JPS643222B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyether resins with increased molecular weight. More specifically, the alkali metal bisphenols represented by the following general formula MO-Ar-OM' (where M and M' are an alkaline earth metal or an alkaline earth metal, and Ar is a divalent aromatic group) salt _or alkaline earth metal salt, and the following general formula ₂
-(Ar' is a group selected from divalent aromatic groups)] A polyether polymer obtained by reacting with a dihalide represented by -(O-Ar-O-R
The present invention relates to a method for further increasing the molecular weight by adding a specific compound in the production of -). The present inventors have already discovered and proposed that the above polyether polymer can be easily produced by applying a phase transfer reaction. Conventionally, it has been known to synthesize polyethers by reacting alkali metal salts of phenols with halides. However, anhydrous conditions are required in this case, and the reaction must also be carried out in a high boiling aprotic polar solvent such as dimethylformamide. Therefore, it takes time to isolate and purify the polymer after the reaction. That is, it is necessary to remove the salt produced as a by-product, which, together with the problem of recovering the aprotic polar solvent with a high boiling point, has disadvantages such as reduced productivity and increased costs. In the present invention, a phase transfer reaction is used, but since water is used as one of the reaction solvents, not only is an operation for removing by-product salts unnecessary, but also halogenated hydrocarbons and aromatic Cheap, low-boiling solvents such as hydrocarbons can be used. Furthermore, when a suitable solvent such as xylene or toluene is used, the polymer can be precipitated from the reaction system, which has the advantage of making purification very easy. The above-mentioned bisphenols and dihalogen compounds are used in substantially equimolar amounts, but as the reaction progresses, the degree of polymerization increases close to saturation, and if a higher molecular weight is desired, a very long time is required. The present inventors have found that in such cases, the degree of polymerization can be easily increased by adding a specific halide or alkali metal salt of bisphenols to the system in an amount of 1 to 100 mol% of the total monomer amount as a second step. They discovered that the polymerization time could be shortened, leading to the present invention. This far exceeds conventional expectations and provides advantages for industrial production. The metal salt of bisphenols used in the present invention is represented by the general formula MO--Ar--OM' (wherein M and M' are alkali metals and Ar is a divalent aromatic group). Specific examples of preferred bisphenols are:

[Formula] (wherein, X is -C(CH ₃ ) ₂ -, -SO ₂ -, -CH ₂ -O
-, -S-) and resorcinol, hydroquinone, 4,4'-
Dihydroxydiphenyl and the like. Depending on the purpose, these compounds may have a halogen atom such as chlorine or bromine, a hydrocarbon group such as a methyl group or an ethyl group, or a substituent such as an alkoxy group in the aromatic nucleus. The above bisphenols may be used alone or as a mixture. Furthermore, it is also possible to use trifunctional or higher functional phenols in place of some of the bifunctional phenols. On the other hand, the dihalogen compound used in the present invention has the general formula X-R-Y (wherein X, Y are halogen atoms, R
is a divalent hydrocarbon group or a substituted hydrocarbon group or -
It is represented by a group selected from CH ₂ —Ar′—CH ₂ —(Ar′ is a divalent aromatic group). To give a preferable specific example, carbon number is 1
dihalides with ~10 saturated hydrocarbon groups, and the general formula, (In the formula, X, Y are halogen atoms, R' is carbon number 1
~4 alkyl group or alkoxy group or halogen atom, n is an integer from 0 to 4). More specifically, methylene chloride, methylene bromide, bromochloromethane, ethylene chloride, ethylene bromide, bromochloroethane, trimethylene chloride, trimethylene bromide, bromochloropropane, tetramethylene chloride, tetramethylene bromide, bromochloromethane, Lubutane, pentamethylene chloride, pentamethylene bromide, bromochlorpentane, hexamethylene chloride, hexamethylene bromide, and o-,
Examples include m-,p-xylylene dichloride and dibromide, bis(chloromethyl)xylene, bis(chloromethyl)durene, and the like. The bisphenols and the dihalogen compound are used in substantially equimolar amounts. It is effective and convenient to use bisphenols by dissolving them in excess caustic soda or caustic potassium aqueous solution. In the present invention, a specific halide-containing compound or alkali metal salt of bisphenols is further added to the above reaction system. As the halide-containing compound, all compounds that can react under the polymerization conditions (so-called active halides) can be used. For example, it may be selected from the monomers that can be used at the start of the reaction; acid dichlorides such as terephthalic acid chloride and sebacic acid dichloride; halohydrins such as epibromohydrin; chloroform;
You can also choose from haloforms such as bromeform. More preferred specific examples include dichloromethane, dibromomethane, bromochloromethane,
Examples include epichlorohydrin, epibromohydrin, chloroform, and bromoform. The bisphenols can be selected from the monomers HO--Ar--OH that can be used at the start of the reaction. Preferably, the following general formula,

[Formula] (wherein, X is -C(CH ₃ ) ₂ -, -SO ₂ -, -
CH ₂ -, -O-, -S-) and resorcinol, hydroquinone, 4,
Selected from 4'-dihydroxydiphenyl, etc. Of course, these aromatic nuclei include halogen atoms such as chlorine and bromine, hydrocarbon groups such as methyl and ethyl groups,
Alternatively, it may have a substituent such as an alkoxy group. Similarly, it is convenient and effective to use the bisphenols to be added as a caustic soda or caustic potassium aqueous solution. The amount of these additives used is in the range of 1 to 100 mol% of the total amount of monomers at the beginning. Although the timing of addition can be arbitrarily adjusted after the start of polymerization, it is preferable to add it after the first stage of polymerization has substantially completed, for example, when the polymerization conversion rate is 90% or more. The present inventors' study results show that when comparing the effects of active halides and bisphenols, for example, bisphenols and 3,
In the case of 6-bischloromethyldurene, it was found that even if the latter was used in a smaller amount, the molecular weight could be sufficiently increased. It is more convenient to carry out the polymerization reaction described above using an organic solvent. Halogenated hydrocarbons such as methylene chloride, chlorobenzene, and orthodichlorobenzene; aromatic hydrocarbons such as toluene and xylene; all those that are immiscible with water and do not react with alkali metal salts of phenols. Available for use. As the catalyst used in the present invention, any known phase transfer catalyst can be used. Examples of quaternary ammonium salts include tetrabutylammonium bromide,
Trioctylmethylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, N-laurylpyridinium chloride, etc. Quaternary phosphonium salts include tetrabutylphosphonium bromide, triethyloctadecylphosphonium bromide, and the like. The amount used is selected from the range of 0.1 to 20 mol%, more preferably 1 to 10 mol%, based on the dihalide. Polymerization reactions using these phase transfer catalysts are usually 0
It can be carried out at any temperature from °C to 100 °C. The polymer thus obtained has excellent thermal properties and has a wide range of uses as molded products such as films and sheets. Hereinafter, the present invention will be illustrated by typical examples, but the present invention is not limited only to these examples. Example 1 p-xylylene dichloride under nitrogen stream
Dissolve 10 mmol in 30 ml of chlorobenzene and 0.3 mmol of trioctylmethylammonium chloride.
Add. 10 mmol of bisphenol A was dissolved in 30 ml of 1N aqueous sodium hydroxide solution, added to the above solution, and reacted at 80°C for 3 hours, then at 100°C for 3 hours. 5.7 mmol of methylene bromide as an active halide was added to this reaction system, and the reaction was continued for an additional hour. When the system was cooled to room temperature, a polyether polymer precipitated. The polymer is separated by filtration, washed with methanol-hydrochloric acid followed by water and dried. Intrinsic viscosity of polymer [η] (32℃
Table 1 shows the results for dimethylacetamide (in dimethylacetamide).
Shown below.

[Table] *Values relative to the total monomer amount at the start of the reaction Clearly, methylene bromide is effective in increasing the degree of polymerization. Examples 2, 3, and 4 Methylene chloride, chloroform, and epibromohydrin were used in place of methylene bromide in Example 1, respectively. The results are shown in Table 2. Similarly, it can be seen that it is effective in increasing molecular weight.

[Table] Example 5 In Example 1, the reaction was carried out by changing the solvent to o-dichlorobenzene. Specific viscosity η _sp (1.0g/
dl, 32°C, in dimethylacetamide) over time is shown in Figure 1. 8.8 hours after the start of the reaction, CH ₂ Br ₂
Add 28.5 mol% of the starting monomer amount, and then add approx.
After 40 minutes, 28.5 mol% (57% total) was added. From the figure, it can be seen that when methylene bromide is not added, the degree of polymerization hardly increases after 8.8 hours from the start, but the degree of polymerization clearly increases with the addition of methylene bromide. Example 6 Under a nitrogen atmosphere, 10 mmol of 3,6-bischloromethyldurene is dissolved in 50 ml of o-dichlorobenzene, and 0.37 mmol of trioctylmethylammonium chloride is added. Bisphenol S (4,
7 mmol of 4'-dihydroxydiphenyl) and 3 mmol of bisphenol A were dissolved in 50 ml of a 1.5N aqueous sodium hydroxide solution, added to the above solution, and reacted at 95°C for 4 hours. In this reaction system, bisphenol
1 mmol of A (5 mol % of the total monomer amount at the beginning) was dissolved in a small amount of aqueous caustic soda solution and added. Figure 2 shows the change in intrinsic viscosity [η] (32°C, in o-dichlorobenzene) over time. As is clear from the figure, the increase in molecular weight is significantly large. In addition, Examples 1 to 5
It can be seen that the effect is greater than that of active halides. The polyether polymer thus produced had a melting point of 260-270°C and a glass transition point of 142°C by DSC. The yield of polymer was 96%. Example 7 The same procedure as Example 6 was carried out. However, the bisphenol was added after 10 hours. The results are shown in Figure 2.
It can be seen that the effect of increasing the molecular weight is remarkable. Example 8 Bisphenol S8m mol and bisphenol
The same procedure as in Example 6 was carried out except that 2 mmol of A was used. A similar increase in molecular weight was observed, and [η] after the jump was 0.68 (at 32°C

[Formula]/1,1,2,2-tetrachloroethane=1/1). The melting point of this polyether polymer is 285-300℃,
The glass transition point determined by DSC was 170°C. The yield of polymer was 98%.

[Brief explanation of drawings]

Figure 1 shows the effect of adding CH ₂ Br ₂ to the polymerization system (Example 5), and Figure 2 shows the effect of adding bisphenols (Examples 6 and 7) to the polymerization system of the present invention. It is a graph showing a change in viscosity [η] or specific viscosity η _sp over time.

Claims (1)

[Claims] 1. In producing the polyether polymer represented by the general formula -(O-Ar-O-R-), the general formula MO-Ar-OM' (where M and M' are alkali alkali metal salt or alkaline earth metal salt of bisphenols represented by a metal or alkaline earth metal (Ar is a divalent aromatic group) and the general formula X-R-Y (wherein, X, Y are halogen atom, R is a divalent hydrocarbon group or substituted hydrocarbon group, or -CH ₂ -
A polyfunctional halide represented by Ar′—CH ₂ —(Ar′ is a divalent aromatic group) is mixed with water and a water-insoluble organic solvent in the presence of a phase transfer catalyst. A high molecular weight polymer that increases the molecular weight of the polyether polymer by reacting the polymer with 1 to 100 mol% of the total monomer amount of a halogen-containing compound or an alkali metal salt of bisphenols to the polymerization system. Method for producing polyether. 2. The method for producing polyether according to claim 1, wherein bisphenols are used as an aqueous solution of caustic soda or caustic potassium. 3 The polyfunctional halide has the general formula (In the formula, X, Y are halogen atoms, R' is an alkyl group or alkoxy group having 1 to 4 carbon atoms, or a halogen atom, n is an integer from 0 to 4) and X-R''-Y (in the formula, X, The method for producing a polyether according to claim 1 or 2, wherein Y is a halogen atom and R'' is at least one compound selected from a hydrocarbon group having 1 to 10 carbon atoms or a substituted hydrocarbon group. . 4. The method for producing polyether according to claim 1, 2, or 3, wherein the halogen-containing compound added is a compound selected from methylene chloride, methylene bromide, bromochloromethane, and mixtures thereof. . 5. The method for producing polyether according to claim 1, 2 or 3, wherein the halogen-containing compound added is a compound selected from haloforms and mixtures thereof. 6. The method for producing polyether according to claim 1, 2 or 3, wherein the halogen-containing compound added is a compound selected from halohydrins and mixtures thereof. 7 The alkali metal salt of bisphenols to be added has the general formula (In the formula, M, M' are alkali metals, X is -C
(CH ₃ ) ₂ ―, ―SO ₂ ―, ―CH ₂ ―, ―O―, ―S
--), and resorcinol, hydroquinone, 4,
Claim 1, which is at least one compound selected from 4′-dihydroxydiphenyl;
The method for producing polyether according to item 2 or 3. 8. The method for producing polyether according to claim 1, wherein the phase transfer catalyst is a quaternary ammonium salt. 9. The method for producing polyether according to claim 1, wherein the phase transfer catalyst is a quaternary phosphonium salt.