JPS63241026A - Polyether polymer containing oligooxyethylene chain - Google Patents

Abstract

PURPOSE:To obtain the title polymer having high abilities to solvate and coordinate metallic ions and a low glass transition point and being useful as a phase transfer catalyst, a polymeric ion conductor, etc., comprising specified units and having a specified reduced viscosity. CONSTITUTION:An oligoethylene glycol glycidyl ether (A) with its OH group being protected with a different group is obtained by reacting an oligoethylene glycol monoether (a) of formula I (wherein R is a 1-12C alkyl, a 2-8C alkenyl, a 3-8C cycloalkyl, a 6-14C aryl, a 7-12C aralkyl or tetrahydropyranyl and n is 1-12) with epichlorohydrin (b) in the presence of an onium salt, a crown ether or the like in basic conditions. 100pts.wt. component A is reacted at 10-80 deg.C in the presence of 0.01-1pt. ring opening polymerization catalyst to obtain the title polymer of formula III, having a reduced viscosity (in a 0.1% benzene solution at 45 deg.C) >=0.01.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polymer that is expected to function as a phase transfer catalyst, ion trapping/separation function, or polymeric conductor material.

(Technical background) In recent years, research has been actively conducted on the application of cyclic or dehydrated polyethers as phase transfer catalysts based on their ability to form complexes or dissolve metal salts, and as electrolytes for complexes containing dissolved metal ions. It is being said. In particular, since the discovery of high electrical conductivity in a composite of high molecular weight polyethylene oxide with alkali metal ions dissolved therein, polymers with polyoxyethylene chains in the molecule have attracted attention, and in particular polymers with polyoxyethylene groups introduced as side chains have attracted attention. Polymers are being synthesized.

Conventionally, polymers with polyacrylic acid, polyphosphazene, or polydiacetylene as the main chain and polyoxyethylene groups as side chains have been known as such polymers, and their catalytic ability and properties as plate electrolytes for metal ion complexes have been studied. It has been reported. However, no polymer has been known so far whose main chain and side chains are composed of similar polyoxyethylene groups.

(Objective of the Invention) An object of the present invention is to provide a novel polymer having a polyoxyethylene group in its side chain and also having a polyoxyethylene group in its main chain.

Polymers with similar polyoxyethylene groups in both side chains and main chains have high solvating or coordinating ability for metal ions, and the glass transition point (Tg) is roughly increased by increasing the degree of freedom of the molecular chain. We can expect it to be lower. The polyether polymer of the present invention is considered particularly preferable as a polymeric ion conductor, and particularly for purposes such as polymeric catalysts and ion trapping/separation, and can provide polymers with a molecule m suitable for various uses. .

(Group Structure of the Invention) The present invention provides that the repeating unit is represented by the following formula (I), and 4
A polyether polymer having oligooxyethylene side chains characterized by a reduced viscosity of 0.01 or more as measured in a 0.1% benzene solution at 5°C.

1+CI+2-CI+-0)- However, in the above formula (I>), R is an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

A group selected from 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 detrahydropyranyl group, where n is 1 to 12
The number is the true number of repetitions of oxyethylene (degree of polymerization) determined by selecting the upper limit.
Or show the average number of repetitions.

The polyether polymer of the present invention can be obtained by polymerizing glycidyl ether of oligoethylene glycol represented by the following formula (I) in which one hydroxy group is protected by another group in the presence of a known ring-opening polymerization catalyst. Obtainable.

However, in the above formula (II), R and n are the above (I
>Same as R and n in the formula.

In addition, the compound of the above formula (n) can be prepared by combining an oligoethylene glycol heptanoether represented by the following formula (III) selected as necessary and epichlorohydrin under basic conditions such as caustic alkali in the presence of an onium salt or crown ether. It can be synthesized by the reaction described below.

IO+CH2-CH2-0HeR(III) However, in the above formula (I[I), R and n are the same as R and n in the formula (I>).

In the above general formulas (I) to (III), examples of when R is an alkyl group include methyl and ethyl.

Groups such as propyl, hexyl, octyl and dodecyl may be mentioned; examples of alkenyl groups include vinyl,
Examples include groups such as allyl. An example of a cycloalkyl group is cyclopropyl.

Examples of groups such as cyclohexyl and methylcyclohexyl, aryl groups include phenyl, tolyl, and naphthyl, and examples of aralkyl groups include benzyl and phenylethyl.

The ring-opening polymerization catalyst used in producing the polyether polymer of the present invention includes a catalyst system mainly composed of organoaluminum, a catalyst system mainly composed of organozinc, and a catalyst system based on tin-phosphate ester condensate. Generally known as high polymerization catalysts, organic tin-phosphoric acid ester condensate catalyst systems are particularly preferred from the viewpoint of polymerization rate and properties of the resulting polymer.

Examples of organoaluminum-based catalysts include trialkylaluminum-water-acetylacetone-based catalysts, and examples of organic dumbbell-based catalysts include, for example, diethylzinc-water-based catalysts. Further, as an organotin-phosphoric acid ester condensate catalyst, US Patent No. 3.
773.694@ Catalysts described in the specification may be mentioned, for example dibutyltin oxide-tributylphosphate-1-condensate.

The polymer of the present invention can be produced using the ring-opening polymerization catalyst (n>
It is obtained by reacting the glycidyl ether of oligoethylene glycol of the formula compound in the presence or absence of a solvent at 10 to 80°C, usually under stirring or shaking.

The amount of catalyst used is 0.000 mm per 100 mm of raw material.
A range of 0.01 to 1 to 4 parts is suitable. During the reaction, it is desirable to keep the water content of the reaction system as low as possible. The resulting polymer has various molecules M depending on the reaction conditions.

For example, various polymers can be obtained, such as low-molecular polymers that are soluble in ordinary solvents, and high-molecular weight polymers that have sufficient strength and are capable of forming films. In the present invention, polymers having a reduced viscosity measured in a 0.1% benzene solution at 45 DEG C. of o.oi or more, preferably o.oi to 3, particularly preferably 0.05 to 3 are suitable. These polymers can be used as solutions or molded products.
It can also be used for various purposes by blending it with other types of polymers.

(Example) Monomer synthesis example 1 Diethylene glycol 7-methyl ether 20g (1,
7X10-1 mol), epichlorohydrin 77 (1(8
, 3 x 10-1 mol) and triethylbenzylammonium chloride (1 (1,7 % caustic soda aqueous solution (2.0 x 10 -1 mol) was added dropwise over 30 minutes.After the addition was completed, the reaction was carried out at the same temperature for 7 hours.

After cooling, add 1 oz of cold water and extract with methylene chloride (io.

miX twice), dried over sodium sulfate, and purified by steam purification under reduced pressure to obtain 23 g (yield: 74%) of the target product, diethylene glycol glycidyl methyl ether.

The physical properties and NMR spectrum assignment of diethylene glycol glycidyl medyl ether (IIa) obtained by 1q are shown below.

nature bp 92℃/2mm1l.

n 91.4339 NMR spectrum assignment (na) Solvent CDα3. Internal standard TMS δ: 2.40-2.95 (2N, m, a) δ:
3.32 (3H, S, b) δ: 2.95~
3.80 (IIH, m, c) Seven mer synthesis example 2 Triethylene glycol glycidyl methyl ether (IIb> was obtained in the same manner as in Synthesis example 1 using 1-lyethylene glycol 7 methyl ether and epichlorohydrin. The physical properties and NMR spectrum assignments of - are as follows.

Properties bp 135°C/4mlllHg nl 1.444O NMR spectrum assignment (IIb) Solvent CDCJ13. Internal standard TMS δ: 2.40-2.95 (2H, m, a) δ: 3
．． 33 (3H, s, b) δ: 2.95-3.
BO (15H, m, c) Monomer Synthesis Example 3 Ethylene glycol glycidyl methyl ether (■C) was obtained in the same manner as in Synthesis Example 1 using ethylene glycol monomethyl ether and epichlorohydrin. The physical properties and NMR spectrum assignment of the monomer are as follows.

Properties bp 5B°G/5mm1IO n111.4228 NMR spectrum assignment (Ilc> Solvent CDCl3. Internal standard TMS δ: 2.40-2.90 (2H, m, a) δ: 3
．． 32 (3H, s, b) δ: 2.90-3.
85 (71-1, m, c) Seventhmer Synthesis Example 4 Ethylene glycol allyl glycidyl ether (■d) was obtained in the same manner as in Synthesis Example 1 using ethylene glycol monoallyl ether and epichlorohydrin. The physical properties and NMR spectrum assignments of the monomer are as follows.

Properties bp 79°C/5 mm 1 g nv 1.4412 NMR spectrum assignment (nd) Solvent CDCl3. Internal standard TMS δ: 2.40 to 2.90 (2H, m, a)
δ: 2.90-3.30 (1H, m, b) δ:
3.30-3.80 (6H, m, c) δ:
3.9B (2H, d, d)'δ: 4.90~
6.25 (3H, m, e) Monomer Synthesis Example 5 Ethylene glycol glycidyl phenyl ether (IIe> was obtained in the same manner as in Synthesis Example 1 using ethylene glycol monophenyl ether and ebichlor didolino. The physical properties and NMR spectrum assignments are as follows.

Properties mp 36.8°C bo 137°C/4mml1g n Dl, 5105 (IIe) Solvent CDα3. Internal group γS! TMSδ: 2.48
~2.90 (2H, m, a)+5:2.90~3
．． 35 (1!-l, m, b) δ: 3.35-4
．． 25 (6H, m, C) δ: 6.60-7.45
(5H, m, d>Septumer Synthesis Example 6 Ethylene glycol benzyl glycidyl ether (If) was obtained in the same manner as in Synthesis Example 1 using ethylene glycol monobenzyl ether and epichlorohydrin.The physical properties of the heptamer and The assignments of NMR spectra 1 to 1 are as follows.

Properties bp 140°C/3mm11g n11.5042 (IIf) Solvent CD (j! 3. Internal standard TMS δ: 2.45-2.85 (2t-(, m, a>δ:
2.90-3.30 (IH, m, b) δ: 3.30
~3.90 (6H, m, c) δ: 4.50
(21-(,S, d>δ near, 25 (5H,
s, e) Monomer Synthesis Example 7 Diethylene glycol glycidyl n-hexyl needle (
ffg) was obtained. The physical properties and NMR spectrum assignments of the monomer are as follows.

Properties bD 145°C/4 mml1 g np 1.4387 NMR spectrum assignment (■g> FJiCDc123. Internal standard TMS δ: 0.87 (3t-1, t, a) δ: 1
．． 08-1.85 (8f-(,m,b)δ:2.
40-2.85 (2H, rn, c) δ: 2.85
~3.90 (131-1, m, d) Monomer Synthesis Example 8 Diethylene glycol glycidyl tetrahydropyranyl ether (II Fl > was obtained in the same manner as in Synthesis Example 1 using diethylene glycol monotetrahydrofyranyl ether and epichlorohydrin.

The physical properties and NMR spectrum assignments of the monomer are as follows.

Properties bp 128℃/2mm11g 11.4584 (II rl) Dissolution a CD (1'3, internal standard TMSδ: 1.
30~1.80 (6 days, m, a) δ: 2.45~
2.90 (2)-1, m, b) δ: 2.90-4.
00 (13H, m, c) δ: 4.50-4.70
(IH, m, d) Seven-mer synthesis example 9 Oligoethylene glycol seven-methyl ether (f4n
381) and epichlorohydrin in the same manner as in Synthesis Example 1, under high vacuum (5xlO-4mmHg/
(180°C) to remove low-boiling substances to obtain oligoethylene glycol glycidyl methyl ether (IIi>).The molecular weight and NMR spectrum assignment of the monomer are as follows.

Average molecular weight by vapor pressure osmometry Rn 462 (n = 8.5> NMR spectrum assignment (IIi) δ: 2.40-2.92 (2H, m, a
) δ: 31', 34 (3H, s, b) δ:
2.92-3.85 (37)1. m, C) Monomer Synthesis Example 10 -Ethylene glycol decyl glycidyl ether (I[j
> obtained. The physical properties and NMR spectrum assignment of the heptamer are as follows.

Properties BP 160℃/1ml! 1gn1i' 1.
4428 NMR spectrum assignment (I[j) Dissolved aICD (j!3. Internal standard TMS δ:O,a9 (3H,t,a)δ:1.05
~1.60 (20H, m, b) δ:2.45~2
．． 90 (2H, m, c) δ: 2.90-3.30
(It-1, m, d>δ: 3.30-3.80
(8H, m, e) Seventhmer Synthesis Example 11 Diethylene glycol decyl glycidyl ether (IIk>) was obtained in the same manner as in Synthesis Example 1 using diethylene glycol monododecyl ether and epichlorohydrin. Physical properties and NMR spectrum of the seventhmer The attribution is as follows.

Properties bp 195℃/0.7mm1l (1nv:1.4
Attribution of 46O NMR spectrum (Ink> Solvent CDC! 13. Internal group QTMS δ: 0.89 (3)-1,t,
a>δ: 1.05 to 1.60 (20H, m, b)
δ: 2.45 to 2.90 (2H, m, c
) δ: 2.90 to 3.30 (1t-1, m, d)
δ: 3.30 to 3.80 (12H, m, e) Catalyst Production Example 1 12.50 g of dibutyltin oxide and 26.6 g of tributyl phosphate were placed in a three-turn flask equipped with a stirrer, a thermometer, and a distillation device. , while stirring under a nitrogen stream for 25 minutes.
The distillate was distilled off by heating at 0° C. for 20 minutes, leaving a solid condensation product (1) as a residue.

Catalyst Production Example 2 Using 10.50 tributyltin chloride and 17.4 liters of tributyl phosphate, the reaction conditions were 3 at 250°C.
A solid condensation product (2) was obtained in the same manner as in Production Example 1 except that the heating time was 0 minutes.

Example 1 The inside of an old 50d glass ampoule was replaced with nitrogen,
To this, 30 mg of condensation product (1) as a catalyst and 1 water
Diethylene glycol glycidyl medyl edel (na) 12 (It) adjusted to 0 ppm or less was charged, and after sealing the tube, the ampoule was reacted for 50 hours at 40°C while shaking. After the reaction, 100 d of benzene was added to the reaction product and dissolved. , 300 d of hexane was added and reprecipitated. This precipitate was taken out, washed with 100 d of hexane, and quickly dried to obtain 1 unit of 8.2 g of polyether polymer (yield 68%).
.

The glass transition temperature of this polymer is -72°C (PERKIN
EL) according to DSC-IB manufactured by tER). Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45° C. was 1.51. Also N
The assignment of the MR spectrum is shown below.

-+CH2-Cl1-0■C]12 Solvent CDα3. Internal standard TMS δ: 3.35 (31-1, S, a) δ:
3.20-3.90 (13H, m, b) The infrared absorption spectrum of this polymer is shown in FIG.

Example 2 Using a synthesis product (2>70 ma as a catalyst and 15 cl of triethylene glycol glycidyl methyl ether (nb) as a 7 mer, the polymerization conditions were 40 °C and 80 °C.
9.2 g of polyether polymer was obtained in the same manner as in Example 1 except for changing the time (yield: 61%).

The glass transition temperature of this polymer was -76°C.

Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45° C. was 0.23.

Further, the assignment of the NMR spectrum is shown below.

(Ctl2-Ctl OF ?HW CD CJl 3 , internal standard TMSδ: 3.
35 (31-1, s, a) δ: 3.10~
3.90 (17H, m, b) The infrared absorption spectrum of this polymer is shown in FIG.

Example 3 Condensation product (1) 30m ( ) as catalyst and ethylene glycol glycidyl methyl ether (
IIC) 15 (yield: 73%) was carried out in the same manner as in Example 1, except that 15 (7) was used and the polymerization conditions were changed to 40° C. for 24 hours.

The glass transition temperature of this polymer was -71°C.

Further, the reduced viscosity of this polymer measured with a 0.1% bempine solution at 45° C. was 1.76.

Further, the assignment of the NMR spectrum is shown below.

-1-C112-CH-O+- ■ CH2 1-1-1-1-2-period-2-notification L-〇-Starvation L ba Solvent CDCl3. Internal standard TMS δ: 3.35 (3H,s, a>δ: 3.3
0 to 3.80 (9H, m, b) The infrared absorption spectrum of this polymer is shown in FIG.

Example 4 Condensation product (1) 40m0 as catalyst and ethylene glycol allyl glycidyl ether (I
Id) Using 15(], the polymerization conditions were 30 at 50'C.
Polyether polymer 10.5CI was obtained in the same manner as in Example 1 except for changing the time (yield 70%).

The glass transition temperature of this polymer was -82°C.

Also, for this polymer, 0.1% at 45°C
The reduced viscosity measured in benzene solution was 1.53.

Further, the assignment of the NMR spectrum is shown below.

(C1-12-CH-O+- 0-CH-CH2-0-Tomori 1st term 2nd term, a
bc solvent CDCl13. Internal standard TMS δ: 3.25 to 3.85 (9t-1, m, a) δ
:3.96 (2H, d, b) δ: 4.90~
6.25 (3 days, m, c) The infrared absorption spectrum of this polymer is shown in FIG.

Example 5 Condensation products as catalysts (2>40 mo and ethylene glycol glycidyl phenyl ether as 7 mos)
IIe) 9.8 g of polyether polymer was obtained in the same manner as in Example 1, except that 15a was used and the polymerization conditions were changed to 60° C. for 18 hours (yield: 65%).

The glass transition temperature of this polymer was -15°C.

Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45° C. was 0.62.

Further, the assignment of the NMR spectrum is shown below.

-+clI2-C1l -0)- "Solvent CDCl13. Internal standard TMS δ: 3.25-4.25 (9 torr, m, a
) δ: 6.60 to 7.45 (5H, m,
b) The infrared absorption spectrum of this polymer is shown in FIG.

Example 6 Condensation product (2>30 mg and 10 g of ethylene glycol benzyl glycidyl ether (IIf) as catalyst
6.7 g of polyether polymer was obtained (yield: 67%) in the same manner as in Example 1, except that the polymerization conditions were 50° C. for 25 hours.

The glass transition temperature of this polymer was -16°C.

Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45° C. was 0.74.

Further, the assignment of the NMR spectrum is shown below.

-+cH2-Ctl -0+- Solvent CDα3. Internal standard TMS δ: 3.10 to 3.90 (9f-1, m, a) δ
:4.45 (2H, S, b) δ near, 23
(5H, s, c) The infrared absorption spectrum of this polymer is shown in FIG.

Example 7 Condensation product (1) 60m0 and diethylene glycol glycidyl-n-hexyl ether (IIc
8.9 g of a polyether polymer was obtained in the same manner as in Example 1, except that h>15 (J was used and the polymerization conditions were changed to 60° C. for 70 hours (yield: 59%).

The glass transition temperature of this polymer was -84°C.

Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45° C. was 0.15.

Further, the assignment of the NMR spectrum is shown below.

and solvent CDCl13. Internal standard TMS δ: 0.8B (3H, t, a
) δ: 1.10 to 1.80 (8H, m, b) δ:
3.20-3.90 (15H, m, c) The infrared absorption spectrum of this polymer is shown in FIG.

Example 8 Condensation product (1) 25ma and diethylene glycol glycidyl tetrapyranyl ether (IIh) as catalysts
) 6a was used, and 3.8 g of polyether polymer was prepared in the same manner as in Example 1, except that the polymerization conditions were changed to 40°C for 50 hours.
was obtained (yield 63%).

The glass transition point of this polymer was -50°C.

Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45° C. was 0.19.

Further, the assignment of the NMR spectrum is shown below.

b Dissolved CDCl23. Internal IQ-TMSδ: 1.25~
1.85 (61-1, m, a) δ: 3.20-4
．． 10 (15H, m, b) δ: 4.40-4.7
5 (1H, m, C) The infrared absorption spectrum 1H of this polymer is shown in FIG.

Example 9 Condensation product (1) 60m (] and oligoethylene glycol (n=8.5) glycidyl methyl ether (IIi>10o) were used as catalysts, and the polymerization conditions were 60°C and 12°C.
5.5 g of polyether polymer was obtained in the same manner as in Example 1 except that the time was 0 hours (yield: 55%).

The glass transition temperature of this polymer was -69°C.

Further, the reduced viscosity of this polymer measured in a 0.11% benzene solution at 45° C. was 0.08.

Further, the assignment of the NMR spectrum is shown below.

-+Cl12-Ctlo)-C(12 0→C1l -C112-0 from the filtrate a Solvent CDα3. Internal standard TMS δ: 3.35 (31-1, s, a) δ: 3
．． 10-3.90 (39H, m, b) The infrared absorption spectrum of this polymer is shown in FIG.

Example 10 Condensation product (2>50 mq and ethylene glycol decyl glycidyl ether (I[j>15 g
11.2 g of a polyether polymer was obtained in the same manner as in Example 1, except that the polymerization conditions were 35° C. for 15 hours (yield: 75%).

The glass transition point of this polymer was 95°C or lower. Further, the reduced viscosity of this polymer measured in a 0.1% benzene solution at 45°C was 0.82. Further, the assignment of the NMR spectrum is shown below.

-Ct12-Ctl-Oh Solvent CDα3. Internal standard TMS δ: 0.89 (3) 7t, a) δ: 1.05
~1.60 (201-i, m, b) δ: 3.2
0 to 3.75 (11f-(, m, c)) The infrared absorption spectrum of this polymer is shown in FIG.

Example 11 50 mg of condensation product (2) and 15 g of diethylene glycol decyl glycidyl ether (nk) as catalyst
Polyether polymer 10.0 (yield 67%) was obtained in the same manner as in Example 1 except that the polymerization conditions were 35° C. for 25 hours.

The glass transition point of this polymer was required to be below 95°C. Also, for this polymer, d′3 at 45°C is 0.1
The reduced viscosity measured in % Benvin solution was 0.22-Q. Further, the assignment of the NMR spectrum is shown below.

+CH2-C)I-0)- Solvent CDα3. Internal standard TMS δ: 0.89 (3H, t, a
>δ: 1.05 to 1.60 (201-(, m, b
) δ: 3.20 to 3.75 (151-1, m, C
) The infrared absorption spectrum of this polymer is shown in FIG.

(Effect of the invention) The polyether polymer of the present invention is a polymeric catalyst.

Polymers that are useful as ion-conducting materials, polymers that have functions such as capturing and separating ions, or intermediates that can provide materials with such functions, and are especially necessary when used as polymeric ion conductors. It is a new polymer that has a low glass transition point and a high boj-note density, and is expected to have unprecedented electrical conductivity.

[Brief explanation of the drawing]

1 to 11 are infrared absorption spectra of polyether polymers obtained in Examples 1 to 11, respectively.

Claims (1)

[Claims] The repeating unit is represented by the following formula (I), and the reduced viscosity measured with a 0.1% benzene solution at 45°C is 0.0.
A polyether polymer having one or more oligooxyethylene side chains. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, in the above formula (I), R is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyl group having 3 to 8 carbon atoms.
The group is selected from a cycloalkyl group having 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.