having an amino group at the terminal and showing the same molecular weight distribution curve as the starting living polymer can be quantitatively obtained. Elemental analysis value of N: 0.81% by weight (calculated value 0.84% by weight) Example 2 Living polymerization with isobutyl vinyl ether using a bifunctional initiator (): except that isobutyl vinyl ether was used instead of methyl vinyl ether and the polymerization temperature was -30°C Polymerization was carried out in the same manner as in Example 1. The obtained polymer is 7600/
= 1.26. Application example 2 Synthesis of telechelic polymer with amino groups at both ends: Add 58.1 mg (0.50
Add a solution of 2.5 ml of n-hexane to 2.5 ml of n-hexane. After this, absorption of methylene groups based on hexamethylene diamine was observed in the NMR chart of the polymer portion from which low-boiling substances and unreacted hexamethylene diamine were removed. Example 3 0.1422 g (1 mmol) of 1,4-divinyloxybutane was dissolved in 40 ml of n-hexane at room temperature,
2 ml of this solution is poured into a reaction vessel, diluted with 3 ml of toluene, and then cooled to -40°C. Here is a 100 mmol/n-hexane solution of hydrogen iodide 1.0
ml, stir and leave for 5 minutes, then add 2 ml of a 50 mmol/toluene solution of iodine, add thereto a solution of 0.36 ml (3.8 mmol) of ethyl vinyl ether dissolved in 2 ml of toluene, and stir thoroughly. Then, polymerization was carried out for 30 minutes. The polymerization rate is
At 100%, n=5000 (theoretical molecular weight 5480), w/
A telescopic living polymer with Mn=1.16 was obtained.

Claims (1)

[Claims] 1 CHR ¹ = CH-O-(CH ₂ ) _o -O-CH=CHR ²
() and HI and I ₂ , and/or and I ₂ as initiators, alkenyl ether
A method for producing polyalkenyl ether, characterized by polymerizing CHR ⁵ =CH(OR ⁶ )(). (R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent either -H or -CH ₃ , and R ⁶ represents an alkyl group or a cycloalkyl group which may be substituted with halogen. n indicates a natural number.)