JPS6351446A - Polyoxymethylene copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition, by bulk polymerizing trioxane with a cyclic ether in the presence of BF3 catalyst, deactivating the catalyst with a metal sulfite and blending the resultant polymer with an alkali metal hydroxide, etc., specific antioxidant and formaldehyde absorption reagent and having improved heat-resistant stability and mechanical properties. CONSTITUTION:Trioxane and a cyclic ether are subjected to bulk polymerization in the presence of a catalyst selected from boron trifluoride, boron trifluoride hydrate and coordination compound of boron trifluoride with an O- or S- containing organic compound, preferably a coordination compound and a metal sulfite is added to deactivate the catalyst. The resultant polymer is then blended with (A) a compound selected from hydroxides, inorganic acid salts, organic acid salts and alkoxides of alkaline (earth) metals, (B) a hindered amine based antioxidant and (C) a reagent capable of absorbing formaldehyde, e.g. amide or urethane compound. The respective amounts of the components are within the range of 0.001-5wt.%, preferably 0.05-3wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an oxymethylene copolymer composition having excellent heat resistance stability and mechanical properties.

<Prior Art> It is known to obtain oxymethylene homopolymers or copolymers by bulk polymerizing trioxane alone or trioxane and a cyclic ether in the presence of a catalyst, for example, in Japanese Patent Publication No. 5234/1983. The obtained polymer is thermally unstable as it is, so in the case of a homopolymer, it is stabilized by blocking the ends by esterification, etc., and in the case of a copolymer, by decomposing and removing unstable ends. Prior to this, it is necessary to stop the reaction by deactivating the catalyst.

In other words, oxymethylene homopolymers or copolymers obtained by cationopolymerization of trioxane, etc., will gradually depolymerize if the catalyst remaining therein is not deactivated, resulting in significant molecular deterioration or thermal damage. tζ becomes extremely unstable.

Regarding the deactivation of boron trifluoride polymerization catalysts, US Pat. No. 2,989,509 proposes the use of aliphatic amines and petrocyclic amines. If these are removed, the polymer is stabilized and no decrease in molecular weight is observed even if it is stored as is for a long period of time.

However, even if the catalyst is deactivated with a common amine compound, if the catalyst is not removed from the polymer by washing, depolymerization will still occur when the polymer is melted or dissolved, resulting in a decrease in molecular weight.

Therefore, after deactivating the catalyst with an amine, it was essential to remove the catalyst from the polymer by a thorough washing operation. For example, Japanese Patent Publication No. 39-8071,
Japanese Patent Publication No. 43-1875 describes a method for stabilizing the terminals of oxymethylene copolymers, but in these methods as well, the polymerization catalyst is deactivated with an amine and washed by washing before stabilizing the terminals. It is being removed.

Recently, as a catalyst deactivator that does not require cleaning or removal,
A trivalent phosphorus compound was discovered and published in Japanese Patent Publication No. 55-42085.
It is stated in the No.

However, in order to produce an oxymethylene copolymer with higher thermal stability, it is essential to deactivate the catalyst, decompose unstable terminals, and add a stabilizer. Various formulations of stabilizers have been known, for example, Japanese Patent Publication No. 34-5440 describes stabilization by kneading polyamide and hindered phenol.

<Problems to be Solved by the Invention> Although the thermal stability is certainly increased by mixing the stabilizer as described above, if it is left in a molten state for a long time during molding etc., it will decompose and foam, resulting in mold failure. I was still not satisfied with the results, including having to pay a deposit. Furthermore, if washing and removal of the catalyst is omitted in the normal catalyst deactivation process using an amine, the heat resistance stability of the polymer will be extremely low no matter what kind of stabilizer is kneaded, and it will not be able to withstand melt molding. Further, even when the catalyst is deactivated using a trivalent phosphorus compound, the heat stability is insufficient. The present inventors have conducted intensive studies to obtain an oxymethylene copolymer composition having extremely excellent heat resistance stability, and as a result, have discovered the present invention.

Means for Solving the Problems> That is, the present invention combines a mixture of trioxano and a cyclic ether with boron trifluoride, boron trifluoride hydrate, and an organic compound containing boron trifluoride and an oxygen atom or a sulfur atom. After bulk polymerization in the presence of at least one polymerization catalyst selected from the group consisting of coordination compounds with An oxymethylene compound prepared by adding and mixing one or more selected from hydroxides, inorganic acid salts, organic acid salts, and alkoxides, a hindered phenolic antioxidant, and an agent capable of reacting with formaldehyde and absorbing formaldehyde. It is a polymer composition.

The cyclic ether used in the present invention means a compound represented by the following general formula.

y, -c-.

Y.

(However, in the formula, Y1 to Y4 are hydrogen atoms, carbon atoms 1 to 6
represents an alkyl group having 1 to 6 carbon atoms and a halogeno-substituted alkyl group having 1 to 6 carbon atoms, which may be the same or different.

Further, X represents a methylene or oxymethylene group, which may be substituted with an alkyl group or a halogen-substituted alkyl group, and m represents an integer of θ to 3. Alternatively, X is −< C
H,)p -0-CH2- or -O-CH2-(CH2
) p -0-CHt-, in which case m
= l, p is an integer of 1 to 3) Among the cyclic ethers or cyclic acecules represented by the above general formula, particularly preferred compounds include ethylene oxide, propylene oxide, 1,3-dioxolane, l,
3-dioxane, 1,3-leoxepane, 1,3.5-
Trioxerth, 1,3,6-trioxocane, epichlorohydrin, etc. are mentioned.

The copolymerized amount of the cyclic ether in this study needs to be in the range of 0.1 to 10 mol%, particularly preferably 0.2 to 6 mol%, based on trioxane, and if it is less than 0.1 mol%, it cannot be obtained. The thermal stability of the resulting composition is low, and if it is more than 10 mol %, the melting point and crystallinity of the resulting composition will be lowered, resulting in poor mechanical strength and moldability, which is not preferred.

In the polymerization catalyst of the present invention, one or more compounds selected from the group of boron trifluoride, boron trifluoride hydrate, and coordination compounds of boron trifluoride and organic compounds having oxygen or sulfur atoms are It can be used in solid, liquid or solution form in a suitable organic solvent.

Examples of the organic compound having an oxygen or sulfur atom that forms a coordination compound with boron trifluoride include alcohol, ether, phenol, sulfide, and the like.

Among these catalysts, coordination compounds of boron trifluoride are particularly preferred, and boron trifluoride/diethyl etherate and boron trifluoride/dibutyl etherate are particularly preferably used.

Examples of the solvent for the polymerization catalyst in the present invention include aromatic hydrocarbons such as benzene, toluene, and quinoa, aliphatic hydrocarbons such as n-hexane, n-hebutane, and cyclohexane, alcohols such as methanol and ethanol, and chloroform. , dichloromethane, halogenated hydrocarbons such as 1,2-dichloroethane, acetone, ketones such as methyl ethyl ketone.

The amount of polymerization catalyst added is 5 to 1 mole of trioxane.
The range is from X10 to 1×10 mol, particularly preferably the range from 1X10 to 1×10 mol.

Although a device for polymerizing trioxane alone or trioxane and a cyclic ether in bulk is known, the bulk polymerization used in the present invention is not particularly limited by the device, and the polymerization amount is 10% by weight or less based on trioxane. Therefore, it can also be applied to polymerization reactions carried out in the presence of an organic solvent such as cyclohexane.

In bulk polymerization, since rapid solidification and heat generation occur during polymerization, an apparatus having strong stirring ability and capable of controlling the reaction temperature is particularly preferably used.

The bulk polymerization apparatus of the present invention having such performance uses a cylindrical barrel as the reaction zone of the kneader 1 having a sigma type stirring blade, and is equipped with a coaxial screw having a large number of interrupted ridges in the barrel, A mixer that operates by meshing this interruption with teeth protruding from the inner surface of the barrel, a conventional screw extruder that has a pair of mutually meshing parallel screws in a long case with a heating or cooling jacket, and two A self-cleaning mixer, etc. that has a large number of paddles on a horizontal stirring shaft, and when the shafts are rotated simultaneously in the same direction, a slight clearance is maintained between each paddle surface and the inner surface of the case. can be mentioned.

In addition, in bulk polymerization, strong stirring capacity is required because the polymerization solidifies rapidly in the early stage of the polymerization reaction. It may be divided into two stages.

The bulk polymerization reaction temperature is preferably in the temperature range from near the melting point of trioxane to near the boiling point, ie, 60-115°C, particularly preferably 60-90°C.

In the early stages of polymerization, the temperature inside the polymerization reactor tends to rise due to reaction heat and frictional heat from solidification, so it is desirable to control the reaction temperature by passing cooling water through the jacket, etc. .

The terminator used in the present invention to deactivate the boron trifluoride catalyst and terminate the polymerization reaction, ie, the metal sulfite salt, is added as it is or as a solution or suspension in an organic solvent and mixed.

When adding a terminator, the temperature is preferably controlled within the range of 0 to 100°C so that depolymerization does not proceed.

In addition, in order to allow the reaction between the terminator and the polymerization catalyst to proceed sufficiently, it is preferable that the polymer be in the form of as fine a powder as possible, so it may be pulverized using a pulverizer before adding the terminator. , and may be milled after addition of the stopper.

Examples of the sulfite metal salt used in the present invention include sodium sulfite, potassium sulfite, calcium sulfite, barium sulfite, etc., and sodium sulfite is particularly preferably used.

Further, although not particularly necessary, in order to further improve the effects of the present invention, phosphine oxytos represented by the following general formula 6 can be used in combination with a metal sulfite salt.

R1 R, -P = 0 ・・・Life・
■R1 (In the formula, R1, R2, and R3 are hydrocarbon groups having 1 to 18 carbon atoms, and may be the same or different.) Specific examples thereof include triphenylphosphine oxyto, tri-n-butylphosphine oxyto, di-n
-butylbenzylphosphine oxide, synchlohexylphenylphosphine oxyto, tritolylphosphine oxyto, etc., among which triphenylphosphine oxyto is preferred.

The effect of the present invention can be realized if the terminator of the present invention is added in an amount equal to or more than the same molar amount as the boron trifluoride catalyst used as the polymerization catalyst, but the amount added is 2 to 50 times the molar amount. is efficient.

Specific examples of hydroxides, inorganic acid salts, organic acid salts, and alkoxides of alkali metals and alkaline earth metals used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and hydroxide. calcium,
Barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium phosphate, sodium borate,
Sodium acetate, magnesium acetate, sodium benzoate, sodium terephthalate, sodium methoxide,
Examples include potassium methoxide, sodium ethoxide, potassium ethoxide, magnesium ethoxide, sodium isopropoxide, sodium phenoxide, n-butyllithium, and the like.

The amount of the alkali metal, alkaline earth metal hydroxide, inorganic acid salt, organic acid salt, and alkoxide used in the present invention is 0.001 to 5% by weight, preferably 0.001 to 5% by weight, based on the oxymethylene copolymer. 05-3 weight 1%. o, oo
If it is less than t% by weight, the thermal stability of the resulting composition will be low, and if it is more than 5% by weight, mechanical properties and hydrolysis resistance will deteriorate, which is not preferable.

Examples of the hinodadophenol antioxidant used in the present invention include compounds represented by the following general formula (Q).

(However, in the formula, x1,
2,2-methylene-bis(4
-methyl-5-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis(3-(3 ,5-
di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis[3-
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,6-hexanethiolubis(3-(3,5-di-tert-phthyl-4-hydroxyphenyl)propionate), 2.4- Bis-
(n-octylthio)-6-(4-hydroxy-3,5
-di-tert-butylanilino)-1,3,5-1 riazine, octadecyl-3-(3h 5-
t-Butyl-4-hydroxyphenyl)propionate, 1,3.5-trimethyl-2,4,6-tris(3,
5-tert-butyl-4-hydroxybenzyl)
Benzene, 2,2-thiobis(4-methyl-6-ter
t-butylphenol), l, 3.5-) Lis (4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isonanuric acid, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, N,N'-hexamethylenebis(3,5- Di-tert-butyl-4-hydroxy-hydrocinnamamide, bis(3,5-di-tert-butyl-4-hydroxybenodylphosphonate ethyl)calcium, N
, N'-bis(3-(3゜5-di-tert-butyl-4-hydroquinphenyl]flopionyl]hydrazine, 2-(2-hydroxy-3,5-bis((Z, α-dimethylbenzyl)phenyl) -2H-benzotriazole, 2-(3,5-tert-7mil-2-hydroxyphenyl)benzotriazole, 2-(3-tert
t-butyl-5-methyl-2-hydroxyphenyl)-
5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)
tert-butyl-2-hydroquinphenyl)benzotriazole, stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or 2,2-bis(3-(3,5-di-tert-phenyl) 4-hydroxyphenylpropanoyloxy)methyl)
-1,3-propanediol-bis(3-(3,5-di-tert-butyl-4-hydroquinphenyl)propionate).

The amount of the hindered phenol antioxidant used in the present invention is 0.001 to 0.001 to the oxymethylene copolymer.
5iit%, preferably 0.05 to 3% by weight. 0
．． If the amount of QO is less than 1% by weight, the thermal stability of the resulting composition will be low, and if it is more than 5% by weight, it will precipitate in the form of white powder on the surface of the oxymethylene copolymer, which is not preferable.

Examples of reagents capable of absorbing formaldehyde used in the present invention include amide compounds, urethane compounds, pyridine derivatives, pyrrolidone derivatives, urea derivatives, triazine derivatives, hydrazine derivatives, and amidine compounds. N-dimethylformamide, N
, N-dimethylacetamide, N,N-diphenylformamide, N,N-diphenylacetamide, N,N-
Diphenylpenozamide, N,N,N,N-tetramethyladipamide, oxalic acid dianilide, adipic acid dianilide, α-(N-phenyl)7cetanilide, nylon 6, nylon 11. Homopolymers or copolymers of lactams such as nylon 12, adipic acid, sepacic acid,
Polyamide homopolymers or copolymers derived from dicarboxylic acids such as decanedicarboxylic acid and dimaic acid and diamines such as ethylenediamine, tetramethylenediamine, hexanoterenediamine, metaxylylenediamine, and lactams. Polyamide copolymers derived from dicarboxylic acids and diamines, polyacrylamide,
Polymethacrylamide, N,N-bis(hydroxymethyl)speramide, poly(r-methylglutamate)
, amide compounds such as poly(r-ethylglutamate), poly(N-vinyl lactam), poly(N-vinylpyrrolidone), and diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate.
Polyurethanes derived from glycols such as 4-butanediol and polymeric glycols such as poly(tetramethylene oxide) glycol, polybutylene adipate, polycaprolactone, melamine, benzoguanamine, acedoguanamino, N-butylmelamine, N-phenylmelamine, N , N-diphenylmelamine, N, N, N
-triphenylmelamine, N-methylolmelamino, N
, N-dimethylolmelamine, N,N,N-1 dimethylolmelamine, 2,4-diamino-6-benzyloxytriazine, 2,4-diamino-6-butoxytriazine, 2,4-diamino-6-cyclo Triazine derivatives such as hexyltriazine, melem, melam, urea derivatives such as N-phenylurea, N,N-diphenylurea, thiourea, N-phenylthiourea, N,N-diphenylthiourea, nonamethylene polyurea, phenyl Hydrazine, lephenylhydrazine, benzaldehyde hydrazone, semicarbazone, ■-methyl-1-phenylhydrazone, thiosemicarbazone, 4-(dialkylamino)
Hydrazine derivatives such as benzaldehyde hydrazone, 1-methyl-1-phenylhydrazone, thiosemicarbazone, dicyandiamide, guantidine, guanidine, aminoguanidine, guanine, g7nacrine, guanochlor, guanoxane, guanosine, amiloride, N
-7 Midino 3-7 E / - Amidine compounds such as 6-chloropyrazinecarboxinamide, poly(2-vinylpyridine), poly(2-methyl-5-vinylpyridine), poly(2-ethyl-5-4 vinylpyridine), 2-
These include pyridine derivatives such as vinylpyridine-2-methyl-5-vinylpyridine copolymer and 2-vinylpyridine-styrene copolymer. Among them, dimic acid polyamide, melamine, guanamine, benzoguanamine, N-methylolated melamine, N-methylolated benzoguanamine, thermoplastic polyurethane resin, dicyandiamide, guanidine, poly(vinylpyrrolidone), poly(2-vinylpyridine), polyurea. , melem, and melam are particularly preferred because oxymethylene copolymers containing them have excellent thermal stability.

The amount of the agent capable of absorbing formaldehyde added is 0.001 to 5% by weight, preferably 0.05 to 3% by weight, based on the oxymethylene copolymer. O,0O
If it is less than 1% by weight, the thermal stability of the resulting composition will be insufficient, and if it is more than 5% by weight, it will precipitate on the surface of the composition or cause the composition to be colored, which is not preferable.

The composition of the present invention polymerizes trioxane and a cyclic ether using a boron trifluoride catalyst, adds a metal sulfite salt or a metal sulfite salt and a phosphine oxide as a catalyst deactivator to stop the polymerization reaction, It is produced by further adding and kneading an alkali metal or alkaline earth metal salt, a hindered phenol antioxidant, and a formaldehyde absorbent. The additives may be added one by one sequentially or may be added all at once. The additives may be added as they are, or may be added as a solution of an organic solvent.

Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-hexane, n-hebutane, and cyclohexane, alcohols such as methanol and ethanol, chloroform,
Examples include halogenated hydrocarbons such as dichloroethane and 1,2-dichloroethane, and ketones such as acetone and methyl ethyl carbonate.

The composition of the present invention may also include fillers such as calcium carbonate, barium sulfate, clay, titanium oxide, silicon oxide, mica powder, carbon fiber, glass fiber, ceramic fiber, 1 Reinforcing agents such as lamid fibers, coloring agents (pigments, dyes), nucleating agents, plasticizers, mold release agents, flame retardants, antistatic agents, conductive agents, adhesives, lubricants, hydrolysis resistance improvers, adhesion aids etc. can be optionally included.

The oxymethylene copolymer composition produced according to the present invention has excellent moldability, mechanical properties, melt stability, and heat aging resistance, so it can be used in a wide range of applications such as mechanical parts, automobile parts, and electrical/electronic parts. It can be used in

<Examples> Next, the present invention will be described with reference to Examples and Comparative Examples. In addition,
The surface condition, mechanical properties, relative viscosity pr, thermal decomposition rate K, and polymer melting point (Tm) of the molded products shown in Examples and Comparative Examples
) and crystallization temperature (Tc) were measured as follows.

Surface condition of molded product: Using an injection molding machine with a 5 oz injection capacity, the cylinder temperature was 230°C, the mold temperature was 60°C, and the molding cycle was 5.
ASTMI dumbbell test specimens and Izotsu impact test specimens were injection molded using a setting of 0 seconds. The surface condition of the obtained AsTMI dumbbell test piece was observed with the naked eye.

Mechanical properties - Tensile properties were measured according to the ASTM D-638 method using the ASTMI dumbbell test piece obtained by the above injection molding. In addition, using Izotsu impact test pieces, ASTM
Impact strength was measured according to D-256 method.

Relative viscosity Pr: p-chlorophenol 10 containing 2% α-pinene
0g? The o and 5y polymers were dissolved therein and measured at a temperature of 60°C.

Thermal decomposition rate Kx: Kx means the decomposition rate when left at X'C for a certain period of time. It was calculated using the following formula.

K x −(Wo-wl) X I OO/ Wo
9, Wo means the sample weight before heating, and W means the sample weight after heating.

The thermal balance device is a DuPont thermal analyzer 109.
0/1091 was used.

Polymer melting point ('rm), crystallization temperature (CTC): After measuring the polymer melting point ('rm) by increasing the temperature at a rate of 10°C/min in a nitrogen atmosphere using a differential scanning calorimeter, 10℃
The temperature was lowered at a rate of 1/min, and the crystallization temperature (Tc) was measured.

Reference example 1 A 3-liter kneader with two Σ-type stirring blades was heated at 60°C.
Heat to 3. Okq, l, 3-dioxolane 112F, and further boron trifluoride/diethyl etherate as a catalyst at 200P based on trioxane weight.
was added as a 10% benzene solution and stirred at 30 rpm.

The contents solidified within a few minutes and the temperature inside the system rose due to reaction heat and frictional heat, so cold air was passed inside the Σ-type stirring blade to cool it down, and the rotation speed was further lowered to lOrpm to raise the maximum temperature to 80°C. was controlled.

Stirring was continued, and the polymer was taken out after 60 minutes.

The obtained polymer was a white powder with Fr=2.37.

This polymer will be referred to as oxymethylene copolymer A.

Reference Example 2 In Reference Example 1, instead of 1,3-dioxolane,
The polymer was bulk polymerized in the same manner as in Reference Example 1, except that ethylene oxide 662 was used.

The obtained polymer was a white powder with Fr=2.40.

This polymer will be referred to as oxymethylene copolymer B.

In the following example, a
A composition was prepared using Oocct Kisser.

Examples 1-4. Comparative Examples 1-2 Various sulfite metal salts were added to the oxymethylene copolymer A obtained in Reference Example 1 in the proportions shown in Table 1, and 1
Kneaded for 5 minutes. After that, 0.13! % of calcium hydroxide and 0.5% by weight of pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxylephenyl)propionate) (C1ba
-Irganox 1010 (manufactured by Geigy) was added, the temperature was raised to 210°C for 10 minutes, and then the temperature was raised to 210°C for 20 minutes at the same temperature.
Kneaded for a minute.

Furthermore, 0.1% by weight of dicyanodiamide was added, and 21
The mixture was kneaded at 0°C for 10 minutes.

For comparison, a composition was prepared using triphenylphosphine instead of the metal sulfite salt.

Table 1 shows the results of various physical property measurements of the obtained composition.

Examples 5-6. Comparative Example 3 Except for using sodium sulfite and triphenylphosphine oxide as catalyst deactivators in the proportions shown in Table 1,
Compositions were produced in the same manner as in Examples 1-4.

For comparison, compositions were prepared using only triphenylphosphinooxide as the catalyst deactivator.

Table 1 shows the results of various physical property measurements of the obtained composition.

Examples 7 to 8 Sodium sulfite, triphenylphosphine oxyto, calcium hydroxide and I
rganox I O10It Simultaneous E+ addition, 3
The mixture was kneaded for 15 minutes at 5°C. After that, it was heated to 210℃ for 10 minutes.
After kneading at the same temperature for 20 minutes, 0.1% by weight of dicyanreamide was added and kneading at the same temperature for 10 minutes to produce a composition.

Table 1 shows the results of various physical property measurements of the obtained composition.

Examples 9 to 10 Sodium sulfite, triphenylphosphine oxide, calcium hydroxide, Ir
Ganox l O10 and dianediamide were added all at once and kneaded at 35°C for 15 minutes. Thereafter, the temperature was raised to 210° C. over 10 minutes, and the mixture was kneaded at the same temperature for 20 minutes to produce a composition.

Table 1 shows the results of various physical property measurements of the obtained composition.

Table 1 clearly shows that the composition of the present invention has excellent physical properties regardless of the type of metal sulfite salt.

It is also found that the heat resistance stability is further improved when triphenylphosphine oxide is used in combination as a catalyst deactivator. However, triphenylphosphine oxide alone
A stable composition is not obtained.

Furthermore, from the results of Example 2 (sequential addition method), Example 7 (bulk addition of ingredients other than formaldehyde absorbent), and Example 9 (-bulk addition method), the composition of the present invention can be prepared using various additive kneading methods. It can be seen that it has excellent physical properties regardless of the condition.

Examples 11-22 Compositions were produced in the same manner as Examples 2.6-10, except that magnesium hydroxide and potassium carbonate were used instead of calcium hydroxide.

Table 2 shows the results of various physical property measurements of the obtained composition.

Table 2 clearly shows that the composition of the present invention has excellent physical properties regardless of the type of alkali or alkaline earth metal salt.

Examples 23 to 34 Triethylene glycol-bisC3-(3-tert-butyl-5-methyl -4-hydroxyphenyl)propionate] (C1ba -Ge
Igy company Irganox245), N, N
'-Hexamethylenebis(3゜5-'; -tert
-butyl-4-hydroxy-humanocinnamaE)'
) (Ciba-Gcigy I rganox1
A composition was produced in the same manner as in Example 2, i3 to 10, except that 098) was used.

Table 3 shows the results of various physical property measurements of the obtained composition.

Table 3 clearly shows that the composition of the present invention has excellent physical properties regardless of the oil used as the antioxidant.

Examples 35 to 46 Compositions were produced in the same manner as in Examples 2.6 to IO, except that melamine and dimic acid polyamide (°milvex'1000, Nippon Zeol Mills) were used in place of renandiamide.

Table 4 shows the results of various physical property measurements of the obtained composition.

Table 4 clearly shows that the composition of the present invention has excellent physical properties regardless of the type of formaldehyde absorbent.

Examples 47 to 52 v Compositions were prepared in the same manner as in Examples 2.6.7.8.9 and 1O, except that the oxine methylene copolymer B obtained in Example 2 was used.

Table 5 shows the results of measuring the physical properties of each composition.

Table 5 clearly shows that even if the copolymerization components are changed, compositions with excellent physical properties can be obtained.

In all of the above examples, the compositions can also be produced using a kneading device such as a -screw or twin-screw extruder.

<Effects of the Invention> The oxine methylene copolymer composition produced according to the present invention has excellent not only melt stability but also mechanical properties, so it can be used in a wide range of applications such as machine groove parts, automobile parts, electrical and electronic parts, etc. It can be used for various purposes.

Claims (1)

[Claims] Polymerization of a mixture of trioxane and a cyclic ether with at least one member selected from the group consisting of boron trifluoride, boron trifluoride hydrate, and a coordination compound of boron trifluoride and an organic compound containing an oxygen atom or a sulfur atom. After bulk polymerization in the presence of a catalyst, a metal sulfite salt is added to deactivate the catalyst, and then the polymer is selected from hydroxides, inorganic acid salts, organic acid salts, and alkoxides of alkali metals and alkaline earth metals. An oxymethylene copolymer composition prepared by adding and mixing one or more hindered phenolic antioxidants and an agent capable of reacting with formaldehyde and absorbing formaldehyde.