WO2005033183A1

WO2005033183A1 - Process for producing copolyacetal

Info

Publication number: WO2005033183A1
Application number: PCT/JP2004/010691
Authority: WO
Inventors: Hiroaki Nakao
Original assignee: Polyplastics Co., Ltd.
Priority date: 2003-09-30
Filing date: 2004-07-21
Publication date: 2005-04-14
Also published as: JP2005105103A; JP4472302B2

Abstract

A process for producing a copolyacetal excellent in flexibility and impact resistance by modifying a polyacetal resin by reaction with other polymer by a simpler and highly versatile technique. A polyacetal resin (A) obtained by polymerization with the aid of a catalyst for cationic polymerization is melt-kneaded together with a specific substance (B), e.g., a polymer having active hydrogen atoms in the molecule, without deactivating the cationic growing ends and the polymerization catalyst. Thus, a copolyacetal is produced.

Description

Method for producing polyester copolymer

The present invention also relates to a method for producing a polyacetal copolymer. More specifically, the polyacetal resin obtained with the thiothion polymerization catalyst is melted with a polymer having a specific reactive functional group, etc., while the growth end of the polymer or the used catalyst is active. The present invention relates to a method for producing a polymer. Background art

Polyacetal resin has a good balance of mechanical properties, chemical resistance, slidability, etc., and is easy to calose, making it a typical engineering plastic. Widely used mainly for parts. In recent years, in addition to conventional injection molding applications, the rate of crystallization and the degree of crystallization have been reduced by the addition of plasticizers and modification by copolymerization to improve workability into films, sheets, fibers, etc., and to increase toughness. Many attempts have been made.

Among them, many attempts to increase the toughness of the polyacetal resin, in particular, disclose many examples of introducing a polymer chain or the like into one polymer chain constituting the polyacetal resin to form a block copolymer.

For example, Japanese Patent Publication No. 35-2194 discloses that formaldehyde is polymerized in the presence of a polymer such as polytetramethylene glycol and a vinyl acetate copolymer to obtain a block copolymer of polyacetylene. It has been proposed. However, although the toughness of this block copolymer is slightly improved, the strength is significantly reduced.

In addition, Japanese Patent Publication No. 62-0202203 discloses that a hydroxyl group, a hydroxyl group, A production method in which formaldehyde is polymerized to an elastomer having two functional groups selected from amino groups is described. However, such blocking due to polymerization is a polymerization due to a long reaction time due to reactivity with one elastomer component and a chain transfer to a reactive functional group. It is expected that control of polymerization will be difficult. This publication also describes a method for producing a blocked polyacetal in which an elastomer having a reactive functional group is introduced by a reaction together with polyoxymethylene and a cyclic ether. However, as can be seen from the examples, a solvent is used in the reaction, which is not a simple and low-cost method, and the feasibility is low. Further, although a reaction in a non-solvent system is also assumed, there is no description of how to carry out the reaction, including Examples, and the details are not clear.

Further, Japanese Patent Publication No. Sho 61-0533369 describes a method for producing stabilized polyoxymethylene by reacting polyoxymethylene with polyalkylene oxide in the presence of a Lewis acid catalyst. This method can be either a solvent or a non-solvent system, but it requires a new addition of Lewis acid in the reaction with polyoxymethylene, and it is undeniable that excess catalyst may be a factor in reducing the molecular weight during the reaction. . Also, this publication intends to stabilize the polymer, and does not mention at all the change in mechanical properties due to the reaction.

Japanese Patent Application Laid-Open No. Hei 7-224274 discloses a method for producing a polyoxymethylene-polyurethane alloy, and Japanese Patent Application Laid-Open No. Hei 3-214624 uses a diisocyanate coupling agent. There is a description about the grafting of a functional compound to a functional oxymethylene polymer skeleton, but these are all cases in which isocyanate is used as a reactant. Although isocyanate has high reactivity and shows an excellent effect as a reactant in polymer modification, it has recently been shunned as an environmentally harmful substance, and a method using no isocyanate compound is desired. Disclosure of the invention

The present invention has been made in view of the above prior art, and has been made of a polyacetone resin having flexibility and excellent impact resistance.

—In the production of Leju J3, the objective is to produce a flexible and impact-resistant polyacetal copolymer by a simpler and more versatile method of modification by reaction with a polymer.

As a result of intensive studies to achieve the above object, the present inventors have found that a polyacetal resin obtained by cationic polymerization can be mixed with a polymer having a specific reactive functional group or a conjugate before passing through the quenche process. It has been found that the desired polymer modification can be performed without addition of a solvent, a reactant, or a catalyst or an initiator for accelerating the reaction by melt mixing, and the present invention has been completed. .

That is, the present invention provides a method for producing a polyacetal resin (A) obtained by polymerization using a cationic polymerization catalyst without performing the cation growth terminal and the deactivation treatment of the polymerization catalyst by the following (B-1) to (B-1). This is a method for producing a polyacetal copolymer, which is characterized by being melt-mixed with a substance (B) selected from B-4).

B-1: Polymer having active hydrogen atoms in the molecule

B-2: Polymer having glycidyl group in the molecule

B-3: Polymer obtained by formalizing an aliphatic polyether having a hydroxyl group in the molecule or an aliphatic polyester having a hydroxyl group in the molecule

B-4: A compound obtained by formalizing an alkyl monool having 6 or more carbon atoms or an alkylene diol having 6 or more carbon atoms.

Hereinafter, the method for producing the polyacetal copolymer of the present invention will be described in detail. In producing the polyacetal copolymer in the present invention, Po Li acetal resin as its base (A) is the main constituent of Okishimechiren units (one CH ₂ 0-) A polyacetal homopolymer or a polyacetal copolymer containing one unit of another comonomer besides oxymethylene groups may be used as long as it is a polymer compound having a unit and is produced using a cationic polymerization catalyst. Further, the polyacetal resin (A) may have a branched structure as well as a linear structure, and may have a crosslinked structure. The degree of polymerization is not particularly limited as long as it can be melt-processed.

When the base polyacetal resin (A) is a polyacetal copolymer, the comonomer units constituting the copolymer include oxyalkylene units having about 2 to 6 carbon atoms, such as oxyethylene groups (—CH ₂ CH ₂ 〇-1) oxypropylene group, oxytetramethylene group, etc. S are included. The content of the comonomer unit needs to be an amount that does not significantly impair the crystallinity of the polyacetal resin (A). For example, the oxymethylene unit 100, which is a main constituent unit of the polyacetal resin (A), may be used. It can be selected from the range of 0.01 to 20 mol, preferably 0.03 to 10 mol, and more preferably 0.1 to 5 mol, per mol. The polyacetal copolymer is obtained by mixing trioxane (a-1) with a cyclic ether compound (a-2) selected from ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal and methylene glycol formal. It is convenient and preferable to obtain the copolymer by using a cationic polymerization catalyst.

When the polyacetal resin (A) serving as the base is a polyacetal homopolymer, such a homopolymer can be obtained by homopolymerizing trioxane / tetraoxane, which is a cyclic oligomer of formaldehyde, using a cationic polymerization catalyst.

Examples of the cationic polymerization medium used in the production of the above-mentioned polyacetal resin (A) include lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium dichloride, antimony trichloride, and pentafluoroethylene. Dani phosphorus, antimony pentafluoride, Boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetate dihydrate, boron trifluoride triethylamine complex compound, etc. To coordination compounds, inorganic and organic acids such as perchloric acid, acetylbutyl chloride, t_butylpropyl chloride, hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid, triethyloxodimethyltetrafluoroborate, and triphenylmethyl Complex salt compounds such as xiafluoroantimonate, aryldiazoniumhexafluorophosphate, aryldiazotetratetrafluoroporate, and alkyls such as getyl zinc, triethyl aluminum, and getyl aluminum chloride Examples include metal salts, heteropoly acids, and isopoly acids. Among them, boron trifluoride, boron trifluoride getyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetate anhydride, boron trifluoride triethylamine complex Boron trifluoride coordination compounds such as compounds are preferred. In the polymerization, it is also possible to use a molecular weight modifier. The present invention provides a polyacetyl resin (A) obtained by polymerization using a cation polymerization catalyst as described above, without subjecting the cationic growth terminal and activation of the polymerization catalyst to a specific substance described below. A method for producing a polyacetal copolymer, which is characterized by melt-mixing and reacting with (B).

In the production of a commercially available ordinary polyacetal resin, a basic compound is added immediately after polymerization to a polymer obtained by polymerization using a cationic polymerization catalyst, or the polymer is added to an aqueous solution thereof. In the present invention, the cation growing end of the catalyst and the polymer is deactivated (quenched) and the product is further processed through a stabilization step. In the present invention, the product reacts with the cation growing end of the polymer in the presence of a catalyst maintaining the activity It is characterized by further reacting with a specific substance (B) having an acidic functional group under melting. The polyacetal resin (A) in which the catalyst and the like are in an active state for the reaction may be in the form of flakes obtained by polymerization, or may be melt-blended once with an antioxidant represented by hindered phenols. May be used. In order to maintain the activity of the catalyst in a more favorable state, avoid contact and mixing with a basic component that causes catalyst deactivation until melt-mixing with the substance (B) having a reactive functional group. There is a need.

In the present invention, the substance (B) to be melt-mixed with and reacted with the polyacetyl resin (A) is selected from the following polymers and compounds.

B-1: Polymer having active hydrogen atoms in the molecule

B-2: Polymer having glycidyl group in the molecule

B-4: Compound obtained by formalizing alkyl monool having 6 or more carbon atoms or alkylene diol having 6 or more carbon atoms

The polymer (B-1) to be melt-mixed with the non-quenched polyacetone resin (A) may be a polymer having an active hydrogen atom in the molecule, and may be a reactive functional group having an active hydrogen atom. And mainly include a hydroxyl group, a sulfoxyl group, an amino group, and a methylcapto group. The polymer (B-1) is preferably a bifunctional polymer having such a reactive functional group having an active hydrogen atom at both ends. In consideration of the reactivity with the polyacetal resin (A) obtained by cation polymerization, the reactive functional group of lima (B-1) is preferably a hydroxyl group.

The molecular skeleton of the polymer (B-1) is preferably a soft segment component which can be an elastomer, for example, an alkylene glycol unit, a polyester or a polyether containing an aliphatic alkylylene nit, and a specific example. Polyethylene glycol, polypropylene alcohol, polytetramethylene glycol, and And monoalkyl ethers thereof, and furthermore, copolymers of polyalkylene glycols represented by a copolymer of polyethylene glycol and polypropylene glycol, and monoalkyl ethers thereof are also effective. Furthermore, polytrimethylene glycol and polyhexamethylene glycol, which are ring-opening polymers of oxetane dioxepane, and their monoalkyl ethers, and aliphatic polyesters represented by poly ε-force prolactone and poly δ-valerolactone Examples of the polymer include a polymer having a structure and a terminal group having a monool or diol. Further, a polymer having a repeating unit of [-0 (CH ₂ ) n-0 CH _r ] (where n = 2 or more) is also effective as a polyester. Examples include poly (dioxolane) diol and poly (dioxepane) diol. In addition, if the polymer has an active hydrogen at the terminal, particularly a hydroxyl group, gen-based polymers such as polybutadiene and polyisoprene having a hydroxyl group at one end or at both ends in addition to the above, and hydrogenated gen-based polymers thereof. Elastomers may be used. Further, bisphenol A or a polymer having a hydrogenated bisphenol A structure or the like can be used as a copolymerization component in one polymer unit.

Of these polymers (B-1), particularly preferably any one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, poly (dioxolane) diol, poly (dioxepane) diol, and monoalkyl thereof It is an ether derivative. Further, the polymer (B-1) preferably has a number average molecular weight of 2000 or more. If the average molecular weight is smaller than 2000, the resulting polymer will have a remarkable reduction in molecular weight due to the chain transfer reaction that occurs during melt mixing, and the desired flexible and impact-resistant polyester resin will be used. The polymer cannot be obtained.

Next, specific examples of the polymer (B-2) to be melt-blended with the non-quenched polyacetal resin (A) will be described. The polymer (B-2) has a glycidyl group in the molecule. The basic skeleton of the polymer (B-2) is a soft segment component that becomes an elastomeric element in the polyacetal copolymer as exemplified in the polymer (B-1). Is desirable. Specific examples include glycidyl ethers of polyalkylene glycols represented by polyethylene glycol, polypropylene alcohol, and polytetramethylene glycol, and polyalkylene glycols represented by a copolymer of polyethylene glycol and polypropylene glycol. Glycidyl ether such as a copolymer of Furthermore, polytrimethylene glycol, which is a ring-opening polymer of oxetane or oxepane, daricidyl ether of polyhexamethylene daricol, and poly-ε polymer having an aliphatic polyester structure represented by 力Daricidyl ether and aliphatic dalicidyl ether having a long-chain alkyl group in the molecule. Further, the above polymer containing a bisphenol A unit or a hydrogenated bisphenol A unit as an intramolecular copolymerization component may be used.

Further, as a polymer (B-3) capable of being melt-blended with a non-quenched polyacetal resin (A) to form a polyacetal copolymer, an aliphatic polyether having a hydroxyl group in the molecule or Examples include polymers obtained by formalizing an aliphatic polyester having a hydroxyl group in the molecule. Examples of the aliphatic polyethers and aliphatic polyesters used in the homogenization include the polyalkylene glycols listed in section (B-1), polyesters containing aliphatic alkyl units, and polyethers. Is preferred. The polymer (B-3) is a formali conjugate obtained by a dehydration reaction by heating a hydroxyl group in the polymer and an aqueous solution of formaldehyde or formalin under an acid-producing catalyst. The polymer used in the formalization reaction is However, it may be a monool having one hydroxyl group in the molecule or a polyol having two or more hydroxyl groups in the molecule. Polymers (B-1 3) are obtained by bimolecular reaction between polymers or by reaction between multiple molecules, Alternatively, it may be a cyclic formal formed by an intramolecular reaction, or a mixture thereof.

Further, the compound (B-4) capable of being melt-mixed with the non-quench polyacetal shelf (A) to form a polyacetal copolymer is an alkyl monool having 6 or more carbon atoms or a carbon monool. It is a compound obtained by formalizing an alkylene diol of number 6 or more. Examples of the diols used mainly include aliphatic alkylene diols, and linear diols such as 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. These 1,2-hydroxyl substituents are exemplified. As long as the alkylene chain has 6 or more carbon atoms, even if it has a branched structure or has a cyclic alignment unit, it can be reacted with the polyacetylene resin (A) by melt-kneading. The formal irrigation compound used is preferably basically a cyclic compound formed by an intramolecular formalization reaction, but may contain a formalized compound formed by an intermolecular reaction.

The non-quenched polyacetal resin (A) and the substance (B) selected from the above (B-1) to (B-4) are melt-mixed and reacted to form a polyacenyl copolymer. In the production, melt kneading by a known single-screw or twin-screw extruder is generally used, but the mixing method is not particularly limited. Melt mixing is performed in a temperature range of 100 to 230 ° C. However, considering that the catalyst is a reaction between a non-quenched polyacetal resin in an active state and another polymer or compound, A range of 50 to 210 ° C. is desirable.

The amount of the substance (B) selected from (B-1) to (B-4) used in the melt mixing is 1 to 50 parts by weight based on 100 parts by weight of the non-quenched polyacetal resin (A). It is preferably in parts by weight. If the amount is less than 1 part by weight, it is difficult to obtain the polyacetal copolymer which is the object of the present invention and is excellent in impact resistance. If the amount is more than 50 parts by weight, strength and rigidity are remarkably reduced. . As described above, the polyacetone resin (A) and the specific substance (B) are melt-mixed and reacted to form a polyacetone copolymer, and the remaining polymerization catalyst is deactivated. The deactivation is performed by adding to the reaction product (polyacetal copolymer) obtained by melt mixing: a base compound or an aqueous solution thereof, or the like, and then melt-mixing the same together with these.

Examples of the basic compound for neutralizing and deactivating the polymerization catalyst include ammonia, amines such as triethylamine, triptylamine, triethanolamine, and tributanolylamine, or alkaline metal and alkaline earth metal. And other known catalyst deactivators. If necessary, a stabilization treatment by a known method, such as decomposition and removal of an unstable end portion by melting and mixing in the presence of a basic compound, or blocking of an unstable end by a stable substance, is performed.

The stabilized polyacetal copolymer can further contain various necessary stabilizers, such as hindered phenolic compounds, nitrogen-containing compounds, hydroxides of alkaline metal or alkaline earth metal, One or more of inorganic salts, carboxylate salts and the like can be mentioned. Further, as long as the present invention is not hindered, general additives for thermoplastic resins, such as coloring agents such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents, surfactants, Alternatively, one or more kinds of organic polymer materials, inorganic or organic fibrous, powdery, and plate-like fillers can be added. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Examples 1 to: L7 and Comparative Examples 1 to 7

As shown in Tables 1-3, the polyacetal tree in non-quenched or quenched state In (A), various polymers or compounds were melt-blended, and a polyacetal copolymer was prepared and evaluated. The results are shown in Tables 1-3.

The method for preparing the used polyacetal resin (A), the method for preparing the polyacetal copolymer by melt-kneading, the substances used for the reaction by melt-kneading (B) ((B-1) ~

The method for evaluating the (B-4) polymer or compound) and the obtained polyacetal copolymer are as follows.

[Preparation of polyacetal resin (A)]

1— 1) Non-quenched polyacetal resin (A)

Trioxane, 1,3-dioxolane and a small amount of methylal as a chain transfer agent are fed to a twin-screw extruder-type continuous polymerization apparatus with a jacket temperature of 8 (TC), and BF is used as a cationic polymerization catalyst. _The polymerization was carried out by supplying _3, and flake-like polyacetal resin (A) was continuously collected from the outlet of the polymerizer.The feed ratio of trioxane and 1,3-dioxolane used in the polymerization was 96: 4. The obtained flake-shaped polyacetal resin (A) is a material that does not require deactivation of the catalyst with a basic compound and that suppresses the progress of chain transfer and decomposition reaction. It was temporarily stored in a freezer at 135 ° C until it was melt-mixed with (B).

1-2) Quench-treated polyacetal resin (A-Quench)

The quench-treated polyacetal resin (A-q: unch) used in Comparative Examples 1 to 3 was prepared by converting the polyacetal resin taken out in a flake form from the outlet of the polymerization machine in the above polymerization into a 5% aqueous solution of triethylamine. After immersing the catalyst for more than an hour to deactivate the catalyst, it is dehydrated and dried, and then with a small amount (0.04% by weight) of an antioxidant (trade name “Ilganox 100”). It was prepared by melt-kneading at 100.

[Preparation of polyacetal copolymer by melt mixing] The melt kneading of the non-quenched poly 7-cetal resin (A) and the selected material (B) with (B-1) to (B-4) forces is performed by a twin-screw extruder (Nippon Steel Works, Ltd.). Manufactured by TEX-30). The cylinder temperature in the melt-kneading is 180 ° (: ~ 200 (die head part), the screw rotation is 120 rpm, and the feed rate is 6 kg / hr. The obtained polyester copolymer is pelletized, Reactivate the catalyst by adding 3 parts of a 5% aqueous solution of triethylamine and 0.2 parts by weight of a hindered phenolic antioxidant (Ilganox 1010; manufactured by Ciba Specialty Chemicals) again by melt mixing. A stabilization treatment was performed together with the treatment.

In Comparative Examples 1 to 3, the same melt-kneading as described above was performed using a quenched polyacetal resin (A-quench). However, the addition of the aqueous solution of triethylamine in the remelting kneading was not performed.

[Material used for the reaction by melt-kneading (B)]

The polymer (B-1), polymer (B-2), polymer (B-3) and compound (B-4) used as the substance (B) in the examples are as follows.

The polymer without active hydrogen (Β ') used in the comparative example is also shown.

(Β-1)

Β— 1— 1) Polyethylene glycol 20000 (Kishida Chemicals / Reagents)

B-1-2) Polypropylene glycol diol type 3000 (Wako Pure Chemicals' reagent)

Β— 1— 3) Polypropylene glycol monobutyl ether (Μη = 4000)

(Aldrich products and reagents))

Β- 1 -4) PEG— PPG— PEG (block polymer; Mn = 580 0) (Sydama Aldrich product / reagent)

B-1-5) Polycaprolactone (diol type) "BRAXEL H5" (manufactured by Daicel Chemical Industries) B- 1 -6) Polytetramethylene glycol “PTG3000” (manufactured by Hodogaya Chemical)

B-1 -7) Poly (3-hydroxybutyric acid) diol (Sigma-Aldrich product / agent)

B-1-8) Polybutadiene "G3000" (manufactured by Nippon Soda), hydroxyl-terminated at both ends B-1-9) Poly (dioxolane) diol (synthetic product)

The synthesis of poly (dioxolane) diol was performed as follows. 200 g of 1,3-dioxolan was poured into a 500 ml polymerization kettle, and the internal temperature was set to 301. As a catalyst, phosphorous tungstate hydrate is added to methyl formate in a concentration 150 times

The solution diluted by (weight ratio) was added in an amount of 20 ppm in terms of phosphorous tungstic acid to carry out polymerization. When the viscosity in the system was sufficiently increased, 1% of a 2% aqueous solution of dioxolane of triethylamine was added as a polymerization terminator. After stirring for another 15 minutes, the system was evacuated to remove unreacted monomers to obtain poly (dioxolane). Further, the obtained polymer is mixed with a 5% aqueous triethylamine solution.

(3% added) and melt kneading to remove the unstable terminal, thereby obtaining a polymer having a stable hydroxyl terminal.

(B-2)

B— 2-1) Polyethylene glycol diglycidyl ether, Mn = 526 (Shimad Aldrich product / reagent)

B-2-1-2) Polypropylene glycol diglycidyl ether, Mn = 640 (Aldrich product, reagent)

B- 2-3) Epoxy / hydroxylated polybutadiene, Mn = 2600 (Aldrich product / reagent)

(B-3)

B— 3— 1) Polypropylene glycol formal (synthetic product) Holma Illui-dani performed as follows. 40 g of polypropylene glycol 400 (manufactured by Shimadama-Aldrich Co., Ltd.) and formalin aqueous solution 2 Om1 are charged into a 20 Om1 eggplant flask, a small amount of benzene (about 10 ml) is added, and 0.2 ml of sulfuric acid is added as a catalyst. did. Flask temperature 100. (: Set to, reflux for about 1 hour, attach a cooling pipe for distillation, raise the temperature in the system to 110, and azeotropically evaporate the water generated by the reaction with benzene. Benzene was added to the system as needed, and the reaction was continued until no more water distilled out After the reaction was completed, the system was neutralized with KOH, and acetone was added. Acetone and a trace amount of water were removed by evaporation, and the resulting reaction product detected a ¹ H-NMR peak at <5 = 4.75 ppm. The formalization reaction was confirmed by the presence of formal unitite.

B—3—2) Formal compound of polypropylene glycol monobutyl ether (Aldrich product. Reagent) (synthetic product; see B-3-1) for synthesis procedure)

(B-4)

B-4-1 1) Formalization of 1,9-nonanediol (Tokyo Kasei Kogyo 'Reagent') (synthetic product; see B-3-1) for synthetic procedure)

B-4-2) Formalization of 1,12-dodecanediol (Tokyo Kasei Kogyo's reagent) (synthetic product; see B-3-1) for synthetic procedure)

(Β ') Polymer without active hydrogen

B '― 1) Polyethylene glycol dimethyl ether, Μη = 500 (Sigma-rich product / reagent)

B '-2) Polypropylene glycol diacrylate, Μη = 900 (Aldrich product / reagent)

B '— 3) Polybutadiene “Β3000” (manufactured by Nippon Soda), both ends ¾methyl type B' —4) Polypropylene “Noblen W101” (manufactured by Sumitomo Chemical Co., Ltd.) [Analysis and evaluation of polyester copolymer]

After dissolving 3 Omg of the obtained polyacetal copolymer polymer in hexafluoroisopropanol, the polymer or compound (B-1) to (B-4) or (Β ') used for melt-kneading (reaction) is dissolved. The precipitate was reprecipitated in a soluble solvent, and unreacted (Β-1) to (Β-4) or (Β ') was removed and analyzed. The re-precipitated polyacetal copolymer was dissolved in 0.6 ml of polymer hexafluoroisopropanol d2 and analyzed by 'H-NMR to obtain (B- 1) to (B-4) The amounts of components introduced were calculated.

Furthermore, the obtained polyacetal copolymer was subjected to a bow I tension test using a Toshiba IS 80EPN molding machine in accordance with ISO standard conditions (9988-2) in order to evaluate tensile strength and elongation and Charpy impact test. Pieces and bending test pieces were collected. The obtained test specimen was left for 48 hours under the conditions of a temperature of 23 ° C and a humidity of 50%, and the tensile test was measured according to IS-527, and the Charpy impact test was performed using a notched bending test specimen according to ISO 179. Was done.

The MFR was measured using a melt indexer (Takara Kogyo Co., Ltd.) based on ISO 133 and using a piston with a load of 2160 g for 7 minutes at the temperature shown below. The amount [g] of the molten resin composition to be used was evaluated by converting it per 10 minutes.

The results are shown in Tables 1-3.

Table 1 Example Example Example Example Example Example Example Example Example Example Example Example

1 2 3 4 5 6 7 8 9 1 0 Riacetar resin (A) wt% 9 5 9 0 95 9 0 9 5 9 5 9 5 9 5 9 5 9 5 Lima-B-1-1) 5 1 0

B- 1 -2) 5

B-1-3) 1 0

B- 1 -4) 5

B-1 -5) 5

B-1 -6) 5

B- 1 -7) 5

B- 1 -8) 5

B- 1 -9) 5

(B) Introduced amount of component Weight% 2.1.4.2.4.4.92.5.4.2.3.03.02.6.4.8

MFR g / 10tnin 4. 4 6. 3 5. 5 6. 6 3. 9 3. 1 5. 0 6. 4 5. 1 3.6 Tensile strength MPa 55 50 54 51 54 56 54 54 52 55 Tensile elongation MPa 59 55 67 53 60 65 62 60 78 50 Charvi-impact (with notch) kJ / m ² 1 0.5 1 2.5 1 1.9 1 1.0 1 1.5 1 3.3 1 2.0 1 0.8 1 2.5 1 0.0

¾ +

1 Example Example Example Example Example Example Example Example Example

1 1 1 2 1 3 1 4 1 5 1 6 1 7 Polyacetal resin (A) Weight% 95 95 95 95 95 95 95

Five

B-2-2) 5

B-2-3) 5

B-3-1) 5

B-3-2) 5

Compound B- 4-1) 3

B-4-2) 3

(B) Introduced amount of component Weight% 3.8 3. 5. 2. 9. 3. 5. 4. 4 2. 1 2. 3

MFR g / IOmin 3.5 5.3.4 3.7 4.2 4.4 3.4 3.7 Tensile strength MPa 53 53 52 54 55 56 56 Tensile elongation MPa 63 67 78 60 53 55 60 KJ / m ² 1 2.0 1 2. 8 1 4.0 1 2. 1 1 0.5 1 0. 2 1 0.3

Table 3

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example τ e. Riacetar-resin (A) Weight% 95 95 95 95 White Riacetar-resin (A-inch) 1 00 95 95

E. Lima B-1-1) 5

B-2-1) 5

B'-1) 5

B'-2) 5

B'-3) 5

B 4) 5

(B) Introduced amount of component (% by weight)-0.0 0 0 0 0 0 0 0 0 0.0 0 0.0

MFR g / 10min 3.3 3.3.4 3.4.3 3.3.3 3.3.5.4.5 Tensile strength MPa 61 60 60 60 60 61 60 Tensile elongation Pa 46 45 43 45 46 49 46 Charpy impact ( Notch) kJ / m ² 8.5 8. 4 8. 6 8. 8 8. 6 8. 8 8.5

Claims

The scope of the claims

1. The polyacetal resin (A) obtained by polymerization using a cationic polymerization catalyst is converted into the following (B-1) to (B-4) A process for producing a polyacetal copolymer, which is melt-blended with a substance (B) selected from the group consisting of:

B-1: Polymer having active hydrogen atoms in the molecule

B-2: A polymer having a glycidyl group in the molecule

2. The method for producing a polyacetal copolymer according to claim 1, wherein the polymer (B-1) is a bifunctional polymer having active hydrogen atoms at both ends.

3. The method for producing a polyacetal copolymer according to claim 1, wherein the active hydrogen atom of the polymer (B-1) is derived from a hydroxyl group.

4. Polymer (B-1) force The method for producing a polyacetal copolymer according to any one of claims 1 to 3, which has an aliphatic polyether skeleton or an aliphatic polyester skeleton.

5. The polymer (B-1) is polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, poly (dioxolane) diol, poly (dioxepane) diol and monoalkyl ether derivatives thereof. 4. The method for producing a polyester copolymer according to claim 1, wherein the copolymer is selected from the group consisting of:

6. The polymer (B-2) is an aliphatic polyether skeleton or aliphatic polyester O 2005/033183 The method for producing a polyacetal copolymer according to claim 1, which has a skeleton.

7. The polyacetal resin (A) is composed of trioxane (a-1) and a cyclic ether compound (a-2) selected from ethylene oxide, 1,3-dioxolan, 1,4-butanediol formal and diethylene glycol formal. The method for producing a polyacetal copolymer according to any one of claims 1 to 6, which is obtained by copolymerization using a cationic polymerization catalyst.

8. The method according to claim 1, wherein 1 to 50 parts by weight of a substance (B) selected from (B-1) to (B-4) is melt mixed with 100 parts by weight of the polyacetal resin (A). The method for producing the polyacetal copolymer according to any one of claims 1 to 7.