JP3231090B2 - Method for producing isobutylene oxide copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a copolymer of isobutylene oxide and another alkylene oxide with good catalytic efficiency.

[0002]

2. Description of the Related Art Polyisobutylene oxide is known as a photodegradable polymer which is easily decomposed by light. In addition, polyisobutylene oxide films have characteristics such as high light transmittance, low water vapor transmittance, and high gas (CO ₂ , O _2, etc.) permeability, and are expected to be used as agricultural and horticultural films. Have been.

[0003] The manufacturing method of such polyisobutylene oxide, diethylzinc / water / t-butylamine catalyst _{[Zn (C 2 H 5)} 2 / H 2 O / t- butylamine = 3/1/1 (mol Ratio)], and a synthesis in a hexane solvent has been reported [Chemistry].
Lett. , 629 (1973)].

[0004]

According to the above-mentioned production method, the amount of polymer produced per reference amount of catalyst is small, and the catalyst efficiency cannot be said to be good. Further, since the polymerization reaction is carried out in a solvent, there is also a problem that the molecular weight distribution represented by the ratio between the weight average molecular weight and the number average molecular weight becomes relatively wide. Accordingly, an object of the present invention is to provide a method capable of polymerizing isobutylene oxide with good catalytic efficiency and producing a polymer having a narrow molecular weight distribution.

[0005]

In view of the above problems, the present inventor has conducted various studies on the polymerization reaction of isobutylene oxide. As a result, the present inventor has used a double metal cyanide complex catalyst as a catalyst and obtained an active hydrogen compound. It has been found that the above object can be achieved by copolymerizing isobutylene oxide and another alkylene oxide under addition.

[0006] Thus, the present invention relates to a method for preparing 5-70 mol% of isobutylene oxide and 30-95 mol% of another alkylene oxide having 2 or more carbon atoms in the presence of a double metal cyanide complex catalyst and an active hydrogen compound. Provided is a method for producing an isobutylene oxide copolymer, characterized in that the copolymerization is carried out at a ratio .

According to the present invention, an isobutylene oxide copolymer can be produced with good catalytic efficiency, and an isobutylene oxide copolymer having a narrow molecular weight distribution can be obtained. Further, by changing the copolymerization ratio, the photodecomposition rate of the produced copolymer can be arbitrarily controlled.

In the present invention, as the other alkylene oxide to be copolymerized with isobutylene oxide, a known or well-known compound having 2 or more carbon atoms and having an epoxy group is widely used without any particular limitation. it can. Preferred examples include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and epibromohydrin. These other alkylene oxides can be used alone or in combination of two or more.

The double metal cyanide complex catalyst used in the present invention includes US Pat.
And those having the structure of the following general formula (1) as shown in Nos. 7 to 9 and the like.

[0010] ^{_{M 1 a [M 2 x (}} CN) y] b (H 2 O) c (R) d ··· (1) provided that, ^{M 1} is Zn (II), Fe (II ), Fe (III ), Co
(II), Ni (II), Al (III), Sr (II), Mn (II), C
u (II), Sn (II), Pb (II), Mo (IV), Mo (VI),
Cr (III), W (IV), etc., and M ² is Fe (II),
Fe (III), Co (II), Co (III), Cr (II), Cr (II)
I), Mn (II), Mn (III), Ni (II), V (IV), V (V), etc., wherein R is an organic ligand, a, b, x and y
Is a positive integer depending on the valence and coordination number of the metal,
c and d are positive numbers depending on the coordination number to the metal.

In the general formula (1), M ¹ is Zn
(II) is preferred, and M ² is Fe (II), Fe (III),
Co (II), Co (III) and the like are preferred. Further, as the organic ligand R, for example, ketone, ether, aldehyde,
Examples include esters, alcohols, and amides.

The double metal cyanide complex represented by the general formula (1) is a metal salt M ¹ _Xa (M ¹ and a are the same as described above, and X is an anion that forms a salt with M ¹ ).
And polycyanometallate (salt) _Ze [M ² _x (C
N) _y ] _f (M ² , x, and y are the same as described above. Z is hydrogen, an alkali metal, an alkaline earth metal, or the like, and e and f are the valences of Z and M ^2. Aqueous solution or a solution of a mixed solvent of water and an organic solvent, and contacting the obtained double metal cyanide with an organic ligand R. It is produced by removing a suitable solvent and an organic ligand R.

Polycyanometallate (salt) _Ze [M ² _x
(CN) _y ] In _f , various metals including hydrogen and alkali metals can be used as Z, and lithium, sodium, potassium, magnesium and calcium are preferable. Particularly preferred polycyanometallates (salts) are the usual alkali metal salts, ie the sodium and potassium salts.

Examples of the active hydrogen compound used in combination with the above-mentioned double metal cyanide complex catalyst include a compound having one hydroxyl group such as a monool, but a polyhydroxy compound having 2 to 8 hydroxyl groups is usually used. Can be effectively adopted. As the polyhydroxy compound,
For example, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol; tetrahydric or higher alcohols such as dextrose, sorbitol, and sucrose; and alkylene oxides in these polyhydric alcohols Molecular weight 300 to 3 obtained by reaction
About 000 polyether polyols. In particular, polyether polyols having a molecular weight of about 300 to 3000 are suitable.

Examples of the active hydrogen compound used in the present invention include compounds having a phenolic hydroxyl group or a methylol group such as bisphenol A, resole and novolak, compounds having a hydroxyl group and another active hydrogen such as ethanolamine and diethanolamine, and monoamines. Such as amines and polyamines, and a molecular weight of 300 to 3 obtained by reacting these amines with an alkylene oxide.
About 000 polyether polyols are also included.
In addition, polyhydroxy compounds such as polyester polyols can be used.

The above active hydrogen compounds can be used alone or in combination of two or more.

The copolymerization reaction in the present invention can be carried out in a solvent or in a solvent-free atmosphere substantially in the absence of an active gas. The solvent in this case is not particularly limited as long as it is a non-aqueous solvent that does not react with a monomer such as isobutylene oxide or another alkylene oxide or a double metal cyanide complex catalyst, and examples thereof include tetrahydrofuran and hexane.

The amount of the double metal cyanide complex catalyst used is as follows:
Although not particularly limited, it is preferably about 10 to 3000 ppm, particularly preferably about 50 to 1000 ppm, based on the active hydrogen compound (initiator) used. The catalyst may be introduced into the reaction system in a lump at first, or may be divided and introduced sequentially.

Although the amount of the active hydrogen compound used is not particularly limited, it is usually about 5% by weight to 90% by weight based on the total amount of isobutylene oxide, other alkylene oxides and the active hydrogen compound. You. If the amount is less than 5% by weight, the copolymerization reaction of the present invention proceeds, but the significance of improving the catalyst efficiency is reduced. Even when the active hydrogen compound is used in an amount of 90% by weight or more, the copolymerization reaction of the present invention proceeds, but the meaning of the target copolymer is reduced.

The copolymerization reaction temperature of the present invention is usually from 0 ° C.
It is selected from a range of about 140 ° C., and is not particularly limited.

The amount of isobutylene oxide to be used can be arbitrarily selected in consideration of the decomposability of the target copolymer by light irradiation or the like. In order to satisfactorily exhibit degradation due to light irradiation, the isobutylene oxide 5 to 70 mol% and having 2 or more other alkylene oxide carbon 30-95
At a ratio of mole% Ru copolymerized. In particular, isobutylene oxide is preferably at least 10 mol%.

On the other hand, to remove the double metal cyanide complex catalyst after the completion of the copolymerization reaction, an alkali such as ammonia is added to decompose (ionize) the double metal cyanide complex catalyst.
After that, a complex can be formed by adding a chelating agent, and this can be easily removed by filtration using an adsorbent.
No. 89617 or 2-289618).

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention.

The conical beaker 300 ml [Preparation of composite metal cyanide complex catalyst, zinc chloride aqueous solution of 7.5 molar _{(10.2g-ZnCl 2 / 10ml-} H
Put 10ml of ₂ O), after heating to 40 ° C., 0.
17 molar potassium hexacyanocobaltate aqueous solution (4.2 g-K ₃ [Co (CN) ₆ ] / 75 ml-H ₂
O) 75 ml were added dropwise. 160 ml of a 50% by weight aqueous solution of glyme (ethylene glycol dimethyl ether) was added, and the mixture was stirred at 40 ° C. for 1 hour to obtain a precipitate. 30% by weight of the obtained precipitate
The aqueous solution was thoroughly washed with a concentrated aqueous glyme solution and a 90 wt% aqueous glyme solution, and filtered. After the filter cake was dried in an oven at 80 ° C. for 1 hour, it was pulverized in an agate mortar to obtain a double metal cyanide complex catalyst.

Example 1 Polyoxypropylene triol 3 having a molecular weight of 1,000
0 g, 7.5 g of propylene oxide, 7.5 g of isobutylene oxide, and 0.015 g of the double metal cyanide complex catalyst of the above preparation example (500 p for the above polyoxypropylene triol as initiator).
pm) in a 200 ml pressure-resistant autoclave,
The mixture was reacted at 120 ° C. for 3 hours under a nitrogen atmosphere to obtain 45 g of an isobutylene oxide copolymer.

The obtained copolymer is transparent and has a number average molecular weight (hereinafter abbreviated as _Mn ) of 1500 as measured by gel permeation chromatography (hereinafter abbreviated as GPC), Weight average molecular weight (hereinafter, referred to as
Abbreviated as _Mw . ) And M _n (M _w / M _n ) is 1.
It turned out to be 10. Further, unreacted monomers (propylene oxide and isobutylene oxide) were not detected by GPC measurement.

Example 2 Polyoxypropylene diol having a molecular weight of 700
0 g, 21.0 g of propylene oxide, 9.0 g of isobutylene oxide, and 0.010 g of the double metal cyanide complex catalyst of the above preparation example (1000 g for the polyoxypropylene diol as the initiator).
ppm) was charged into a 200 ml pressure-resistant autoclave and reacted at 130 ° C. for 4 hours under a nitrogen atmosphere to obtain 40 g of an isobutylene oxide copolymer.

The obtained copolymer was measured by GPC.
_Mn was 2800 and _Mw / _Mn was 1.16. Further, unreacted monomers (propylene oxide and isobutylene oxide) were not detected by GPC measurement.

The obtained copolymer was treated with an ammonia buffer (NH 4) containing a chelating agent (ethylenediaminetetraacetic acid).
After stirring with _3- CH ₃ COONH ₄ ), the mixture was dehydrated, an adsorbent was added, and the mixture was filtered. When the content of Zn (II) derived from the double metal cyanide complex catalyst was examined for the obtained purified copolymer, the Zn (II) was not detected.

In the above copolymerization reactions of Examples 1 and 2, even when ethylene oxide was used instead of propylene oxide, almost the same results were obtained.

[0031]

According to the method of the present invention, it is possible to obtain a copolymer having a narrow molecular weight distribution in which the ratio of the weight average molecular weight to the number average molecular weight is 1.50 or less. In addition, the composition ratio of isobutylene oxide and other alkylene oxide is set to a predetermined value.
Since it can be arbitrarily changed within the range, it is also recognized that a copolymer having a controlled rate of decomposition by light can be smoothly and advantageously obtained.

Further, by using a polyhydric alcohol or the like as the active hydrogen compound, a copolymer reactive at both ends can be obtained, and a new type of photodegradable polymer can be synthesized.

Moreover, such a copolymer can be produced with good catalytic efficiency. For example, a double metal cyanide complex catalyst is added to an active hydrogen compound (initiator) for 10 to 10 minutes.
Even at a low concentration of 3000 ppm, the desired copolymer can be produced smoothly and advantageously.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References US Patent 3,418,849 (US, A) US Patent 3,829,505 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 65/00-65 / 48 WPI / L

Claims (1)

(57) [Claims] (1) isobutylene oxide in the presence of a double metal cyanide complex catalyst and an active hydrogen compound;
A method for producing an isobutylene oxide copolymer, characterized by copolymerizing 30 mol% and another alkylene oxide having 2 or more carbon atoms in a proportion of 30 to 95 mol% .