JPH0768336B2 - Process for producing polyether copolymer having oligooxyethylene side chain - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention has a function as a special rubber material or a modifying material for other polymers, a function as a phase transfer catalyst, a function for capturing and separating ions, or a polymer conductor. The present invention relates to a novel polyether copolymer that can be expected to function as a material.

(Technical background) As a polyether copolymer having a main chain of an oxyethylene chain, for example, there is an epichlorohydrin-ethylene oxide copolymer, which is industrially used as an oil resistant rubber having excellent cold resistance. On the other hand, cyclic or chain polyethers, especially polyethers containing oxyethylene units, have been extensively studied and widely used for phase transfer catalysis based on their complex-forming ability or dissolving ability for cations such as metal ions. Has been done. Further, since high conductivity of a system in which an alkali metal ion is dissolved in high molecular weight polyethylene oxide has been found, a polymer having a polyoxyethylene chain in the molecule has been attracting attention as an ionic conductor. Also, the pharmacological action of substances having polyoxyethylene in the side chain has been found.

Based on such various findings, it has been interesting to introduce polyoxyethylene into polymers, and various kinds of polymers of this kind have been synthetically studied.

For example, a polymer having polymethacrylic acid, polyphosphazene, polydiacetylene, etc. as a main chain and a polyoxyethylene group as a side chain has been synthesized, and its properties as an ionic conductor or an effect as a phase transfer catalyst have been reported. Despite the interest from these various effects, polymers containing oxyethylene chains in both the main chain and side chains have not been known so far.

(Object of the invention) The object of the present invention is useful for the purpose of a special rubber material or a modified material of other polymers, and also functions as a polymer ion conductor, a phase transfer catalyst, an ion capturing / separating function, and the like. It is an object of the present invention to provide a process for producing a novel polymer having a polyoxyethylene group in its side chain and having a polyoxyethylene group in its main chain, which polymer is useful as a polymer material.

The present invention can provide a polyether copolymer having a molecular weight according to these various uses.

(Structure of the Invention) The present invention relates to a structural unit whose main chain structure is represented by the following formula (I):
Poly having an oligooxyethylene side chain consisting of 30 to 99 mol% and 70 to 1 mol% of a structural unit represented by the following formula (II), and having a reduced viscosity of 0.01 to 3 measured with a benzene solution of 0.1% at 45 ° C. In producing the ether copolymer, the monomers represented by the following formulas (III) and (IV) are used,
A method for producing a polyether copolymer having an oligooxyethylene side chain, which comprises polymerizing a heat condensate of an organic tin and a phosphoric acid ester as a ring-opening polymerization catalyst.

However, in the formulas (I) and (III), R ¹ has 1 to 1 carbon atoms.
A group selected from an alkyl group having 2 to 2, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and a tetrahydropyranyl group. And n is a number from 1 to 12.

In the formulas (II) and (IV), R ² is a hydrogen atom or an atom or a group optionally having a substituent, which is selected from an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group, and In the formula (II), constituent units having different R ² may be present in the same polymer chain.

The polyether copolymer of the present invention comprises a glycidyl ether of oligoethylene glycol in which one hydroxy group represented by the above formula (III) is protected by another group, and a monomer selected from the above formula (IV) with organotin. It is obtained by polymerizing a heat condensate with a phosphoric acid ester as a ring-opening polymerization catalyst.

The compound of the above formula (III) is prepared by optionally selecting oligoethylene glycol monoether represented by the following formula (V) and epichlorohydrin in the presence of an onium salt or crown ether under basic conditions such as caustic alkali. It can be synthesized by reacting.

^{_{HOCH 2 -CH 2 -O n R 1}} (V) where in the above formula (V), R ¹ and n are formula (I) of
Same as R ¹ and n.

In the above general formulas (I), (III) and (V), examples of the case where R ¹ is an alkyl group include groups such as methyl, ethyl, propyl, hexyl, octide and dodecyl. Examples of groups include groups such as vinyl, allyl and the like. Examples of cycloalkyl groups are groups such as cyclopropyl, cyclohexyl, and methylcyclohexyl, examples of aryl groups are groups such as phenyl, tolyl, naphthyl, and examples of aralkyl groups are groups such as benzyl and phenylethyl. Can be mentioned respectively.

Specific examples of the compound of the general formula (IV) for forming the structural unit (II) of the polyether copolymer of the present invention include alkene oxides such as ethylene oxide, propylene oxide and butadiene monoxide, cyclohexene oxide, vinylcyclohexene. Cycloalkyl epoxides such as oxides, epoxides having an aromatic ring such as styrene oxide and α-methylstyrene oxide, epoxides having halogens such as epichlorohydrin, epibromohydrin and epiiodohydrin,
Glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether, glycidyl acetate, glycidyl propionate,
Examples thereof include glycidyl esters such as glycidyl benzoate and glycidyl cinnamate, and epoxyalkanoic acid esters such as methyl glycidate and methyl 3,4-epoxybutyrate.

One of these or two or more of them may be used as a copolymerization component. That is, the constitutional unit (II) of the polyether copolymer of the present invention may have constitutional units formed from the above-mentioned two or more kinds of monomers in the same polymer chain.

As the ring-opening polymerization catalyst used when producing the polyether copolymer of the present invention, a heat condensate catalyst system of organotin and phosphoric acid ester known as a high polymerization catalyst is preferable. This catalyst system imparts favorable properties to the rate of polymerization or the resulting polymer. Details of this catalyst system are described in the Applicant's US Pat. No. 3,773,394, and include, for example, dibutyltin oxide-tributylphosphate condensates.

The polyether copolymer of the present invention comprises a glycidyl ether of oligoethylene glycol of the formula (III) compound and the formula (IV) compound in the presence or absence of a solvent of 10 to 80 using the above ring-opening polymerization catalyst. Obtained by reacting at 0 ° C., usually with stirring or shaking. The amount of the catalyst used is appropriately in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the raw material monomer. It is desirable that the water content of the reaction system during the reaction be as low as possible. The polyether copolymer becomes a polymer having various molecular weights depending on the reaction conditions.

For example, it is possible to obtain various polymers such as a low molecular weight polymer soluble in an ordinary solvent, or a high molecular weight polymer having sufficient strength and capable of forming a film.

For many of these purposes, polyether copolymers have a ratio of the constituent units of formula (I) and formula (II) in the range of 30-99: 70-1.
It has a reduced viscosity of 0.01-3, preferably 0.05-, measured at 0.1% benzene solution at 45 ° C.
It is in the range of 3. These polymers can be used for various purposes as a solution, as a molded product, and by blending with other polymers.

(Example) Monomer Synthesis Example 1 20 g of diethylene glycol monomethyl ether (1.7 x 10
^-1 mol), epichlorohydrin 77g (8.3 × 10 ^-1 mol) and triethylbenzylammonium chloride 0.436g
(1.7 × 10 ^-3 mol) was placed in a flask equipped with a reflux condenser, a thermometer and a stirrer, and 17 g (2.0 × 10 ^-1 mol) of 48 wt% caustic soda aqueous solution was added in 30 minutes while heating and stirring at 50 ° C. Dropped. After the dropping was completed, the reaction was carried out at the same temperature for 7 hours. After cooling, 100 ml of cold water was added, methylene chloride extraction (100 ml × 2 times) was performed, and the product was dried over sodium sulfate and purified by distillation under reduced pressure to obtain 23 g of diethylene glycol glycidyl methyl ether (yield 74%) as a target product. .

The physical properties and NMR spectrum assignment of the obtained diethylene glycol glycidyl methyl ether (IIIa) are shown below.

Property bp 92 ℃ / 2mmHg ▲ n ³⁰ _D ▼ 1.4339 NMR spectrum assignment Solvent CDCl ₃ , internal standard TMS δ: 2.40 to 2.95 (2H, m, a) δ: 3.32 (3H, s, b) δ: 2.95 to 3.80 (11H, m, c) Catalyst production example Stirrer, thermometer In a three-necked flask equipped with a distillation apparatus, 12.5 g of dibutyltin oxide and 2 of tributylphosphate.
6.6 g was added, and the mixture was heated at 250 ° C. for 20 minutes while stirring under a nitrogen stream to distill off the distillate to obtain a solid condensed substance as a residue.

Examples 1 to 3 The inside of a glass ampoule having an inner volume of 50 ml was replaced with nitrogen, and the above-mentioned condensation material as a catalyst and dibutylene glycol glycidyl methyl ether (IIIa) and epichlorohydrin adjusted to a water content of 10 ppm or less were used in Table 1. Was charged in a molar ratio as shown in (1), and after sealing the tube, the ampoule was shaken and copolymerized under the catalyst amount and reaction conditions shown in the same table.
After the reaction, 100 ml of benzene was added to the reaction product to dissolve it, and then 300 ml of hexane was added to cause reprecipitation. The precipitate was taken out, washed with 100 ml of hexane, and then dried to obtain each copolymer. The component composition ratio of the obtained copolymer is first
Shown in the table. Infrared spectra of the copolymers obtained in Examples 1 to 3 are shown in FIGS. 1 to 3, respectively, and ¹ H-NMR spectra are shown in FIGS. 4 to 6.

(Effects of the Invention) The polyether copolymer of the present invention can provide a new material having a function as a phase transfer catalyst, an ion conductive material, and an ion trapping / separating function as a special rubber material.

[Brief description of drawings]

1 to 3 are infrared absorption spectra of the copolymers obtained in Examples 1 to 3, and FIGS. 4 to 6 are copolymers obtained in Examples 1 to 3, respectively. 2 is a ¹ H-NMR spectrum of

Claims (1)

[Claims] 1. A main chain structure is substantially 30 to 99 mol% of a structural unit represented by the following formula (I) and 70 to 1 mol% of a structural unit represented by the following formula (II).
In producing a polyether copolymer having an oligooxyethylene side chain having a reduced viscosity of 0.01 to 3 measured at 45 ° C. in a 0.1% benzene solution, the following formulas (III) and (IV) A process for producing a polyether copolymer having an oligooxyethylene side chain, which comprises polymerizing a heat-condensation product of an organic tin and a phosphoric acid ester as a ring-opening polymerization catalyst using the monomer represented by: However, in the formulas (I) and (III), R ¹ has 1 to 1 carbon atoms.
A group selected from an alkyl group having 2 to 2, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and a tetrahydropyranyl group. And n is a number from 1 to 12. In the formulas (II) and (IV), R ² is a hydrogen atom or an atom or a group optionally having a substituent, which is selected from an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group, and In the formula (II), constituent units having different R ² may be present in the same polymer chain.