JPS62240320A - Production of polyether - Google Patents

Abstract

PURPOSE:To obtain a high-molecular weight polyether at low cost. useful for rubber materials, polymer plasticizers, polymer modifiers, etc., by reaction between alkali metal alcoholate of polyalkylene ether polyol with specific molecular weight and polyfunctional halogen compound. CONSTITUTION:The objective polyether with a molecular weight 20,000-1,000,000 can be obtained by reaction, pref. at 60-130 deg.C, between (A) alkali metal alcoholate of polyalkylene ether polyol (pref polyoxyethylene and/or oxypropylene polyol) with a molecular weight >=200, pref. 1,000-3,000 and (B) polyfunctional halogen compound (pref. methylene dihalide) in a molar ratio pref. >=1/3 in the presence of, if needed, (C) a catalyst (pref. interphase transfer type catalyst).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing high molecular weight polyether.

[Prior Art] Polyalkylene ether polyols are usually produced by adding alkylene oxide to an active hydrogen atom-containing compound in the presence of an alkaline catalyst, and the crude polypropylene glycol obtained using such a catalyst is It is known to produce polypropylene glycol having a molecular weight of 500 to 10,000 by reacting equimolar amounts of polyfunctional halogen compounds.

[Object of the invention] The object of the present invention is to provide a method for producing polyethers having a significantly higher molecular weight than conventional ones.

[Structure of the Invention] The present invention comprises: an alkali metal alcoholate (a) of a polyalkylene ether polyol having a molecular weight of at least 200 and a polyfunctional halogen compound (b).

1 reaction in the presence of catalyst (c) if necessary to 20,000 to 1
This is a method for producing a high molecular weight polyether, characterized by producing a polyether having a molecular weight of 1,000,000.

The raw material polyalkylene ether polyol (a) used as a starting material in the present invention includes polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids,
Compounds with a structure in which alkylene oxide is added to a polyfunctional compound containing an active hydrogen atom such as phosphoric acid, and these two
Examples include mixtures of more than one species.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1
, 4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, bis(
Dihydric alcohols such as hydroxymethyl)cyclohexane and bis(hydroxyethyl)benzene; glycerin,
Trimethylolpropane, pentaerythritol, diglycerin, alpha-methyl glucoside, sorbitol, xylit.

Tri- to octavalent polyhydric alcohols such as mannitol, dipentaerythritol, glucose, fructose, and sucrose; Examples of amines include ammonia, C1-C20 alkylamines (butylamine, etc.), monoamines such as anilino; ethylenediamine , aliphatic polyamines such as trimethylene diamine, hexamethylene diamine, and diethylene triamine; piperazine, N-aminoethyl piperazine, and other heterocyclic polyamines described in Japanese Patent Publication No. 55-21044; alicyclic polyamines such as dicyclohexylmethane diamine and isophorone diamine; Formula polyamines: Aromatic polyamines such as phenylene diamine, tolylene diamine, diethyl tolylene diamine, xylylene diamine, diphenylmethane diamine, diphenyl ether diamine, polyphenylmethane polyamine: and monoethanolamine, jetanolamine, triethanolamine, triisopropylene Alkanolamines such as patoolamine; polyhydric phenols include pyrogallol,
Polyhydric phenols such as hydroquinone, bisphenols such as bisphenol A; and polycarboxylic acids such as aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid. can be given.

Two or more kinds of the above-mentioned active hydrogen atom-containing compounds can also be used.

Examples of the alkylene oxide added to the active hydrogen atom-containing compound include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1
．． Examples include 2-, 2.3-, 1.3-butylene oxide, styrene oxide, and epichlorohydrin. Alkylene oxides may be used alone or in combination of two or more types, and in the case of review, block addition (chip type, balanced type, active secondary type, etc.), random addition, or a mixture of both [after random addition, chip type, etc.] It has 0 to 50 wt% (5 to 40 wt%) ethylene oxide chains arbitrarily distributed in the molecule, and 0 to 30 wt% (5 to 25 wt%) ethylene oxide chains are chipped at the end of the molecule. [object] may also be used. Among these alkylene oxides, preferred are EO alone, PO alone, PO and E
A combination of O (random, block, and a mixture of both). The addition of alkylene oxide can be carried out in the usual manner, either without catalyst or in the presence of a catalyst (alkaline catalyst, amine catalyst, acidic catalyst) (particularly in the latter stages of alkylene oxide addition) at normal pressure or under pressure. under pressure 1
It is done in stages or in multiple stages.

The polyalkylene ether polyol thus obtained may be used as it is (crude polyether polyol), or a purified product from which the catalyst has been removed by a conventional method may be used.

Further, the polyalkylene ether polyol may be reacted with a small proportion of polyisocyanate (listed below) to further increase the molecular weight (polyether/polyisocyanate equivalent ratio: preferably 1.2 to 10/1, for example). is 1.5 to 2/1).

The molecular weight of polyalkylene ether polyol is usually 20
0 to 20,000, preferably SOO to 10,000, more preferably 1,000 to 3,000. The weight (molecular weight per hydroxyl group) of the polyalkylene ether polyol is usually 100 to 10,000, preferably 250 to 5,
000, more preferably 500 to 1,500. The functionality of the polyalkylene ether polyol is usually 2 to 8, preferably 2 to 3, particularly preferably 2. The degree of unsaturation of the polyalkylene ether polyol is preferably as low as possible, usually 0.1 or less, preferably 0.05 or less, more preferably 0.02 meq/g. In addition, the primary hydroxyl group content of polyether polyol is usually O~100.
% preferably 30-100% more preferably 50-10
0%, most preferably 70-100%.

Polyalkylene ether polyol has its terminal water r!
At least a portion of the i group is converted into a metal alcoholate group and subjected to reaction with a polyfunctional halogen compound.

The method of alcoholation is not particularly limited, and examples include: ■ reaction with caustic alkali (NaOH, KOH, etc.); ■ metal alcoholate of lower alcohol (ct13ON);
(a, CH30, etc.), (2) a method of reacting with an alkali metal (Na, etc.), (2) a method of reacting with a metal hydride (Nap, Kll, etc.), and a combination of two or more of these methods. There are several methods. Among these, (1), (2), and (2) Zaraani (especially the method using Na0tl) are preferred. In the method (2), it is preferable to use an excess of caustic alkali, and the amount used is usually 1.5 mol or more, preferably 2 mol or more, and most preferably 3 to 20 mol, most preferably 4 to 10 mol, per vL of water. It is a mole. In the methods ① to ③, the amount of alcoholating agent used is usually 0.8 to 2 mol per hydroxyl group, preferably 0.95 mol.
~1.2 mol. The alcoholation reaction is usually O~1
It can be carried out at any temperature from 80'C, preferably from 30 to 150'C.

In the present invention, the polyalkylene ether polyol is reacted with the metal alcoholate (a). Examples of the polyfunctional halogen compound (b) include the following.

(1) Polyhalogenated hydrocarbons: (1) Saturated or unsaturated polyhalogenated aliphatic hydrocarbons such as methylene chloride, methylene bromide, methylene fluoride.

Methylene iodide, monochloroheptanobromomethane.

Chloroform, carbon tetrachloride, trichloromonofluoromethane, trichloroethane, tetrachloroethane, 1,
1-dichloroethane, 1,2-dichloroethane, 1,1
-dichloroethylene, 1,2-dichloroethylene, 1,
2-dibromoethylene, 1,2-dichloropropane, 1
, 4-dichlorobutane, 1,4-dibromobutane, 1.
6-dichlorohexane, 1,1-dichloro-2,2-dimethylpropane, di(bromomethyl)methane, trichlorethylene, tetrachlorethylene, 1,2-dichloroethylene, 1,2-dibromoethylene, 3.4
-dichloro-1-butene; (11) aromatic ring-containing polyhalogenated hydrocarbons such as benzal chloride, benzal bromide, bis(chloromethyl)benzene (o-, m- and p-
-xylylene dichloride], bis(bromomethyl)benzene.

Tris(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, dichlorodiphenylmethane, bis(chloromethyl)naphthalene.

Bis(dichloromethyl)benzene, 1,3-dimethyl-
4,6-di(chloromethyl)benzene, etc.

(2) Multi-halogenated ethers: (i>multi-halogenated aliphatic ethers such as bis(chloromethyl)ether, bis(chloromethyl)thioether, 2,2°-dichloroethyl ether, 1,2-bis(2 -chloroethoxy)ethane: (drunk) polyhalogenated aromatic ethers e.g. 4.4-
Bis(chloromethyl)diphenyl ether; (iii) polyhalogenated aromatic aliphatic ethers such as bis(chloromethoxy)benzene, tris(chloromethoxy)benzene, etc.

(3) Polyhalogenated ketones: (1) Polyhalogenated aliphatic ketones such as bis(chloromethyl)ketone: (11) Polyhalogenated aromatic ketones such as 4.4゛-bis(chloromethyl)diphenyl ketone ;(iii)
Polyhalogenated araliphatic ketones such as bis(chloroethoxy)benzene, tris(chloromethoxy)benzene, etc.

(4) Polyhalogenated alcohols: e.g. trichloromethanol, 1,3-dichloro-2
-Propertool, bis(chloromethyl)formal, etc.

(5) Acid halide (acid chloride, etc.): For example, dichloroacetyl chloride, terephthaloyl chloride, etc.

(6) Other polyfunctional halogen compounds: for example, cyanuric chloride, dichloromaleic anhydride, phosgene, etc.

These may be used alone or in combination of two or more.

Among these, polyhalogenated hydrocarbons and polyhalogenated ethers are preferred, and polyhalogenated aliphatic hydrocarbons [especially methylene dihalides (methylene chloride, methylene bromide, methylene fluoride, methylene iodide, monochloromonobromomethane)],
Methylene chloride is most preferred.

According to the invention, a metal alcoholate (a) and a polyfunctional halogen compound (b) of a polyalkylene ether polyol are combined.
), the amount of (b) used is (a) 1
Per mole, usually 3 moles or more, preferably 6 moles or more, roughly preferably 8 to 200 moles, most preferably 10 to 100 moles
It is a mole.

The reaction between (a) and (b) can be carried out in the presence of a catalyst (c) and/or a solvent, if necessary.

As (c), a phase transfer catalyst can be used.

As the phase transfer catalyst, there are known ones: for example, JP-A-57
-156475@Those described in the publication [quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, macrocyclic ethers, etc.] can be used; representative examples include tetrabutylammonium bromide, trioctyl Oil-soluble liquids such as methylammonium chloride and benzyltriethylammonium chloride
grade ammonium salt, tetraphenylphosphonium chloride.

Examples include quaternary phosphonium salts such as tritetraphenylmethylphosphonium chloride.

The amount of (c) used is usually 0.1 to 20 mol%, preferably 1 to 10 mol%, based on (a).

As the solvent, an inert solvent having no active hydrogen atoms is preferable. Examples of such solvents include ethers (diethyl ether, dioxane, tetrahydrofuran, etc.), aliphatic, aromatic or alicyclic hydrocarbons (n-hexane, benzene, toluene, xylene, cyclohexane, etc.), halogenated hydrocarbons ( Methyl chloride, methyl bromide,
methyl iodide, etc.).

The reaction between (a) and (b) is continued until a polyether having a molecular weight of 20,000 to 1,000,000 (preferably 30,000 to 500,000, particularly preferably 50,000 to 300,000) is obtained. This is done until viscosity is reached. Adjustment of molecular weight is
This can be carried out by changing the reaction molar ratio of (a) and (b), and the larger the molar ratio of (b)/(a), the easier it is to obtain a polyether with a larger molecular weight.

The reaction product of (a) and (b) is produced by a conventional method.
salts), catalysts, and solvents can be removed and purified.

The high molecular weight polyether obtained by the present invention can be used as a paper processing agent without any rubber components or polymer plasticizers.

Can be used as a fiber treatment agent and polyurethane raw material;
After introducing an olefinically unsaturated group at the end.

Hydrolyzable silicon functional groups (
A polyether having a hydrolyzable silyl group can also be used, and furthermore, the terminal can be aminated by a known method to convert it into a polyether polyamine. The high molecular weight polyether obtained by the method of the present invention is also a useful material for applications such as sealants, caulking materials, paints, adhesives, and epoxy curing agents.

Furthermore, the polyether obtained by the present invention can be reacted with a polyisocyanate having a low ratio of 1 to 1 to produce a urethanized polyether having a higher molecular weight (equivalent ratio of polyether/polyisocyanate of 1 to 1: For example 1
~10/1, preferably 1.2-2/1).

When using the polyether obtained by the present invention for producing a polyurethane raw material or urethanized polyether, the polyisocyanate to be used has a carbon number (NGO
Aromatic polyisocyanates having 6 to 20 carbon atoms (excluding the carbon in the group) (e.g. tolylene diisocyanate, diphenylmethane diisocyanate, etc.), aliphatic polyisocyanates having 2 to 18 carbon atoms (e.g. hexamethylene diisocyanate, etc.), 4 to 15 carbon atoms alicyclic polyisocyanates (such as isophorone diisocyanate), aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms (such as xylylene diisocyanate), and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, etc.). modified products containing groups, biuret groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups, etc.) and patent applications 1982-1991.
Polyisocyanates other than those described in No. 60 can be used. Among these, commercially readily available polyinsyanates such as 2,4- and 2,6-T
DI and mixtures of these isomers.

Crude TD1.4,4°- and 2.4'-MD I and mixtures of these isomers, polyarylene polyisocyanate (PAPI>, also called crude MDI), and urethane groups and carbodiimide groups derived from these polyisocyanates. , allophanate groups, urea groups, biuret groups, and polyisocyanurate groups are preferred.

In addition, when producing polyurethane, if necessary, for example, known blowing agents (for example, methylene chloride, monofluorotrichloromethane, water, etc.) described in Japanese Patent Application No. 199160, known catalysts (for example, triethylenediamine, etc.) may be used. Tertiary amines (metal catalysts such as tin octylate, dibutyltin dilaurate, lead octylate, etc.) can be used.

The amount of blowing agent used depends on the desired density of the polyurethane (e.g. 0
．． 01-1.49/cm>, and the catalyst can vary, e.g.
It is used with a raw content of ~5%. Other additives that can be used in polyurethane production include emulsifiers and surfactants as foam stabilizers, with polysiloxane-polyoxyalkylene copolymers being particularly important.

Other additives that can be used as necessary during polyurethane production include flame retardants, reaction retardants, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides, and carbon black, oxidizers, etc. Known additives include zinc, calcium oxide, lead dioxide, titanium oxide, diatomaceous earth, glass fiber and its crushed products (cut glass, milled glass, glass flakes, etc.), talc, mica, and other fillers.

In the present invention, when the polyether (q) is used for producing polyurethane, the isocyanate index is usually 65 to 12.
0 (preferably 75-110, particularly preferably 85-10
5). Furthermore, polyin cyanurate is introduced into the polyurethane by increasing the isocyanate index significantly higher than the above range (polyisocyanate 1-index 300 to 1,000).
) is also possible.

Polyurethane can be produced by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method. Various types of unfoamed or foamed polyurethanes can be produced in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using low or high pressure mechanical equipment. Furthermore, polyurethane can also be produced by removing gas such as dissolved air in the raw materials or air mixed during mixing by a vacuum method before and after mixing the raw materials (especially before mixing the raw materials).

The polyether obtained in the present invention is particularly produced by non-foaming or low foaming (density 0.8-1) by the RIM (reaction injection molding) method.
．． RI of 4g/cm, especially 0.95-1.49/cd)
It is useful for producing M-molded polyurethane elastomer (hereinafter referred to as RIM urethane). Molding by the RIM method can be carried out under the same conditions as conventional methods.

For example, raw materials whose temperature is usually controlled at 25-90'C (2-4
components) at a pressure of 100 to 200 Kg/cIIiG, and preheated at 30 to 200'C (preferably 60 to
This can be carried out by pouring into a mold whose temperature is controlled to 90° C. and then removing the mold within 0.1 to 5 minutes. The molded product that is released after demolding can be made into a product as it is, but it is desirable to further perform annealing (after-curing) to make it into a product. In this case, the annealing conditions are usually 60 to 180'C x 0.3 to 100 hours, preferably 80 to 100 to 150C x 0.3 to 100 hours, particularly preferably 120 to 140'C x 1 to 30 hours.

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. The composition of the raw materials used in the Examples and Comparative Examples is as follows. Note that part and % represent @mouth part and mold opening %, respectively.

(1) PP-2000: Polypropylene glycol with a molecular weight of approximately 2,000 obtained by reacting 76 parts of propylene glycol with 2,000 parts of PO in the presence of a KO+1 catalyst (
Hydroxyl value 55.2 mgKOH/g, degree of unsaturation 0.01
6 meq/g).

(2) Polyethylene glycol with a molecular weight of approximately 3,000 obtained by reacting 106 parts of PE-3000 diethylene glycol with 3,000 parts of EO in the presence of a Na011 catalyst (hydroxyl value: 36.9 mgKOIl/(), degree of unsaturation) 0
．． 002 meq/g).

(3) PEP-1500: Polyethylene propylene glycol with a molecular weight of about 1,500 (hydroxyl value 73.4 mg) obtained by reacting a mixture of 750 parts of EO/750 parts of PO with 76 parts of propylene glycol in the presence of a KOH catalyst.
KOH/(J, degree of unsaturation o, oo9 meq/g).

(4) Liquid caustic soda: 48% Na011 aqueous solution.

(5) Solid caustic soda: 98.5% pure NaOH0 (
6) TOHAC: trioctylmethylammonium chloride.

Example 1 PP-20002,0 was placed in a reaction vessel equipped with a dropping device, a continuous flow cooling device, a gas introduction tube, a temperature recorder, and a stirring device.
00 parts of liquid caustic soda and 600 parts of liquid caustic soda were charged, the temperature was gradually raised while stirring, and dehydration was carried out under reduced pressure at a temperature of 80 to 150'C to distill out about 160 parts of water.

Next, after cooling to 120'C, 700 parts of methylene chloride was added dropwise over about 2 hours, and aging was carried out at about 80C for 20 hours. Thereafter, unreacted methylene chloride was removed by a conventional method. Further, the obtained crude product was washed with water in a toluene-water system to remove caustic soda and common salt, and then roughly purified by removing volatile components under reduced pressure.

In this way, approximately 1,000 parts (90% yield) of a slightly yellowish, very viscous polyether was obtained.

The hydroxyl value of this polyether is 21110KOH
/lll, viscosity (25℃) is approximately 300,000 cps, GPC (
The estimated molecular weight by gel vermin-shun chromatography) was about 50,000.

Example 2 The method of Preparation Example 1 was repeated except that PE-3000 was used instead of PP-2000 and 1,000 parts of methylene bromide was used instead of 700 parts of methylene chloride.

Approximately 1,700 parts of polyether that is solid at room temperature (yield: 85
%)was gotten. The freezing point of this polyether is approximately 75℃
The molecular weight estimated by GPC was about 140,000.

Example 3 PEP-15001,50 was added to the same reaction vessel as Example 1.
0 copies.

300 parts of solid caustic soda, 75 parts of water, OMAC30
The mixture was heated to 80° C. with stirring, 1,200 parts of monochloromonobromomethane was added dropwise over about 3 hours, and the mixture was aged at the same temperature for 15 hours. After that, purification was carried out in the same manner as in Example 1, and about 1 liter of polyether, which is solid at room temperature,
300 parts (87% yield) were obtained. The freezing point of this polyether is approximately 50°C, and the molecular weight estimated by GPC is approximately 8.
It was 10,000.

[Effect of the invention] According to the method of the present invention, compared to the method according to the prior art,
Polyethers with extremely high molecular weights (Example 1-3: 50,000 to 140,000) can be produced easily and inexpensively.

The high molecular weight polyether obtained by the present invention can be used in various applications, such as rubber materials, polymer plasticizers, polymer modifiers, paper processing agents, fiber processing agents, and surfactants.

It is useful as a raw material for polyurethane, a raw material for curable resins, and many other uses, and its practical value is extremely high.

By reacting the polyether with polyisocyanate, the polyether obtained by the present invention has better elongation, impact resistance, flexibility, water resistance, weather resistance, etc. than polyurethane obtained from conventional polyether. We can produce excellent polyurethane; especially high hardness RIM urethane (exterior materials such as automobile bumpers, fenders, door panels, housings and parts of electrical equipment, etc.), energy absorption, and cushioning for automobiles, furniture, etc. It is useful for highly elastic soft or semi-rigid polyurethane foam, foamed or non-foamed rigid polyurethane, and polyurethane suitable for adhesives and coating materials.

Claims (1)

[Scope of Claims] 1. Alkali metal alcoholate (a) of polyalkylene ether polyol having a molecular weight of at least 200
and a polyfunctional halogen compound (b), optionally in the presence of a catalyst (c), to produce a polyether having a molecular weight of 20,000 to 1,000,000. manufacturing method. 2. (a) and (b) are reacted in a ratio of at least 3 moles of (b) per 1 mole of (a).
Manufacturing method described in section. 3. The molecular weight of (a) is 1,000 to 3,000.
A manufacturing method according to claim 1 or 2. 4. The manufacturing method according to claim 1, 2 or 3, wherein (b) is methylene dihalide. 5. The manufacturing method according to any one of claims 1 to 4, wherein the polyalkylene ether polyol is polyoxyethylene and/or oxypropylene polyol. 6. The manufacturing method according to any one of claims 1 to 5, wherein (a) is an alkali metal alcoholate. 7. The manufacturing method according to any one of claims 1 to 6, wherein a phase transfer catalyst is used as (c). 8. The manufacturing method according to any one of claims 1 to 7, wherein the reaction is carried out at a temperature of 60 to 130°C.