JPS59129247A - Polyoxymethylene composition - Google Patents

Abstract

PURPOSE:To provide a polyoxymethylene compsn. which reduces molding strains and has improved high cycle performance, consisting of a linear polyoxymethylene and a specified branched polyoxymethylene obtd. by polymerizing formaldehyde or trioxane. CONSTITUTION:A compsn. consists of a linear polyoxymethylene and a branched polyoxymethylene having a structure wherein an alkylene oxide is added to a polyhydric alcohol obtd. by polymerizing formaldehyde or trioxane in the presence of an adduct having at least three alcoholic hydroxyl groups per molecule or by copolymerizing formaldehyde or trioxane with a cyclic ether in the presence of said adduct. Preferred cyclic ethers are ethylene oxide, ethylene glycol formal and 1,4-butanediol formal from the viewpoint of improving the mechanical properties of the linear polyoxymethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyoxymethylene A[4] product having extremely small molding distortion and high cycle performance. More specifically, it has a structure in which linear polyoxy7 methylene and alkylene oxide are added to polyalcohol,
and - in the presence of an addition compound having at least three or more alcoholic hydroxyl groups in the molecule, bomaldehy l-' or U l-! The present invention relates to a low distortion, high cycle polyoxymethylene composition comprising a branched polyoxymethylene obtained by homopolymerizing J-oxane or by copolymerizing formaldehyde or trioxane with a cyclic ether.

Polyoquinomethylene is used in a wide range of fields as an engineering plastic with excellent mechanical properties. Polyoxy/methylene is usually shaped using an injection molding machine for these uses.

Polyoxymethylene is prone to molding distortion during injection molding due to its fast crystallization rate, high crystallinity, and anisotropy during resin flow. In molded products, this distortion appears as warpage.

As a last resort to eliminate molding distortion, use t'g? Kosho 3
Japanese Patent Publication No. 7-8816 proposes the addition of polyalkylene glycol, Japanese Patent Publication No. 37-881.5 proposes the addition of an aliphatic alcohol, and Japanese Patent Publication No. 37-1617.4 proposes the addition of glycerin. These methods have the drawback of deteriorating the mechanical properties of the resin and impairing the inherent performance of polyoxymethylene.

On the other hand, in Japanese Patent Publication No. 48-8254, it is said that it is possible to homogenize the crystal structure by adding an inorganic nucleating agent.
Publication No. 48 also mentions the addition of inorganic compounds. Although inorganic nucleating agents function as excellent nucleating agents, they have deficiencies that greatly reduce the thermal stability of polyoxymethylene. Polyoxymethylene to which an inorganic nucleating agent is added tends to undergo thermal decomposition during molding.

Special Publication No. 56-42623, Special Publication No. 57-1994
In Publication No. 2, there is a proposal to add branched/reticular polyoxy/methylene. In these publications, 1.4-
Branching and
There is a description that it synthesizes reticular polyoxymethylene. These branched/reticular polyoxy/methylenes have a function as a nucleating agent, and the size of the spherulites of the molded article is reduced by the addition of these branched/reticular polyoxy7-methylenes. However, when these branched/reticular polyoxy7-methylenes are added, the molded product becomes hard and brittle.

That is, the addition improves strengths such as hardness, yield stress, tear strength, and torsional strength, but conversely decreases toughness such as elongation.

The feature of polyoxy7methylene is that it has well-balanced mechanical properties, and it is never desirable that toughness such as elongation decreases due to the addition of these branched or network polyoxymethylenes.

The present inventors have extensively studied methods for reducing molding distortion of polyoxymethylene and improving cycle performance without compromising the well-balanced mechanical properties of polyoxymethylene. , completed the invention described in detail below.

The present invention (d) has a structure in which linear polyoxymethylene and algylene oxide/do are added to a polyhydric alcohol, and -
In the presence of an additive compound (hereinafter referred to as an addition compound) having at least three alcoholic hydroxyl groups in the molecule, formaldehyde or trioxane is homopolymerized, or formaldehyde P or trioxane is combined with a cyclic ether. It is a composition consisting of a branched polyoxy/methylene (P) obtained by copolymerizing a small branched polyoxy/methylene (abbreviated as a lower branched polyoxy/methylene).

Features of the composition of the present invention are that it maintains the mechanical properties of linear polyogyamethylene without sacrificing it at all, and has low strain and high cycle performance.

The present invention will be explained in detail below.

The first linear polyoxine methylene used in the present invention is
It is a combination of formaldehyde and trioxane, and has a chain structure of oxy/methylene groups.

The second linear polyoxy/methylene is a copolymer of formaldehyde or hatrigysan and a cyclic ether compound, and has a JVA structure in which oki/methylene groups are randomly inserted between chains of oki/methylene groups. be.

The third linear polyoxy/methylene is 1. It is a copolymer obtained by the reaction of an IP criximethylene homopolymer and a cyclic ether compound, and it is
It has a structure equivalent to J oxy/methylene.

Cyclic ether compounds that are components of linear polyoxy/methylene include alkylene oxy/121 ethylene glycol formals such as ethylene oxide, propylene oxy/1, butylene oxy/-, styrene oxy, cyclohexene oxy7P, etc. There are cyclic formals such as glycol formal, triethylene glycol formal, and 1,4-r tanediol formal.

Among these cyclic ether compounds, ethylene oxide, ethylene glycol formal, and 1,4-butanediol formal are particularly useful from the viewpoint of improving the mechanical properties of linear polyoxymethylene.

When synthesizing these linear polyoxymethylenes, an anionic polymerization catalyst is used for homopolymerization of formaldehyde, an anionic polymerization catalyst and a cationic catalyst are used for copolymerization of formaldehyde, and a cationic polymerization catalyst is used in all other cases. be done.

The linear polyoxymethylene is stabilized using known terminal stabilization methods (eg, terminal esterification, terminal etherification, terminal hydrolysis) before addition.

The melting index (MI) of linear polyogyne methylene under ]90C1216Ky [As'rM-r 1238-57T] is 0.01. -70 (gr/1
0 minutes).

From the viewpoint of satisfying practical mechanical properties, it is much more important to have a value in the range of 01 to 30 than 1 point.

The first type of branched polyoxymethylene that can be used in the present invention is a polymer obtained by selectively polymerizing formaldehyde or trioxane in the presence of an addition compound.

The second type of branched polyoxymethylene is a polymer obtained by copolymerizing formaldehyde-trioxane and a cyclic ether in the presence of an addition compound.

Cyclic ethers that are components of branched polyoxymethylene include alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, ethylene glycol formal, diethylene glycol formal, triethylene glycol formal, There are cyclic formals such as butanediol formal.

Among these cyclic ethers, ethylene oxide and ethylene glycol formal are particularly important from the viewpoint of chain branching efficiency.

Additional compounds that can be used in the present invention are:

It is a compound that has a structure in which alkylene oxide is added to a polyhydric alcohol, and has at least three or more alcoholic hydroxyl groups in one molecule.

The additive compound is usually triol, -ftriol.

It is obtained by adding alkylene oxy/P to a polyhydric alcohol such as pentaol or hexaol.

Examples of polyhydric alcohols include triols such as glycerin, trimeterol prono-ξ, sorbitan monoester, and cyclycerin monoester; tetraols such as pentaerythritol, diglycerin, and sorbitan; hexaols such as fructose and cricose; and hexaols such as norbitol. There is.

Among these polyhydric alcohols, glycerin, 1-rimeterolpropane, sorbitan monoester, penquerythritol, and diglycerin are particularly preferred from the viewpoint of ease of availability and purification.

In the present invention, the alkylene oxy 7F to be added to the polyhydric alcohol includes ethylene oxy.

Propylene oxide, butylene oxide, inbutylene oxy7P, oxetane, 3,3-bis(chloromethyl)
Oxetane, TetrahyP Lofuran.

Oxepane, Styrene Oxide, Cyclohexene Oxide 7
There are de etc. Among these alkyleneoxy 1', especially ethylene oxide 7 propylene oxy/15. Butylene oxy 1, inbutylene oxy/1:'', styrene oxide and/chlorhexene oxide are useful, and ethylene oxide is particularly suitable.

The point to be noted here is the number of moles of alkylene oxide added to the polyhydric alcohol. That is, only when using branched polyoxymethylenes obtained using alkylene oxy/P adducts to polyhydric alcohols, these branched polyoxy/methylenes are added to linear polyoxy/methylenes.
It becomes possible to impart low distortion and no cycleability to the composition without impairing the mechanical properties of methylene at all. When using a compound in which 1 mol of alkylene oxide is added per 1 mol of polyhydric ano/col, when using polyhydric alcohol directly, Compared to the case where a chemical agent is used, the decrease in mechanical properties, especially toughness, is only noticeable.I have to say that this is a truly remarkable effect.

The average number of moles of alkylene oxide added per mole of polyhydric alcohol (needs to be between d1 and 150).

The lower limit of the number of moles added is limited from the viewpoint of suppressing deterioration of mechanical properties, and the upper limit is limited mainly from the viewpoint of chain branching efficiency during polymerization in which the addition compound is used. That is, when the average number of added moles exceeds 150, the chain transfer efficiency (chain branching efficiency) of the addition compound during homopolymerization/copolymerization of formaldehy P or trioxane decreases.

When the chain branching efficiency decreases, the effect of adding the branched polyoxymethylene produced also decreases, and low strain and cycleability cannot be sufficiently achieved.

From this point of view, a more preferable range of the average V number of added monomers is 2 to 70.

Here, specific examples of the compound are as follows.

Glycerin ethylene oxide adduct (average molecular weight goo
), glycerin propylene oxide adduct (average molecular weight 660), trimethylolzolo・gunetherenoxo1sa・propylene oxide? lI1. Atsuke'JJOi
(average molecular weight 1,050. ethylene oxide/propylene oxide 7t' = 3/1 (W'+ ratio)), norbitan monolaurate ethylene oxide adduct (average molecular weight λ000), nrubitan monolaurate buterene oxide Diglycerin monoacetate isobutylene oxine P adduct (average molecular weight 1.630), pentaerythritol ethylene oxide adduct (average molecular weight 1,500), penquerythritol TetrahyP lofuran additive (average molecular weight 1
, 870), diglycerin ethylene oxide 7) 4-phrase addition (
average molecular weight 810), norbitane propylene oxide adduct (average molecular weight @ 5,800), fructo-styrene oxide adduct (average molecular weight TTL, 250), glucose styrene oxide 7F adduct (average molecular weight 1.78
0), polyhydroxyboriolefin cyclohexene oxide adduct (average molecular weight 4.890, synthesized by epoxidizing and hydrogenating the double bonds of polybutadiene and containing an average of 38 alcoholic hydroxyl groups in one molecule) In the synthesis of these branched polyoxymethylenes, an anionic polymerization catalyst is used for homopolymerization of formaldehyde, an anionic polymerization catalyst and a cationic polymerization catalyst are used for copolymerization of formaldehyde, and other polymers are used. In both cases, cationic polymerization catalysts are used.

After the branched polyoxymethylene is polymerized, it can be stabilized using a known stabilization method and then used for addition, or it can also be used for addition without being stabilized.

Branched polyoquinomethylene 190C12,16K? The melting index under the standard ASTM-D 1238-57T must be between 001 and 30. That is, the branched polyoquinomethylene that can be used in the present invention is 19
It is necessary to be sure to melt at 0C.

When a branched/reticular polymer that does not melt is used, a decrease in mechanical properties, especially toughness, is observed. Therefore, in the present invention, a branched/network polymer that does not melt cannot be used.

When a polyfunctional monomer (comonomer, termonomer) such as 1,4-butane digly/dyl ether is used, the resulting polymer is usually crosslinked and becomes network-like. Polymers that have been reticulated by crosslinking no longer melt and cannot be used in the present invention.

The branched polyoxy/methylene used in the present invention only has branches and is never crosslinked or networked. Therefore, it is essentially a two-width composite that melts.

The heavier MI range of the extremely branched polyokine methylene is from 0.05 to 10.5 (gr/10 min).

The amount of branched polyoxymethylene added to 100 parts by weight of linear polyoxymethylene is in the range of 0.001 to 20 parts by weight. The lower limit of the amount added is 1 year from the viewpoint of molding distortion, and the upper limit of the amount added is limited from the viewpoint of ease of injection molding, and the more preferable range of the amount added is 0.05 to 5 parts by weight.

The size of the spherulites of linear polyoxy/methylene to which branched polyoxy/methylene is added is smaller than that in the case of explosive addition. From this fact, it is thought that the branched polyoxymethylene functions as a nucleating agent when the molten resin containing the branched polyoxymethylene is cooled and solidified.

Since this function is exhibited, it is presumed that the composition of the present invention provides a molded article with extremely small molding distortion during molding.

Even if the molding time of the composition of the present invention is shortened, especially the cooling time, the molded product does not become distorted, and the composition of the present invention gives a good molded product even with an extremely short molding time (molding cycle). . That is, the composition of the present invention has small molding distortion and 7/· cycle properties.

It is also possible to further add and use a conventionally known compound as a stabilizer for polyoxymethylene to the composition of the present invention. The first of the known stabilizers are thermal stabilizers, such as amide compounds, polyamides, amidine compounds, melamine, polyvinylpyrrolidone, and the like. The second known stabilizer is an antioxidant, such as a hindered phenol compound. A third type of well-known stabilizers are light stabilizers, such as benzotriazole compounds, hydroxy/benzophenone compounds, and the like.

These stabilizers are commonly linear polyoxymethylene 100
005 to 10 heavy h (part, more brutal 1st) to Tontobe
Part is added to (rl O,] ~ 5 r, <-.

In producing the polyoxymethylene composition of the present invention (d,
It is necessary to mix each component with each other in powder or granular form, and then homogenize using a melting device such as an extruder.

The present invention will be specifically explained below using Examples.

The meanings of the terms in the examples are as follows.

MI: Melting index (AS'T'M-DI238-57T) addition amount (p
II'r'): Linear polyoxy/methylene 1
Antioxidant AO-A; 2,2-methylenebis(4-
Methyl-6-t-butylphenol) antioxidant Ao-
+i: Pentaerythritol-tetragis (3-(
3,5-di-t-butyl-4-hydroxy-7phenol)
Propione-1 Crystallization temperature 2 A sample weighing 3.0g I)
) and heated at 2000't at a rate of 10C/min 7.2
Hold at 00C for 5 minutes. Then, it was cooled at a rate of 1067 minutes [1 it A degree showing a peak value of 1.1 is defined as the crystallization temperature. The higher the crystallization temperature, the faster the crystallization speed during molding, and the more cycleable it is.

Warpage: Determined based on the following molding conditions and measurement conditions, the smaller the lj value, the smaller the warpage value, the less molding distortion.

Molding conditions 1 doll) How many days steel? OA Molded product shape 11 ra Thickness, diameter 15 (1+nrn disk Center gate mold temperature 70C Cylinder temperature 195C Injection pressure 45 KF!/cm2G Injection time 12 seconds Cooling time 20 seconds Measurement conditions Molded product 25C150%R,H, After leaving it for 48 hours under
Measured using a dial gauge (unit: 1,/100+nm), the value of warpage is expressed as the maximum deviation of the circumference from the reference plane in μ units, with the center of one disc being the opposite surface.

Spherulite size: Cut a sample piece from the molded product using a microtome and measure using a polarized light microscope chain.

Tensile strength/tensile yield point elongation: A, Measured according to STM-G-638.

Example 1 (]) Blowing linear polyoxy/methylene anhydrous formaldehyde into /chlorohexane containing dibutyltin dilaurate as a polymerization catalyst,
Polymerization was carried out at 56tZ'. After the polymer was separated from cyclohexane, the terminals of the polymer were acetylated with acetic anhydride to stabilize the polymer. MI of this polymer
was 15.2 (grl 10 minutes).

(2) Branched polyoxy 7 methylene anhydrous formaldehyde, dibutyltin dilaurate as a polymerization catalyst, trimethylolpropane ethylene oxy 71'' adduct (average molecular weight 310, average molecular weight 310. Number of moles added 4
) was blown into chlorohexane and polymerized at 56C. After separating the polymer from cyclohexane, one polymer was stabilized by acetylating the ends of the polymer with acetic anhydride. The MI of this polymer is L 4 (grl t
o minutes).

(3) After adding the following compounds to the linear polyoxymethylene of composition (1), melt-mix them in a 50 mm $ extruder d).

(2) Branched polyoxymethylene 0.4PHR nylon 66 0.5PHRAO-A
O,3PHR The Ml of this composition is]
, 5.1 (gr710 min), and the crystallization temperature is 1
It was 51.0tZ:. The warpage of the molded product of the ox octopus composition was 130μ, and the spherulite size was 8μ. Based on these facts, it has become clear that the composition has both low molding distortion and equality. The tensile strength of the sweet octopus molded product is 760K! ; 17 cm2, the tensile elongation at yield point was 50%, and the rigidity (strength) and toughness were not decreased at all.

Example 2 (4) Linear, IP cryokymethylene 98% of anhydrous trioxane and 2% of ethylene oxide were mixed in a Nigu with two Σ blades, then 1. Boron trifluoride dibutyl etherate as a polymerization catalyst was added to initiate polymerization. After 15 minutes, tributylamine was added to stop the polymerization. A 5% triethylamine-water mixture was then added to the polymer and fed to a 65 rnrn extruder with a pentator. The MI of the polymer that underwent melt hydrolysis in the extruder to remove the terminal unstable portions was 9.0 (gr7
10 minutes).

(5) Branched polyoxy/methylene anhydrous trioxane 97.5%, ethylene oxide'2
．． 0%1 Glycerin zolopyrene oxide adduct as molecular weight regulator (combined chain branching agent) 05% (average molecular weight 2'l
o, average number of added moles of propylene oquin F 3) After mixing in the entire Nigu, boron trifluoride diethyl etherate as a polymerization catalyst was added to initiate polymerization. After 2-0 minutes, the combination was stopped and the polymer was then stabilized by subjecting it to melt hydrolysis in the extruder. MI of this polymer
was 0.95 (g r/10 min).

(6) The following compounds were added to the linear polyoxy/methylene of composition (4), and then melt-mixed in a 65 mm extruder.

(5) Branched polyoxymethylene 0.5PHR melamine 0.3PI-IRAO-B
O,4PHR
The physical properties of this composition were as follows.

, MI 9.0 (gr/10 minutes) Crystallization temperature 146.8C Warpage 140μ Spherulite size 7μ Tensile strength 650 K9-/Sune 2 Tensile yield elongation 60% This composition'FA has low molding distortion and high cycleability At the same time, it maintains excellent mechanical properties.

Example 3 (7) Linear Polyoxymethylene - Polyoxymethylene was prepared in hexane at a concentration of 25%. Ethylene oxide was blown into this) experimental suspension, and the θ degree i0.05 mole of ethylene oxide/F' was
It was adjusted to be l-hexane. Next, boron trifluoride digteretherate was added to this suspension at 60C.
The mixture was allowed to react for 10 minutes. During this time, ethylene chloride was continuously supplied so as to maintain the amount of 0.05 mole/hexane. After the reaction has stopped, the polymer is separated from the solvent and 1
Then, it was stabilized by a melt hydrolysis method. The M I of this polymer was s, s (gr/10 min), and a random copolymer in which oxy/ethylene groups were randomly inserted into polyoxymethylene was obtained.

(8) Branched oxymethylene copolymer Anhydrous trioxane 95%, ethylene glycol polymer 3% 1 molecule 41 regulator (cum-branching agent) Toshiteno Pentaerythri I
・-ruethylene oxide ・/do adduct (average molecule ('J: 5
80. Ethylene oxide 7J11 mole number 10)
Tin tetrachloride was added to the 2% mixture and mixing continued for 15 minutes. After the 4-year assembly was stopped, catalyst residue was removed by washing the combined vehicle three times with 7 types of water. MI t' of this small merger:L
, 5.4 (gr/]O min).

(9) The following compounds were added to the linear polyoxymethylene of composition (7), and the mixture was melt-mixed using a 6Frlnm extruder.

(8) Branched polyoxy7 methylene 1.0PHR di//
Andiamide 0.4PHFtAO-A
0.4PHRPEG 6000
1. OPi-IR.

The physical properties of this composition are as follows.

MI 8.9 (gr710 minutes) Crystallization temperature 147.2U Warpage 120μ Spherulite size 7μ 3 bow strength 3 650 Kp / ram2 Tensile yield point elongation 63% This wall product also has low molding distortion and cycleability It also has.

Comparative Example 1 The following compounds were added to the linear polyoxymethylene obtained in Example 1 (1), and then mixed with a molten crystal using a 50+U+91 extruder.

Nylon 66 0.5PHR A, Q -40,3PHR This composition has the following physical properties.

M I 15.2 (gr/10 min) Crystallization temperature
], 46.9C Warpage 360μ Spherulite size 215 It Tensile strength 750 Kg/ (-m2 Tensile elongation at yield point 5o% When the branched polyoxymethylene obtained in (2) of Example 1 is not added, Molding distortion is also severe, and high cycle performance is not sufficient.

After adding the following compounds to the linear polyoxy 7-methylene obtained in (4) of Example 2, the mixture was mixed with the melted sub-container using a 65 mm 1 extruder.

Noramine 0.3Pl (R AO-80,4PHR The composition has the following physical properties.

to 4 T 9.0 (gr/ 1.0
minutes) Crystallization temperature 144.5? l: Reverse Li 390μ Spherulite size 250μ Tensile strength 645Ky/α2 Tensile yield point elongation 60% When the branched polyoxyethylene/methylene obtained in Example 2 (5) is not added, molding strain is also large. - Cycleability is also insufficient.

Examples 4 to 18 00) Linear polyoxymethylene Linear polyoxy/methylene was synthesized from the starting materials and cyclic ether compounds shown in Table 1.

(11) Branched polyoxymethylene A branched polyoxy/methylene was synthesized from the starting materials, cyclic ethers, and addition compounds shown in Table 2.

The amounts added are also shown in Table 2.

(12) Composition To the linear polyoxy/methylene shown in Table 1, the branched polyoxy/methylene shown in Table 2 and the stabilizer shown below were added and melt-mixed using a 50InUI91 extruder.

Nylon 6/6-10 binary copolymer 0.5phrA
OA 0.4 phr Table 3 shows the physical properties of these compositions. In each of the examples, a composition having low distortion and cycleability is desired.

From Examples 15 to 18, it can be seen that when the amount of branched polyoxine methylene added is increased, the strain becomes smaller and the high cycle and first life tend to improve.

In each of the examples, a 7-layer acid compound exhibiting both rigidity (strength) and toughness was obtained.

(Margin) 1st Table 3 Comparative Examples 3 to 9 03) Linear Polyoxymethylene Linear polyoxymethylene was synthesized from the compounds shown in Table 4.

θ(a) Branched/reticular polyoxymethylene A branched/reticular polyoxy7-methylene was synthesized from the compounds shown in Table 5. The amount of moat added is also shown in Table 5.

051 Composition The branched/network polyoxy/methylene shown in Table 5 and the stabilizer shown below were added to the linear polyoxy/methylene shown in Table 4, and the mixture was melt-mixed using a 50ffl+N extruder.

Nylon 6/6-10 binary copolymer 0.5 phr
AO-A O, 4 phr The physical properties of these compositions are shown in Table 6. Although strain is certainly reduced by adding branched/reticular polyoxymethylene, the polymer becomes hard and brittle, resulting in a noticeable decrease in elongation. That is, although the rigidity (strength) is improved by adding branched/reticular polyogiamethylene, the toughness is conversely reduced.

Table 4 1) Gravel polyoxy/methylene same as Example 4 2
) Example 2 // 3) Example 15 // 4) Example 3 /1 5) Example 9 〃 6) Example 11/1 7) Example 6 〃 6 Table Comparative Example 10 Used in Example I The procedure was carried out in the same manner as in Example 1, except that trinotyrol pro-ξ was used in place of the trimeterol-pron-ethylene oxy/1-ethylene adduct (all the same reagents as in Example 1 were used).

(The physical properties of the composition B were as follows.

M I 14.9 (gr/10 min) Crystallization temperature
150.9 tl:' Warpage 196 μ Spherulite size 38 μ Tensile strength 790 Kp/, 2 Tensile elongation at yield point 32% A composition was prepared by adding the polymer obtained by directly using trimenalolupan without a tether of Nylene Oquine P. In this case, there is a noticeable decrease in elongation.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] (+) An addition compound having a structure in which linear polyoxymethylene and alkylene oxide are added to a polyhydric alcohol, and - having at least three or more alcoholic hydroxyl groups in the molecule. A polyoxymethylene composition (2) consisting of a branched polyoginonotylene obtained by singly bundling formaldehyde P or trioxane or by copolymerizing formaldehyde or trioxane with a cyclic ether in the presence of a linear polyoxymethylene composition (2) (3) The polyoxymethylene composition according to claim 1, wherein the polyoxymethylene is a homopolymer of formaldehyde or trioxane.
The polyoxymethylene composition (4) according to claim 1, which is a polymer, wherein the linear polyoxymethylene is a copolymer obtained by reacting a polyoxy7notylene homopolymer with a cyclic ether compound. Range of the polyoxymethylene composition according to item 1 (5) A compound in which the cyclic ether compound as a component of the linear polyoxymethylene is carried from the group consisting of ethylene oxide, ethylene glycol formal, and 1,4-butanediol formal. 190 C12,16Kp standard load (ASTM-D) of linear polyoxymethylene polyoxy/methylene silk composition (6)
1238-57T), the melting index (MI) is 0.
Composition (7) branched polyoxymethylene of 190 C, Z16 according to any one of claims 1 and 2 to 4, which is in the range of 01 to 70 (gr/10 min)
K9 standard type (ASTM, -D 1238-57T)
The melting index (MI) below is 0.01~30 (g
r/10 minutes) according to claim 1, i? Lyoxymethylene paste composition (8) The amount of branched polyoxymethylene added to 100 parts by weight of linear polyoxymethylene is o, oi ~ 20
The polyoxymethylene composition (9) according to claim 1, which is in the scope of car groin, wherein the cyclic ether that is a component of the branched polyoxymethylene is ethylene oxide or ethylene glycol polymer. Polyoxomethylene composition (In) as described in item 1. A patent in which the polyhydric alcohol is a compound selected from the group consisting of glycerin, trinotyolpropane, "fulvitan monoester, pentaerythrol, and diglycerin. Polyoxygen/ as described in claim 1
Methylene composition (marked polyoxymethylene paste composition (12) according to claim 1, wherein the alkylene oxide is ethylene oxide 7) The alkylene oxide is propylene oxide 7
The polyoxymethylene composition (13) according to claim 1, which is a compound selected from the group consisting of do, butylene oxide, isobutylene oxide, styrene oxide, and cyclohexene oxide.
The polyoxy/methylene composition according to claim 1, wherein the average number of added moles of alkylene oxy/):'' per mole is in the range of 1 to 150.