JPS5915334B2 - Manufacturing method of polyacetal polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyacetal polymer, and particularly to a method for producing a polyacetal polymer having unprecedentedly excellent lubricating performance and antistatic performance.

Polyacetals are usually obtained by polymerizing formaldehyde or trioxane.

Japanese Patent Publication No. 41-21638 discloses that an acetal, alcohol, carboxylic acid, or carboxylic acid anhydride is added as a chain transfer agent during the polymerization reaction of trioxane. Further, JP-A-48-29843 describes copolymerization of trioxane in the presence of polyether. As a result of extensive studies on molecular weight modifiers, the present inventors found that a certain compound functions as a good molecular weight modifier and that the polyacetal 1 aggregate produced by 6 has extremely excellent lubricating performance and antistatic performance. , we have completed the present invention.

That is, the present invention is based on the general formula (RO: selected from hydrogen, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, each of which may be the same and may be one, or may be different.

m=2-6, n=1-1,000, R1: alkyl group,
Substituted alkyl group, aryl group, substituted aryl group, R2:
in the presence of a compound selected from the group consisting of an alkylene oxide adduct to an alcohol and an alkylene oxide adduct to a carboxylic acid having a structure represented by hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group) The present invention relates to a method for producing a polyacetal polymer characterized by reacting trioxane or polyoxymethylene. In the present invention, sufficiently dehydrated and purified trioxane and polyoxymethylene can be used as starting materials for synthesizing polyacetal polymers. Here, polyoxymethylene means oxymethylene unit + CH2
It is a linear polymer consisting of repeating O÷ and having a stable group such as a hydroxyl group, an alkoxyl group, a carboxyl group, or a urethane group at both ends of the polymer. Polyoxymethylene can be synthesized by homopolymerizing formaldehyde and trioxane. The number average molecular weight of polyoxymethylene must be at least 10,000 or more, but from the viewpoint of improving the physical properties of the polyacetal polymer produced as a result of the reaction, it is necessary to have a number average molecular weight of 30,000 or more.
More preferably, it is between 0 and 500,000. The compound that can be used as a molecular weight regulator in the present invention is an alcohol represented by the general formula RlOH (R1: alkyl group, substituted alkyl group, aryl group, substituted aryl group) or R2COOH (R2: hydrogen, alkyl group). , substituted alkyl group, aryk group, substituted aryl group), the general formula (RO: hydrogen,
They are selected from alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups, and may be the same or different.
Also good.

It is a compound to which alkylene oxide represented by m=2 to 6 is added. Examples of the alcohol include methyl alcohol, ethyl alcohol, Sec-butyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, ceryl alcohol, myricyl alcohol, oleyl alcohol, Examples include 3-ethyl-6-undecanol, phenol, p-butylphenol, p-octylphenol, p-nonylphenol, benzyl alcohol, p-butylbenzyl alcohol, and the like.

Among these alcohols, long-chain aliphatic alcohols having 8 or more carbon atoms and p-alkyl-substituted phenols are preferred from the viewpoint of improving the lubricating performance of polyacetal polymers, and lauryl alcohol and stearyl alcohol are preferred because of their easy availability. Particularly preferred are alcohols, eicosanol, p-octylphenol and p-nonylphenol. Examples of carboxylic acids include acetic acid, propionic acid,
Caproic acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, ricinoleic acid, phenylacetic acid, cinnamic acid, benzoic acid, p-octylbenzoic acid, α-naphthalic acid, etc. There is.

Among these carboxylic acids, from the viewpoint of improving the lubrication performance of the polyacetal polymer, long-chain aliphatic carboxylic acids having 8 or more carbon atoms are preferred, and from the viewpoint of easy availability, lauric acid, stearic acid, and oleic acid are preferred. and ricinoleic acid are particularly preferred. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, ethylene oxide, xetane, 3,3-bis(chloromethyl)
Oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, oxepane, etc.

Among these alkylene oxides, ethylene oxide is particularly preferred from the viewpoint of improving antistatic performance.
From the viewpoint of easy availability, ethylene oxide and propylene oxide are particularly preferred. These alkylene oxides can be used alone or in combination of two or more.

Alternatively, for example, propylene oxide can be added to the alcohol or carboxylic acid first, then ethylene oxide can be added thereto, and then propylene oxide can be added thereto. The number of moles (r) of alkylene oxide added per mole of alcohol or carboxylic acid must be in the range of 1 to 1,000.

In order to improve the lubricating performance and antistatic performance of the polyacetal polymer, it is preferable that n be large, while from the viewpoint of ease of production and purification, it is preferable that n be small. Based on both of these constraints, the most preferable range of n is 2 to 2
Between 50 and 50. Here, alkylene oxide adducts to alcohols used as molecular weight regulators in the present invention,
The alkylene oxide adduct to carboxylic acid will be specifically explained.

The first group of alkylene oxide adducts to alcohols represented by are compounds represented by the general formula r--1 (R3: hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group).

Examples include ethylene glycol monostearyl ether, ethylene glycol dioleyl ether, polyethylene glycol dilauryl ether, polyethylene glycol distearyl ether, polypropylene glycol monolauryl ether, and the like.

The second group is a compound represented by the general formula (R4: hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group).

Examples include diethylene glycol monostearyl ether monoacetate, polyethylene glycol monooleyl ether monopropionate, polybutylene glycol monostearyl ether monocaproate, and the like. Then R
The first group of alkylene oxide adducts to carboxylic acids having the structure 2♀0+({)NlO→ are compounds represented by the general formula.

Examples include tetraethylene glycol monolaurate, polyethylene glycol monostearate, polytetramethylene glycol monooleate, and the like. The second group is compounds represented by the general formula (R5: hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group).

Examples include triethylene glycol dicaproate, polyethylene glycol dilaurate, and polypropylene glycol distearate. It is desirable that alkylene oxide adducts to alcohols and carboxylic acids be purified by methods such as distillation, adsorption, dry drying, etc. before being used in polymerization reactions as molecular weight modifiers.

Further, these compounds can be used alone, or two or more kinds can be mixed and subjected to the polymerization reaction. A catalyst known as a cationic polymerization catalyst is used in the reaction of the present invention.

For example, tin tetrachloride, tin tetrabromide, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony pentafluoride, boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride acetic acid. So-called Friedel-Crafts type compounds such as anhydrate, boron trifluoride coordination compounds such as boron trifluoride triethylamine complex compounds,
perchloric acid, acetyl perchlorate, hydroxyacetic acid,
Inorganic and organic acids such as trichloroacetic acid, p-toluenesulfonic acid, triethyloxonium tetrafluoroborate, triphenylmethylhexafluorantimonate,
Complex salt compounds such as allyldiazonium hexafluorophosphate, allyldiazonium tetrafluoroborate,
Examples include alkyl metals such as diethylzinc, triethylaluminum, and diethylaluminum chloride.
The cationic polymerization catalyst is 0.0,
It is used in a range of 0005 to 5 parts by weight.

The reaction of the present invention is carried out without a solvent or in an organic medium. In the case of a solvent-free reaction, the starting materials are in a solid state,
It is maintained in a molten or gaseous state, and a molecular weight regulator and a cationic polymerization catalyst are added thereto to start the reaction.
In the case of a reaction in an organic medium, a cationic polymerization catalyst is added to the organic medium containing the starting materials and a molecular weight regulator to initiate the reaction. Organic media that can be used in the present invention include n-pentane, n-hexane, n-
Aliphatic hydrocarbons such as heptane, n-octane, cyclohexane, and cyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, chloroform,
Examples include halogenated aliphatic hydrocarbons such as carbon tetrachloride, ethylene chloride and tritalolethylene, and halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene.

These organic media may be used alone or in combination of two or more. The molecular weight regulator is used after being uniformly dissolved or dispersed in the reaction system.

The concentration of the molecular weight regulator in the system can be easily determined by experiment, depending on the molecular weight requirements of the desired polyacetal polymer. The reaction temperature is usually -20 to 23
It is set between 0℃, but in the case of no solvent, it is set between 20 and 21℃.
It is more preferably between 0°C, and more preferably between -10 and 120°C when an organic medium is used.

There is no particular restriction on the reaction time, but it is set between 5 seconds and 300 minutes.

After a predetermined period of time has elapsed, a basic substance is added to the reaction system and the reaction is terminated.

The resulting polymer is stabilized by blocking unstable terminals by a method such as esterification. The stabilized polyacetal polymer is put into practical use with the addition of a stabilizer and the like. The features of the method for producing the polyacetal polymer of the present invention, which have been described in detail above, are listed below. (1) The polyacetal polymer produced by the method of the present invention has particularly excellent lubricating performance and antistatic performance.

(2) By using a molecular weight regulator, excellent performance can be imparted to the polyacetal polymer, and at the same time, the molecular weight of the polyacetal polymer can be arbitrarily controlled.

Measurement items in the following examples are as follows.

Reduced viscosity: Polymer concentration 0.5 gr/in p-chlorophenol-tetrachlorethylene (1:1 weight ratio) solution
Measured at 60°C with dl f9Rv222: The polymer that had been terminally stabilized using acetic anhydride was heated at 222°C under vacuum for 6
It is the amount of heat remaining after heating for 0 minutes, and is an index of the thermal stability of the polymer.

Friction coefficient: 2,2-methylene-bis(4-methyl-
6-tert-butylphenol) and 0.75 parts of a terpolymer of polycaprolactam/polyhexamethylene adipamide/polyhexamethylene sebamide were added, mixed using a 50 mmφ extruder, and then molded. Measured using a thrust type friction and wear tester, mating material: metal (S4
5℃) Load: 10k9/beam tooth 112? /Sec The friction coefficient is an index of lubrication performance.

Surface electrical resistance: The surface electrical resistance of the same polymer at 20℃,
50%R. H. Measured below, it is an indicator of antistatic performance.

Example 1 500 parts of sufficiently purified trioxane (hereinafter, parts are parts by weight) was placed in a secondary tank having two Σ-type stirring blades.

), C,8H37O(CH2CH2O)40C18H3
7 (polyethylene glycol distearyl ether, average number of added moles of ethylene oxide: 40) was charged and heated to 70°C.

Next, 0.25 part of boron trifluoride dibutyl etherate was added to this second reactor and stirred for 70 minutes. Immediately thereafter, 8 parts of tributylamine was added to stop the polymerization.
The contents were taken out from the kneader and washed with acetone to obtain 506 parts of polyacetal polymer. The reduced viscosity of this polymer was 1.83, a desired value, and the Rv was 99%, indicating excellent thermal stability. When a stabilizer was added to a polymer that had been terminally stabilized using acetic anhydride and molded, a very tough molded product could be obtained. The friction coefficient of this molded product is 0.16, and the surface electrical resistance is 5×1
011Ω, and had excellent lubrication performance and antistatic performance. Example 2 Formaldehyde gas with a purity of 99.9% was mixed with 1 x 10-
Polyoxymethylene dihydroxide having a number average molecular weight of 2.3 x 105 was obtained by introducing it into cyclohexane containing 4 mol/l of dibutyltin dilaurate.

150 parts of the polyoxymethylene dihydroxide thus obtained, CllH23CO(CH2CH2O)3
An autoclave containing 5.8 parts of 0H (ethylene oxide adduct to lauric acid, average number of moles of ethylene oxide added: 30) and 500 parts of toluene was heated to 75°C.
Next, 0.12 parts of boron trifluoride diethyl etherate was added to the autoclave and stirred for 40 minutes. After adding 10 parts of tributylamine to the autoclave, the contents were taken out, washed and dried to obtain 152 parts of a polyacetal polymer. The reduced viscosity of this polymer is 1
．． 75, Rv 99%, and had the desired molecular weight and excellent thermal stability. Further, the friction coefficient of this polyacetal polymer was 0.23, and the surface electrical resistance was 6×10 11 Ω, indicating excellent performance. Example 3 1500 parts of polyoxymethylene dimethoxide having a number average molecular weight of 1.5 x 105, propylene oxide adduct to nilphenol, average addition mole of propylene oxide 15
) were mixed in a sufficiently dried hopper and extruded using a 30m71Lφ extruder with L/D=35 equipped with a ventro.

The time required for extrusion was 28 minutes, and the temperature of the molten resin at the die exit was 190°C. Boron trifluoride 0.12
This catalyst solution was forcibly added from a vent hole using a metering pump at a rate of 2 parts per minute over the 28 minutes required for extrusion. The average residence time of the resin from the vent hole to the die exit is 30 seconds, and the molten resin coming out of the b die is 1.1 seconds.
% by weight of potassium carbonate aqueous solution, and 1481 parts of polyacetal polymer was recovered as a strand. The reduced viscosity of this polymer was 1.83, which was a desired value.
Further, Rv was 99%, friction coefficient was 0.18, and surface electrical resistance was 4×10 15 Ω. The excellent lubricating performance of this polymer is due to the use of the molecular weight modifier of the present invention. Example 4 300 parts of trioxane, C,lH23〒0(CH2CH2O)20CCH3 (compound obtained by acetylating an ethylene oxide adduct to lauric acid, average number of added moles of ethylene oxide 20) 15
A reaction vessel containing 1,800 parts of benzene was heated to 55°C, and then 0.30 parts of tin tetrachloride was added to the reaction vessel.
Stirred for 0 minutes.

After adding 15 parts of tributylamine to the reaction vessel, the contents were taken out, washed and dried to obtain 298 parts of a polymer. This polymer has a reduced viscosity of 1.58 and a friction coefficient of 0.
24, a polymer with surface electrical resistance of 8×10 11 Ω and excellent performance was obtained. Examples 5-10 Example 1
Among the reagents used in Example 1, all the same reagents as in Example 1 were used, except that the molecular weight regulator shown in Table 1 was used instead of polyethylene glycol distearyl ether, and the procedure was carried out in the same manner as in Example 1.

The results obtained are shown in Table 1. In all Examples, polymers with excellent lubrication performance and antistatic performance were obtained. Comparative Example 1 The same reagents as in Example 1 were used, except that methylal was used instead of polyethylene glycol distearyl ether, and the same procedure as in Example 1 was carried out.

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ (R_0: selected from hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group, each of which may be the same or different) m = 2 to 6, n = 1 to 1,000, R_1: alkyl group, substituted alkyl group, aryl group, substituted aryl group, R_
2: hydrogen, alkyl group, substituted alkyl group, aryl group,
The method is characterized by reacting trioxane or polyoxymethylene in the presence of a compound selected from the group consisting of alkylene oxide adducts to alcohols and alkylene oxide adducts to carboxylic acids having a structure represented by a substituted aryl group). A method for producing a polyacetal polymer. 2. The production method according to claim 1, wherein the alcohol is a long-chain aliphatic alcohol having 8 or more carbon atoms. 3. The manufacturing method according to Claims 1 and 2, wherein the alcohol is lauryl alcohol, stearyl alcohol, or eicosanol. 4. The manufacturing method according to Claim 1, wherein the alcohol is p-alkyl-substituted phenol. 5 Alcohol is p-octylphenol or p-
Claims 1 and 4 which are nonylphenol
Manufacturing method described in section. 6. The production method according to claim 1, wherein the carboxylic acid is a long-chain aliphatic carboxylic acid having 8 or more carbon atoms. 7. The manufacturing method according to claims 1 and 6, wherein the carboxylic acid is lauric acid, stearic acid, oleic acid or ricinoleic acid. 8. The method according to claim 1, wherein the alkylene oxide is ethylene oxide. 9. The method according to claim 1, wherein the alkylene oxide is propylene oxide. 10. The production method according to any one of claims 1 to 9, wherein the number of moles (n) of alkylene oxide added per mole of alcohol and carboxylic acid is in the range of 2 to 250. 11 A patent claim in which the alkylene oxide adduct to alcohol is a compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_3: hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group) The manufacturing method described in Scope 1. 12 A patent claim in which the alkylene oxide adduct to alcohol is a compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_4: hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group) The manufacturing method described in Scope 1. 13. The production method according to claim 1, wherein the alkylene oxide adduct to carboxylic acid is a compound represented by the general formula ▲There are numerical formulas, chemical formulas, tables, etc.▼. 14 A patent claim in which an alkylene oxide adduct to a carboxylic acid is a compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_5: hydrogen, alkyl group, substituted alkyl group, aryl group, substituted aryl group) The manufacturing method according to item 1. 15 Claim 1 in which the reaction is carried out without a solvent
Manufacturing method described in section. 16. The method according to claim 1, wherein the reaction is carried out in an organic medium.