JPH01108203A - Manufacture of polyalkenyl ether - Google Patents

Abstract

PURPOSE:To produce in a high yield the title polymer which has a narrow molecular weight distribution and a desired molecular weight, by polymerizing an alkenyl ether in the presence of respectively specified organoaluminum com pound, cation donating compound and ester compound. CONSTITUTION:An alkenyl ether (A) of formula I (wherein R<1> is H or CH3; and R<2> is a monovalent organic group) is polymerized in the presence of an organoaluminum compound (B) of formula II (wherein R<3> is R<2>; X is halogen; 0<=m<3, and n<=3, with m+n=3) with the molar ratio of (A) to (B) of 2-1,000, a cation donating compound (C) (e.g., H2O or CH3COOH) with the molar ratio of (A) to (C)<=2, and an ester compound (D) (e.g., ethyl acetate) with the molar ratio of (A) to (D)>=0.1, if desired, in a solvent (E) (e.g., hexane) in an amount 1-100 times by volume as much as the component (A) at 100 deg.C or below to produce a polyalkenyl ether having a degree of polymerization of 2 or above and a molecular weight distribution of 1.3 or below.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing polyalkenyl ether.

(Prior art) Conventionally, alkenyl ethers are only polymerized by cationic polymerization, but in the case of cationic polymerization, migration and termination reactions are likely to occur and living growth does not occur. However, the present inventors have recently discovered that alkenyl ethers undergo living growth when an initiator consisting of HI and Step 2 is used, and thus alkenyl ethers have a narrow molecular weight distribution. He discovered scales that can form polymers and block copolymers [Proceedings of the Society of Polymer Science and Technology, 32, 1].
87°188.190, 1439.1443 (1983
)).

However, when an initiator consisting of HI and Step 2 is used as described above, living polymerization progresses only after polymerization at a low temperature of -15°C or lower, so the polymerization rate is also low, and from an industrial standpoint, it is difficult to Moreover, if the initiator concentration is too low to obtain a high molecular weight polymer, side reactions due to impurities will become noticeable, making it difficult to obtain a high molecular weight polymer. ,there were.

Therefore, the present inventors further discovered that a system using an initiator consisting of an organoaluminum compound and an oxygen-containing compound, especially an initiator in which the oxygen-containing compound is an ester, has a high polymerization rate because living polymerization proceeds even near room temperature. was found to be large and industrially advantageous (patent application 1986-10).
No. 3654).

(Problems to be Solved by the Invention) However, in the case of the conventional system using the above-mentioned initiator, living polymerization proceeds even around room temperature, and the molecular weight distribution of the polyalkenyl ether produced becomes narrow. Since it is difficult to define the molecular weight by the amount of initiator, there is a problem in that the most important molecular weight cannot be controlled.

The present invention solves the above-mentioned conventional problems and provides a novel production method that enables industrially advantageous production of polyalkenyl ethers with a desired molecular weight and a narrow molecular weight distribution by making it possible to control the molecular weight. The purpose is to provide.

(Means for Solving the Problems) The present inventors have conducted intensive research to achieve the above object, and as a result, have arrived at the present invention. That is, the present invention provides an alkenyl ether represented by the general formula (1) (wherein, R1 represents a hydrogen atom or a methyl group, and R2 represents a monovalent organic group).
Below, alkenyl ether (1),! :Abbreviated. )
, general formula CI) R3mA p X n --- (l ) (
In the formula, R3 represents a monovalent organic group, X represents a halogen atom, m and n are m+n=3 and O<m×3.0×n
<Indicates the number 3. ), a cation-supplying compound Ci), and an ester compound [■
The gist of this invention is a method for producing a polyalkenyl ether, which is characterized by polymerization in the presence of the following.

The initiator used in the process of the invention is of the general formula CI)
It consists of an organoaluminum compound represented by, a forepaw cation supplying compound (1), and a forepaw ester compound (IV').

In the organoaluminum compound represented by the general formula (II), R3 represents a monovalent organic group, specific examples of which include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, etc. , there are no particular restrictions. Moreover, X represents a halogen atom,
m and n are m+n=3 and 0(m(3,0(n(3
Indicates the number of Specific examples of such organoaluminum compounds include diethylaluminum chloride, diethylaluminum 710mide, diisobutylaluminum chloride, diethylaluminium hydride, dimethylaluminum sesquichloride, diethylaluminum sesquichloride, and diethylaluminum sesquichloride.

Diisobutylaluminum sesquichloride, methylaluminum chloride, ethylaluminum chloride, ethylaluminum 760mide, ethylaluminum iosito, ethylaluminum fluoride, inbutylaluminum chloride, octylaluminum chloride,
Examples include ethoxyaluminum dichloride, vinylaluminum dichloride, phenylaluminum dichloride, aluminum trichloride, aluminum tripromide, and the like. The amount of one type or a mixture of two or more of these organoaluminum compounds to be used is generally a molar ratio of raw material monomer (1)/organoaluminum compound (II).
) = may be in the range of 2 to 1000, preferably 10 to
A range of 1000 is sufficient.

The forepaw cation-supplying compound CII [) is a proton-supplying compound represented by the following general formula] HA ...... CI), such as R20, CF 3 CO
OH, CC13COOH, CH3CO0H, HCOOH
.

H3P0. , σ)OH, HCJ, etc.
Among these, especially R20, CH3CO0H, CF3C
OOH is preferred. In addition, the following addition compound CV) obtained by reacting only the alkenyl ether [I] and the cation supplying compound (1) in advance: CH2R" -CH(OR2)
It can also be used as a compound of the form (V). This addition compound (V) is a forefoot alkenyl ether [1]
and forepaw cation supplying compound CI) were added in equivalent amounts, and the mixture was heated at 60°C.
It is obtained by stirring and reacting under heating for 3 hours.

Forepaw cation supplying compound (1) or the above addition compound (V
) is important because the degree of polymerization is determined by the molar ratio of [I]/cap] (100% polymerization rate). That is, in order to obtain a desired degree of polymerization, depending on the degree of polymerization, (III
) or CV), i.e. CI) / CII[) or C
Since it is only necessary to determine the molar ratio of I)/(:V), setting the molecular weight becomes very easy.

Note that the molar ratio of CI)/(1) or CI)/[V) may be any value as long as it is 2 or more.

To use the cation-supplying compound cap in this way,
One type may be used, or two or more types may be mixed. Moreover, these may be used in bulk or after being diluted with an inert solvent.

Specific examples of the paw ester compound (IV) include ethyl acetate, butyl acetate, phenyl acetate, ethyl butyrate, ethyl stearate, ethyl benzoate, phenyl benzoate, diethyl phthalate, diethyl inphthalate, and the like.

When using these ester compounds [), one type may be used, or two or more types may be mixed. Moreover, these may be used in bulk or after being diluted with an inert solvent. The amount of these ester compounds fJ) to be used is preferably [I]/(I>0.1 (molar ratio), and CI)/(IV)<0.1 (molar ratio). In some cases, the system of the polymerization process of the present invention is unlikely to be a completely living system. That is, the amount used in the method of the present invention is preferably CI)/(IV)≧0.
．． 3 (molar ratio), particularly preferably CI)/(N)≧
0.5 (molar ratio). This ester compound (IV)
If it is not used, a living system will not be formed at all, and polymerization will occur with normal movement and termination.

The alkenyl ether which is the raw material monomer of the method of the present invention is represented by the general formula (1), in which R1 represents a hydrogen atom or a methyl group, and R2 represents a monovalent organic group, such as an alkyl group, aryl group, aralkyl group, alkenyl group, alkoxyalkyl group, aryloxyalkyl group, etc., which may be substituted with a hetero group. These monomers may be used alone or in combination of two or more. 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 51 types shown in 1.2.3 and 4 of Table 1 below.

The degree of polymerization of the polyalkenyl ether may be any degree as long as it is 2 or more.

When carrying out a polymerization reaction, it may be carried out using
Use a solvent. Desirable solvents include aliphatic hydrocarbons such as n-hexane/cyclohexane, aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride and methylene chloride.

The charging ratio of solvent and raw material monomer is usually 1:1 to 100:
1 is preferred. Particularly preferred is 5:1 to 30:1.

The polymerization temperature in the method of the present invention is suitably selected from +100°C or lower. This means that living polymerization can occur even at temperatures around room temperature or higher, so the polymerization rate is high and no cooling device is required, so its industrial significance is particularly great. Of course, there is no problem in polymerizing at a low temperature of 0° C. or lower, as is conventional practice.

The polyalkenyl ether produced here has a total average molecular weight of -191, Mn: number average molecular weight. ).

Here, the Mw/Mn ratio is determined by GPC (JASCO Corporation TR).
I ROTAR chromatograph, column: Showa Denko polystyrene gel A302, A80 Kame A304; inner diameter 81
1I11 length so ox).

(Example) Next, the present invention will be explained in more detail using examples.

Example 1 Add 0.5 ml of imptylated vinyl ether (fk) to n-hexane (omg) sufficiently purified under a nitrogen atmosphere to dissolve it (0.76 mol/E), and add 0.5 ml of acetic acid thereto. Ethyl was added (1.0 mol/l) and heated to +40°C. There acetic acid diluted in hexane (40 mmol/l) 0.5 mJl and a hexane solution of ethylaluminum dichloride (40 mmol/l) 0.5
mj and mj were added in this order to start polymerization, and the polymerization was continued for 18 hours. Thereafter, the polymerization was stopped with methanol containing a small amount of aqueous ammonia. The stopped mixture was first washed with an aqueous hydrochloric acid solution (5 to 10 vol%) and then with water to remove the catalyst residue, and the solvent was evaporated to recover the product.

As a result, the conversion rate was 96chi and Mn=1.5xto'.

A polymer with Mw/Mn=1.07 was obtained. This Mn
The value agrees well with the calculated value (1,83×10') assuming that one molecule of polymer is produced from one molecule of acetic acid.

Example 2 In place of ethyl acetate in Example 1, 0.5 ml of ethyl benzoate was added (0.7 mol/l), and the polymerization time was 1.
The same procedure as in Example 1 was carried out except that the time was changed to 0 hours.

As a result, with a conversion rate of 100%, Mn=1.9X1 o4
.

A polymer with Mw/Mn=1.12 was obtained.

Example 3 Trifluoroacetic acid or water was used instead of acetic acid in Example 1, and in both cases, the polymerization temperature was 0°C, and the concentration of ethylaluminum dichloride was 20 mmol/! The polymerization time was 4 hours in the former case and 6 hours in the latter case.
The same procedure as in Example 1 was carried out except that the time was 5 hours.

As a result, in the former case, the conversion rate was 89chi, and Mn==1.6X
IO', a polymer with Mw/Mn=1.07 was obtained,
In the latter case, the conversion rate is 92%, and Mn=t, 6xto, Mw/
A polymer with Mn=1.09 was obtained.

Comparative Example 1 When polymerization was carried out according to the method of Example 1 without using ethyl acetate, the conversion rate was too% in 0.5 hours, but the MW
/Mn=25, and the molecular weight distribution was broadened.

Example 4 The same procedure as in Example 1 was carried out except that an adduct of isobutyl vinyl ether and acetic acid [V] (having the general formula %) was used in place of acetic acid in Example 1.

As a result, the conversion rate was 95 cm, and Mn = 1.7 x 10'.

A polymer with Mw/Mn=1.04 was obtained.

Example 5 The same procedure as in Example 4 was carried out except that the polymerization temperature in Example 4 was changed to 0°C, the concentration of ethylaluminum dichloride was changed to 10 mmol/71, and the polymerization time was changed to 50 hours.

As a result, with a conversion rate of 1001%, Mn=1.8X 10
'.

A polymer with Mw/Mn=1.05 was obtained.

Example 6 The concentration of the adduct C/V of inbutyl vinyl ether and acetic acid in Example 5 was doubled (8 mmol/J) or 1X.
The same procedure as in Example 5 was carried out, except that the polymerization time was changed to 2 times (2 mmol/71) and the polymerization time was changed to 20 hours in the former case and 95 hours in the latter case.

As a result, in the former case, the conversion rate is 91ch, Mn=1, OX
l 0', Mw/Mn=1.07 novolimer was obtained, and Mn was about - of Example 5 (calculated value Mn=0
．． 9X10'). Also, in the latter case, the conversion rate is 100%,
A polymer with Mn-41X10', Mw/Mn = 1.06 was obtained, and Mn was almost twice that of Example 5. Example 5 was carried out in the same manner as in Example 5, except that ether was used and the polymerization time was 48 hours.

As a result, with a conversion rate of 92chi, Mn==1.7X1 o4
.

A polymer with Mw/Mn==1.15 was obtained.

Example 8 Except for using ethylaluminum sesquichloride in place of ethylaluminum dichloride in Example 5,
Even when polymerization was carried out in the same manner as in Example 5, Mw/Mn=
1.19 polymers were obtained.

Comparative Example 2 In Example 5, when BF3(OC2H5)2 was used instead of ethylaluminum dichloride, Mw/M
A polymer with a broad molecular weight distribution of n=16 was obtained.

(Effects of the Invention) As is clear from the above results, the production method of the present invention can produce polyalkenyl ethers with a narrow molecular weight distribution and their high molecular weight products at an unprecedented industrial advantage of below +100°C. Not only can they be produced at high temperatures and in high yields, but their molecular weights can also be controlled, which is a remarkable effect of industrial value. In particular, the ability to produce polyalkenyl ethers with a narrow molecular weight distribution even above room temperature is of revolutionary significance from an industrial perspective. In addition, since the polymer terminals produced here are living, it is possible to obtain block copolymers with other polymers,
It is also possible to introduce a functional group at the end and use it as a macromer. Also, depending on the type of monomer,
It is also possible to make it hydrophilic through a polymer reaction, or to produce a hydrophilic/hydrophobic block copolymer, and use it as a novel surfactant.

Claims (2)

[Claims] (1) General formula [I] CHR^1=CH(OR^2)...[I] (In the formula, R^1 represents a hydrogen atom or a methyl group, and R^2
indicates a monovalent organic group. ) is represented by the general formula [II] R^3mAlXn......[II] (wherein, R^3 represents a monovalent organic group, X represents a halogen atom, and m and n represent m+n =3 and 0≦m<3,0
Indicates the number of <n≦3. ), a cation-supplying compound [III], and an ester compound [IV]. (2) The method for producing a polyalkenyl ether according to claim 1, wherein the amount of the ester compound [IV] is ester compound/alkenyl ether [I]≧0.1 (molar ratio).