JPS62240321A - Production of polyoxytetramethylene - Google Patents

Abstract

PURPOSE:To obtain the titled high-molecular weight polymer useful for rubber materials, elastomers, polymer plasticizers, etc., by reaction between alkali metal alcoholate of polyoxytetramethylene glycol with specific molecular weight and polyfunctional halogen compound. CONSTITUTION:The objective polymer with a molecular weight 4,000-1,000,000 (pref, 20,000-1,000,000) can be obtained by reaction, pref. at 60-130 deg.C between (A) alkali metal alcoholate of polyoxytetramethylene glycol with a molecular weight >=500 (pref. 700-3,000) 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 polyoxytetramethylene.

[Conventional technology] Polyoxytetramethylene glycol (hereinafter referred to as PTHG)
Tetrahydrofuran (abbreviated as TIIF) is usually prepared in the presence of an acidic catalyst (Lewis acid and/or protonic acid).
(abbreviated as )) is produced by ring-opening polymerization.

[Problems to be Solved by the Invention] In the conventional PTHG production method, when the molecular weight exceeds 4,000, it becomes difficult to control the molecular weight and it is difficult to obtain a product of stable quality.

[Means for Solving the Problems] The present invention comprises: an alkali metal alcoholate of polyoxytetramethylene glycol having a molecular weight of at least 500 (a) and a polyfunctional halogen compound (b), optionally a catalyst (c). 4.000 to 1 in one reaction in the presence of
This is a method for producing high molecular weight polyoxytetramethylene, which is characterized by producing polyoxytetramethylene having a molecular weight of 1,000,000.

As the raw material PTHG (a) used as a starting material in the present invention, those obtained by ring-opening polymerization of PTHG in the presence of an acidic catalyst can be used.

As an acidic catalyst, Lewis 1 (FeCJ!3゜T i
C14,5nci4.5bCJ! s, Aj! F3
.

BF3, PFs, etc.), protonic acids (IF, HCJ!
.

HB r, to! 2 SO4, f-1sO3F,
H3O3C1゜HCJ! 04, etc.), solid catalysts (montmorillonite minerals, zeolites, silica/alumina catalyst 1 strong acid type ion exchange resin, etc.), and composite systems of two or more of these (combined use of Lewis acid and protonic acid, protonic acid and solid catalyst) Lewis acid-acetic anhydride system, protonic acid-acetic anhydride system, Lewis acid-acetic anhydride system using these together with an acylium ion precursor (e.g. acetic anhydride)
Examples include blended catalyst systems such as protonic acid-acetic anhydride systems.

The amount of catalyst used is 100 parts of THF (indicates the mold recess.

(same below) per 2 usually 0.5 to 30 parts, preferably 1 to 30 parts
There are 20 copies. The polymerization temperature is usually 60°C or lower, preferably -50 to +50°C, particularly preferably -10 to +40°C.
It is.

The thus obtained Pg)fG may be used as it is (crude 2g), or a purified product from which the catalyst has been removed by a conventional method may be used.

In the present invention, P-iG includes not only a polymer of THE alone but also a copolymer of TI and alkylene oxide (hereinafter abbreviated as AO). Examples of AO include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as po), 1.2-, 2.3-, 1°3-butylene oxide, styrene oxide, epichlorohydrin, etc., and two or more of these. Mixtures may be mentioned. Ratio of HF and AO (molar ratio or weight ratio)
is usually 1:0 to 1:0.5. Preferably 1:
0-1:0.3. The method of copolymerization of THE and AO and the copolymerized product are those described in Japanese Patent Application No. 59-247530 and Japanese Patent Application No. 59-279962, and in accordance therewith (the type of AO and/or Examples include those manufactured by changing the ratio).

The molecular weight of PTHG is usually 500 to 5,000, preferably 600 to 4,000, and more preferably 700 to 3,00.
It is 0.

In addition, P-D) IG contains a small proportion of polyisocyanate (1
It may be further made into a polymer by reacting it with a compound listed in No. 12 (PTMG/polyisocyanate ratio: for example, 1.2 to 10/1, preferably 1.5 to 2/1).

PTHG is subjected to a reaction with a polyfunctional halogen compound by converting at least a portion of its terminal hydroxyl groups into metal alcoholate groups.

The method of alcoholation is not particularly limited, and examples include: ■ reaction with caustic alkali (NaOH, KOH, etc.); ■ metal alcoholate of lower alcohol (cH3ONa).
, Ct130, etc.), ■ method of reacting with alkali gold R (Na, etc.), ■ method of reacting with metal hydride (NaH, H, etc.), and combinations of two or more of these methods. There are several methods. Among these, (1), (2), and (especially, the method using NaOH) are preferred. In the method (2), the caustic alkali is preferably used in excess, and the amount used is usually 1.5 mol or more, preferably 2 mol or more, more preferably 3 to 20 mol, and most preferably 4 to 10 mol per hydroxyl group. be. ■
In the method of ~■, the amount of alcohol-1-forming agent used is usually 0.8 to 2 mol per hydroxyl group, preferably 0.95 to 1.
It is 2 moles. Alcoholation reaction is usually O~180'
C. Preferably, it can be carried out at any temperature from 30 to 150°C.

When alcoholating PTHG, before or after alcoholation, in addition to PTMG, a small proportion [5
A mixture of the metal alcoholate (a) of PTMG and the metal alcoholate (ao) of polyalkylene ether polyol can be obtained by using a polyalkylene ether polyol in an amount of less than 0 mol %, particularly 30 mol % or less.

Polyalkylene ether polyols include polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids,
Examples include compounds having a structure in which AO is added to a polyfunctional compound containing an active hydrogen atom such as phosphoric acid, and mixtures of two or more thereof.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1
, 4-butanediol, 1,6-hequinanediol, diethyl glycol, neopentyl glycol, bis(
dihydric alcohols such as hydroxymethyl) cyclohexane and bis(hydroxyethyl) penpine; glycerin;
Trimethylolpropane, pentaerythritol, diglycerin, α-methyl glucoside, turgotol, xylit.

Tri- to octa-valent polyhydric alcohols such as mannitol, dipentaerythritol, glucose, fructose, and sucrose; Examples of amines include ammonia, C1-C20 alkyl amines (butylamine, etc.), monoamines such as anisono; ethylene diamine , 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; dicyclohexylmethane diamine, isophorone diamine, etc. Alicyclic polyamines; aromatic polyamines such as phenylene diamine, tolylene diamine, diethyl tolylene diamine, xylylene diamine, diphenylmethane diamine, diphenyl ether diamine, polyphenyl methane polyamine; and monoethanolamine, jetanolamine, triethanolamine, Alkanolamines such as triisopropanolamine; 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. Acid can be given.

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

As the AO added to the above active hydrogen atom-containing compound,
Examples include EO, Po, 1.2-, 2.3-, 1.3-butylene oxide, styrene oxide, and epichlorohydrin. AO may be used alone or in combination of two or more types, and in the latter case, block addition (chip type, balanced type, active secondary type, etc.), random addition, or a mixed system of both (two or more molecules after random addition) It has 0 to 50 weight percent (5 to 40 weight percent) of ethylene oxide chains arbitrarily distributed therein, and has 0 to 30 weight percent (5 to 25 weight percent) of EO chains tipped at the end of the molecule) But that's fine. Among these AOs, preferable ones are EO alone, P
O alone, PO and EO in combination (random, block, and mixed systems). The addition of AO can be carried out in a conventional manner, either without a catalyst or in the presence of a catalyst (alkaline catalyst, amine catalyst, acidic catalyst) (especially in the latter stages of AO addition) under normal or elevated pressure. It is carried out in one stage or in multiple stages.

Further, the polyalkylene ether polyol may be made to have a higher molecular weight by reacting with a small proportion of polyinsyanate (described below) (Equivalence ratio of polyalkylene ether polyol/polyisocyanate: for example, 1.
2 to 10/1, preferably 1.5 to 2/1).

The molecular weight of polyalkylene ether polyol is usually 50
0 to 20,000, preferably 500 to 1 o, ooo, and more preferably i, ooo to 3,000. Equivalent weight of polyalkylene ether polyol (molecular weight per hydroxyl group)
is usually 100 to 10,000, preferably 250 to 5.0
00, 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 0 to 100%.
Preferably 30-100%, more preferably 50-100%
% most preferably 70-100%.

In the present invention, PTHG is reacted with metal alcoholate (a). As the polyfunctional halogen compound (b),
These include:

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

Methylene iodide, monochloromonobromomethane.

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, tetra(bromomethyl)methane, trichlorethylene, tetrachlorethylene, 1,2-dichloroethylene, 1,2-dibromoethylene, 3,4-
Dichloro-1-butene; (1i) aromatic ring-containing polyhalogenated hydrocarbons such as benzal chloride, benzal bromide,
Bis(chloromethyl)benzene (o-, m- and 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: (1) Multi-halogenated aliphatic ethers such as °bis(
chloromethyl)ether, bis(chloromethyl)thioether, 2,2°-dichloroethyl ether, 1.2-
Bis(2-chloroethoxy)ethane; (it) polyhalogenated aromatic ethers e.g. 4.4
°-Bis(chloromethyl)diphenyl ether: (m) Polyhalogenated aromatic aliphatic ethers such as bis(chloromethoxy)benzene and tris(chloromethoxy)benzene.

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

(4) Polyhalogenated alcohols: For example, 1-dichloro-methanol, 1,3-dichloro-
2-propertool, bis(chloromethyl>formal, etc.).

(5) @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 ff1 (especially methylene dihalides (methylene chloride, methylene bromide, methylene fluoride,
methylene iodide, monochloromonobromomethane)], and methylene chloride is most preferred.

According to the present invention, in reacting the metal alcoholate of PTHG (a) and the polyfunctional halogen compound (b),
The amount of (b) used is per mole of (a) (metal alcoholate of (a) and polyalkylene ether polyol (ao
) is used in combination, the amount is usually 3 moles or more, preferably 6 moles or more, more preferably 8 to 200 moles, and most preferably 10 to 100 moles, per 1 mole of the total of (a) and (a'').

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 publication [quaternary ammonium salts, quaternary phosphonium salts, quaternary alumnium salts, macrocyclic ethers, etc.] can be used; typical examples include tetrabutylammonium bromide, trioctyl Oil-soluble quaternary salts 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 relative to (a) [when (a) and metal alcoholate (a') of polyalkylene ether polyol are used together, relative to the total of (a) and (ao)]. .1 to 20 mol%, preferably 1 to 10 mol%.

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) (and (a') if necessary) is performed using a polyoxygenate having a molecular weight of 20,000 to 1,000,000 (preferably 30,000 to 500,000, particularly preferably 50,000 to 300,000). This is carried out until tetramethylene is obtained, for example until the viscosity reaches the target viscosity. To adjust the molecular weight, use (a) and (
It can be carried out by changing the reaction molar ratio of b),
The larger the molar ratio of (b)/(a) is, the easier it is to obtain polyoxytetramethylene 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 polyoxytetramethylene obtained by the present invention can be used as is as a rubber component, a polymer plasticizer, a paper processing agent,
It can be used as a fiber treatment agent and polyurethane raw material 11.Also, after introducing an olefinic unsaturated group at the terminal, it is reacted with a silicon hydride compound to form a polyoxy resin having a hydrolyzable silicon functional group (hydrolyzable silyl group). Tetramethylene can also be used, and furthermore, the terminal can be aminated by a known method to convert it into polyoxytetramethylene polyamine. The polymer "polyoxytetramethylene" obtained by the method of the present invention is a sealing material.

It is also a useful material for applications such as caulking materials, paints, adhesives, and epoxy hardeners.

In addition, polyoxyna 1 to ramethylene obtained by the present invention can be reacted with a small proportion of polyisocyanate to further produce polymer-blocked urethanized polyoxytetramethylene (equivalent of polyoxytetramethylene/polyisocyanate). Ratio: For example, 1 to 10/1, preferably 1.2 to 2/1) When using the polyoxytetramethylene produced by 1q according to the present invention as a raw material for polyurethane or for producing urethanized polyoxytetramethylene, the polyisocyanate used is , Aromatic polyisocyanates with a carbon number of 6 to 20 (excluding carbon in the NGO group) (e.g. tolylene diisocyanate, diphenylmethane diisocyanate, etc.), aliphatic polyisocyanates with a carbon number of 2 to 18 (e.g. hexamethylene diisocyanate, etc.), carbon Alicyclic polyisocyanate having a number of 4 to 15 (e.g. isophorone diisocyanate, etc.), having 8 carbon atoms
~15 aromatic aliphatic polyisocyanates (e.g. xylylene diisocyanate, etc.) and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified products, etc.) and patent application No. 1991-1983
Polyinsyanates other than those described in No. 0 can be used. Among these, commercially readily available polyisocyanates such as 2,4- and 2,6-TD
I and a mixture of these minohites, crude TDI, 4,4
°- and 2.4'-MD I and mixtures of these isomers, polyarylene polyincyane i (PAPI), also called crude MDI, and urethane groups, carbodiimide groups, and allophanate groups derived from these polyisocyanates. , urea group.

Modified polyisocyanates containing 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 the specification of Japanese Patent Application No. 59-199160, known catalysts (for example, triethylenediamine, etc.), Tertiary amines (metal catalysts such as tin octylate, dibutyltin dilaurate, lead octylate, etc.) can be used.

The blowing agent used is based on the desired density of the polyurethane (e.g. o
, oi to i, 4 g/cd), and the catalyst can be varied, e.g. from about 0,001 to
It is used in small amounts of about 5%. Other additives that can be used in polyurethane production include surfactants as emulsifiers and cell stabilizers, especially polysiloxanes.
Polyoxyalkylene copolymers are 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.

When the polyoxytetramethylene obtained in the present invention is used for producing polyurethane, the isocyanate index is usually 65 to 120 (preferably 75 to 110, preferably 85 to 105). In general, polyisocyanurate is introduced into polyurethane by making the isocyanate index significantly higher than the above range (polyisocyanate index is 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. The production of polyurethane is usually carried out 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 polyoxytetramethylenes obtained according to the invention are particularly useful in polyurethane elastomers and sheet materials. Ex 1 to 9 are prepared by combining organic diisocyanate, polyoxytetramethylene (bifunctional) obtained in the present invention, and optionally other polymeric diol and/or chain extender in the presence or absence of a solvent, It can be produced by reaction. Sheet materials can be produced by applying a solution of such an elastomer to a substrate and dry or wet processing. The organic diisocyanate, other polymeric diol, chain extender, solvent, application method, and wet treatment method are described in Japanese Patent Application No. 5
Examples include those described in No. 9-247530.
In addition, the polyoxytetramethylene obtained in the present invention is
No foaming or low foaming (density 0.8 to 1.4 g/crd, especially 0.95 to 1
．． It is useful for producing RIM molded polyurethane elastomer (hereinafter referred to as RIM urethane) of 4tj/Cl1l). 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 to 90'C (2
~4 components) at a pressure of ioo~200 Kg/criG, and preheated at 30~200'C (preferably 6
After pouring into a mold whose temperature is controlled at 0 to 90°C, 0.1
This can be done by demolding within 5 minutes. The molded product obtained after molding can be made into a product as 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 60-180°C x 0.3-100 hours, preferably 80-160'C x 0.3-100 hours, more preferably 100-150'C x 0.3-100 hours, particularly preferably 120-140°C. 'CX1 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 parts and % represent parts by weight and % by weight, respectively.

(1) PT-2000: Molecular weight approximately 2,000 (7) PT
)tG (hydroxyl value 55.7 no.087g).

(2) PT-1500: PT)I with a molecular weight of approximately 1,500
G (0+1/(]) with a hydroxyl value of 75.1 mg.

(3) Liquid caustic soda: 48% NaOH aqueous solution.

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

Example 1 PT-2000500 was placed in a reaction vessel equipped with a dropping device, a reflux condenser, a gas introduction pipe, a temperature recorder, and a stirring device.
and 180 parts of liquid caustic soda, gradually raised the temperature while stirring, and dehydrated under reduced pressure at a temperature of 80 to 150°C.
About 45 parts of water was poured into the river. Next, 200 parts of methylene chloride was added dropwise to the mixture, which was cooled to 120° C. over about 2 hours, and aged at about 80° C. for 20 hours. Then, 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, about 450 parts (yield: 90%) of 1 q of polyoxytetramethylene, which is solid at room temperature, was obtained.

The hydroxyl value of this polyoxytetramethylene is 3m
The molecular weight estimated by gKOH/g and GPC (gel permeation chromatography) was about 350,000.

Example 2 In the same reaction vessel as in Example 1, 500 parts of PT-1500.

120 parts of solid caustic soda, 30 parts of water and 10 parts of HAC were charged, the temperature was raised to 80'C with stirring, 450 parts of monochloromonobromomethane was added dropwise over about 3 hours, and the mixture was aged at the same temperature for about 15 hours. . Thereafter, purification was performed in the same manner as in Example 1, and about 450 parts of polyoxytetramethylene (yield: 90%), which was solid at room temperature, was obtained. The estimated molecular weight of this polyoxytetramethylene by GPC is about 11
It was 10,000.

[Effects of the Invention] According to the method of the present invention, compared to the prior art,
Polyoxytetramethylene with a significantly high molecular weight (more than 30,000) can be easily and inexpensively produced:
Moreover, the molecule m can be easily controlled, and products of constant quality can be easily produced.

In addition, conventional PT)fG was limited to linear (bifunctional) ones, but the one according to the present invention can freely change the functionality, and is not only linear (bifunctional) but also branched. state (
(trifunctional or higher) can also be produced.

The high molecular weight polyoxytetramethylene obtained by the present invention has various uses, such as rubber materials, raw materials for elastomers (polyurethane, polyether polyester elastomers, etc.), and polymer plasticizers.

Polymer modifier 1 is useful in many applications such as paper treatment agents, Ili fiber treatment agents, surfactants, polyurethane raw materials, curable resin raw materials, and many other uses, and its practical value is extremely high.

By reacting the polyoxytetramethylene 19 with polyisocyanate, the polyoxytetramethylene obtained in the present invention has better elongation, impact resistance, bending resistance, and water resistance than polyurethane obtained from conventional polyoxytetramethylene. , polyurethane with excellent weather resistance etc. can be produced; in particular, polyurethane elastomer, sheet material (porous sheet material by wet method and dry method), RIM urethane (
Exterior materials such as automobile bumpers, fenders, door panels, housings and parts of electric appliances), high hardness and high elasticity soft or semi-rigid polyurethane foams and foams for energy absorption and cushioning of automobiles, furniture, etc. It is useful for non-foaming rigid polyurethane, polyurethane suitable for adhesives, and coating materials.

Claims (1)

Claims: 1. Alkali metal alcoholate of polyoxytetramethylene glycol having a molecular weight of at least 500 (a
) and a polyfunctional halogen compound (b), optionally in the presence of a catalyst (c), to produce polyoxytetramethylene having a molecular weight of 4,000 to 1 million, A method for producing high molecular weight polyoxytetramethylene. 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 manufacturing method according to claim 1 or 2, wherein (a) has a molecular weight of 700 to 3,000. 4. The manufacturing method according to claim 1, 2 or 3, wherein (b) is methylene dihalide. 5. The molecular weight of polyoxytetramethylene is 20,000 to 100
The manufacturing method according to any one of claims 1 to 4, wherein the manufacturing method is 10,000. 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.