WO2020137414A1 - Composition de résine polyacétal, et procédé de fabrication de celle-ci - Google Patents

Composition de résine polyacétal, et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2020137414A1
WO2020137414A1 PCT/JP2019/047575 JP2019047575W WO2020137414A1 WO 2020137414 A1 WO2020137414 A1 WO 2020137414A1 JP 2019047575 W JP2019047575 W JP 2019047575W WO 2020137414 A1 WO2020137414 A1 WO 2020137414A1
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group
polyacetal resin
polyacetal
resin composition
formula
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PCT/JP2019/047575
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English (en)
Japanese (ja)
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直裕 喜来
栄次 増田
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ポリプラスチックス株式会社
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Priority to CN201980062586.5A priority Critical patent/CN112752779B/zh
Publication of WO2020137414A1 publication Critical patent/WO2020137414A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/04—Copolyoxymethylenes

Definitions

  • the present invention relates to a polyacetal resin composition having excellent mechanical properties and a method for producing the polyacetal resin composition.
  • Polyacetal resin has excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, etc., and is mainly used as electrical materials, automobile parts, precision machinery as structural materials and mechanical parts. Widely used for parts. However, with the expansion of fields in which polyacetal resins are used, the required properties tend to become more sophisticated, complex, and specialized. As such required properties, further improvement is required for improving rigidity and suppressing generation of formaldehyde while maintaining the excellent slidability, appearance, etc. originally possessed by the polyacetal resin.
  • Patent Document 1 Attempts have also been made to improve the rigidity by blending a polyacetal copolymer having a branched structure introduced therein (Patent Document 1), but at the time of polymerization of the polyacetal copolymer having a branched structure introduced, a cationic polymerization catalyst, depending on the type of comonomer, In particular, when a protonic acid is used as a polymerization catalyst, the initiation of polymerization may be delayed and the polymerization may suddenly and explosively occur, which is a problem from the viewpoint of production stability.
  • Patent Document 2 a copolymer obtained by copolymerizing trioxane and a compound having two or more glycidyl ether groups in one molecule has been proposed (Patent Document 2).
  • Patent Document 2 a compound having a plurality of epoxy groups represented by glycidyl ether groups and a plurality of ether oxygens as functional groups for polymerization.
  • a protic acid is used as a polymerization catalyst, polymerization does not occur at a low catalyst amount, and increasing the catalyst amount causes a phenomenon in which a sudden violent polymerization reaction occurs after an irregular induction period, making polymerization control difficult. ing.
  • An object of the present invention is to provide a polyacetal resin composition having an improved level of mechanical properties and a method for producing the polyacetal resin composition.
  • the present inventor as a result of diligent studies to achieve the above-mentioned object, based on a polyacetal resin as a base, by blending a polyacetal copolymer obtained by copolymerizing a trioxane and a specific siloxane compound, it has not been previously predicted.
  • the inventors have found that it is possible to improve mechanical properties to some extent and have reached the present invention described below.
  • the above-mentioned copolymer (B) is a polyacetal copolymer (B) obtained by copolymerizing a cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring as a comonomer.
  • Me represents a methyl group. 5.
  • Polyacetal resin obtained by mixing 0.1 to 100 parts by mass of a polyacetal copolymer (B) obtained by copolymerizing at least a trioxane (a) and a siloxane compound (b) represented by the formula (1) A method for producing a composition.
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • X is R 1 or an organic group having an epoxy group, respectively.
  • two or more of plural X's are organic groups having an epoxy group, and plural R 1's and X's may be the same or different.
  • the polyacetal resin composition of the present invention comprises a polyacetal resin (A), a trioxane (a) and a siloxane compound (b) represented by the formula (1).
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • X is R 1 or an organic group having an epoxy group, respectively.
  • two or more of plural X's are organic groups having an epoxy group, and plural R 1's and X's may be the same or different.
  • a polyacetal copolymer (B) obtained by copolymerizing a cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring, and a polyacetal resin composition containing the polyacetal copolymer (B).
  • the compounding amount of the polyacetal copolymer (B) is 0.1 to 100 parts by mass, preferably 0.3 to 100 parts by mass, relative to 100 parts by mass of the polyacetal resin (A). It is a department.
  • the polyacetal resin (A) which is the substrate of the resin composition of the present invention, is a polymer compound having an oxymethylene unit (—CH 2 O—) as a main constituent unit, and an acetal homopolymer (for example, manufactured by DuPont, USA). (Trade name “Delrin” and the like), and acetal copolymers containing other comonomer units in addition to the oxymethylene group (for example, product name “Duracon” manufactured by Polyplastics Co., Ltd.) are included.
  • an acetal copolymer is particularly preferable in terms of its thermal stability and the like.
  • the comonomer unit has an oxyalkylene unit having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms) (eg, oxyethylene group (—CH 2 CH 2 O—), oxypropylene group, oxy). Butylene groups, etc.) are included.
  • the content of the comonomer unit is an amount that does not significantly impair the crystallinity of the resin, for example, as a proportion of the constitutional unit of the polyacetal polymer, generally 0.01 to 20 mol%, preferably, It can be selected from the range of 0.03 to 10 mol %, and more preferably 0.1 to 7 mol %.
  • the acetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like.
  • the acetal copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.
  • the degree of polymerization, branching degree and crosslinking degree of the polyacetal resin (A) are not particularly limited as long as they can be melt-molded.
  • the polyacetal copolymer (B) of the present invention comprises a trioxane (a) and a siloxane compound (b) represented by the formula (1).
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • X is R 1 or an organic group having an epoxy group, respectively.
  • two or more of plural X's are organic groups having an epoxy group, and plural R 1's and X's may be the same or different.
  • a polyacetal copolymer (B) obtained by copolymerizing a cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring, as the case may be.
  • the trioxane used in the present invention is a cyclic trimer of formaldehyde, which is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is used after being purified by a method such as distillation. ..
  • the component (b) used in the present invention is a siloxane compound represented by the formula (1).
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • X is R 1 or an organic group having an epoxy group, respectively.
  • two or more of plural X's are organic groups having an epoxy group, and plural R 1's and X's may be the same or different.
  • R 1 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Saturated monovalent aliphatic hydrocarbon groups such as alkyl groups such as n-butyl group, t-butyl group and heptyl group, unsaturated monovalent fatty acids such as alkenyl groups such as vinyl group, allyl group, isopropenyl group and butenyl group.
  • Group hydrocarbon group preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, and more preferably methyl group. ..
  • the organic group in X represents a compound composed of C, H, N and O atoms
  • specific examples of the epoxy group-containing organic group include 2-(3,4-cyclohexyl)ethyl group and 3-glycidoxy group.
  • examples thereof include a propyl group, and a 2-(3,4-cyclohexyl)ethyl group is preferable from the viewpoint of stability of the polymerization reaction.
  • the number of carbon atoms in the organic group is preferably 1 to 20, and more preferably 3 to 15.
  • a 2-(3,4-cyclohexyl)ethyl group with an alkylene group having 1 to 5 carbons interposed is preferable from the viewpoint of polymerization stability and mechanical strength.
  • the siloxane compound of the formula (1) can be produced by a method described in a known document, for example, JP 2010-229324 A or JP 2016-204288 A. When these production methods are applied, a 6-membered ring, 10-membered ring or 12-membered cyclic siloxane having 3, 5 or 6 units of siloxane units bonded may be produced as a by-product, but their presence is There is little influence on the production of the polyacetal copolymer of the present invention, and it is sufficient that the 8-membered cyclic siloxane of the present invention is contained in an amount of 80% by mass or more.
  • the reason why the control of the polymerization is facilitated is that the siloxane ring structure of the formula (1) causes the epoxy group, which is a copolymerization reaction point, to have a relatively high molecular weight. It is speculated that this is because the reaction probability is improved because it is fixedly arranged outside.
  • a particularly preferred siloxane compound is the following compound (b-1).
  • Me represents a methyl group.
  • the component (b) is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.03 to 1 part by mass, based on 100 parts by mass of trioxane. ..
  • cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring can be further used as a comonomer.
  • the cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in the ring of the present invention is a compound generally used as a comonomer in the production of a polyacetal copolymer. Specific examples include 1,3-dioxolane, 1,3,6-trioxocane and 1,4-butanediol formal.
  • the component (c) is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of trioxane. ..
  • the method for producing the polyacetal copolymer (B) of the present invention comprises a trioxane (a), a specific cyclic siloxane compound (b) having two or more epoxy groups in the molecule represented by the formula (1), and a cation. It is characterized in that it is copolymerized in the presence of a polymerization catalyst.
  • ⁇ Cationic polymerization catalyst As the cationic polymerization catalyst, a known polymerization catalyst in cationic copolymerization containing trioxane as a main monomer can be used. Typically, a protic acid and a Lewis acid are given.
  • protic acid examples include perfluoroalkane sulfonic acid, heteropoly acid and isopoly acid.
  • perfluoroalkanesulfonic acid examples include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, pentadecafluoro.
  • examples thereof include heptane sulfonic acid and heptadecafluorooctane sulfonic acid.
  • Heteropolyacid refers to a polyacid produced by dehydration condensation of different oxygen acids, which has a specific different element in the center and is a mononuclear or multinuclear compound formed by condensation of condensed acid groups sharing an oxygen atom. It has complex ions.
  • Isopoly acid is also referred to as iso-polyacid, homonuclear polycondensation acid or homopolyacid, and refers to a high molecular weight inorganic oxygen acid composed of a condensate of an inorganic oxygen acid having a single V- or VI-valent metal. ..
  • the heteropoly acid examples include phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, phosphotungstovanadic acid, silicotungstic acid, silicomolybdic acid, silicomolybd.
  • the heteropolyacid is preferably selected from silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, and phosphotungstic acid.
  • isopoly acid examples include paratungstic acid, isopolytungstic acid exemplified by metatungstic acid, paramolybdic acid, isopolymolybdic acid exemplified by metamolybdic acid, metapolyvanadate, isopolyvanadate. Etc. Among them, isopolytungstic acid is preferable from the viewpoint of polymerization activity.
  • Lewis acid examples include halides of boron, tin, titanium, phosphorus, arsenic and antimony, and specifically, boron trifluoride (and its ether complex), tin tetrachloride, titanium tetrachloride, pentafluoride. Examples thereof include phosphorus oxide, phosphorus pentachloride, antimony pentafluoride, and complex compounds or salts thereof.
  • the amount of the polymerization catalyst is not particularly limited, but it is preferably 0.1 ppm or more and 50 ppm or less, more preferably 0.1 ppm or more and 30 ppm or less, based on the total of all monomers.
  • the amount of terminal groups can be adjusted by using a component for adjusting the molecular weight in addition to the above components.
  • the component for adjusting the molecular weight include chain transfer agents that do not form unstable terminals, that is, compounds having an alkoxy group such as methylal, monomethoxymethylal, and dimethoxymethylal.
  • the method for producing the polyacetal copolymer (B) of the present invention is not particularly limited.
  • the polymerization apparatus is not particularly limited, and a known apparatus is used, and any method such as batch type or continuous type is possible.
  • the polymerization temperature is preferably maintained at 65°C or higher and 135°C or lower.
  • Cation polymerization catalyst is preferably diluted with an inert solvent that does not adversely affect the polymerization.
  • Deactivation of the polymerization catalyst after the polymerization can be performed by a conventionally known method. For example, after the polymerization reaction, a basic compound or an aqueous solution thereof can be added to the reaction product discharged from the polymerization machine or the reaction product in the polymerization machine.
  • the basic compound for neutralizing and deactivating the polymerization catalyst is not particularly limited. After polymerization and deactivation, washing, separation and recovery of unreacted monomers, drying and the like are further performed by a conventionally known method, if necessary.
  • the polyacetal copolymer obtained as described above preferably has a weight average molecular weight corresponding to polymethylmethacrylate determined by size exclusion chromatography of 10,000 to 500,000, and particularly preferably 20,000 to 150,000.
  • the amount of hemiformal terminal group detected by 1H-NMR is preferably 0 to 4 mmol/kg, particularly preferably 0 to 2 mmol. /Kg.
  • the amount of impurities, especially water, in the total amount of monomers and comonomers to be used for polymerization is 20 ppm or less, and particularly preferably 10 ppm or less.
  • the resin composition of the present invention preferably contains various known stabilizers selected as necessary. Examples of the stabilizer used herein include any one or more of hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, carboxylates, and the like. it can.
  • thermoplastic resin for example, weathering (light) stabilizer, colorants such as dyes and pigments, lubricants, nucleating agents, release agents, charging An inhibitor, a surfactant, or an organic polymer material, an inorganic or organic fibrous, powdery, or plate-like filler can be added alone or in combination of two or more.
  • weathering (light) stabilizer for example, weathering (light) stabilizer, colorants such as dyes and pigments, lubricants, nucleating agents, release agents, charging
  • An inhibitor, a surfactant, or an organic polymer material, an inorganic or organic fibrous, powdery, or plate-like filler can be added alone or in combination of two or more.
  • a melt-kneading apparatus is used for producing the polyacetal resin composition of the present invention.
  • the melt-kneading device is not particularly limited, but has a function of kneading the melted polyacetal resin and polyacetal copolymer, and preferably has a vent function, for example, a uniaxial or at least one vent hole or A multi-screw continuous extrusion kneader, a co-kneader, etc. may be mentioned.
  • the melt-kneading treatment is preferably performed within a temperature range from the melting point of the polyacetal resin and the polyacetal copolymer to 260°C. If the temperature is higher than 260°C, the polymer is decomposed and deteriorated, which is not preferable.
  • the polyacetal resin (A) and the polyacetal copolymer (B) used in the examples and comparative examples are as follows.
  • the polyacetal resin (A) was prepared as follows. A twin-screw paddle type continuous polymerizer was continuously fed with a mixture of 96.7% by mass of trioxane (TOX), 3.3% by mass of 1,3-dioxolane (DO), and 800 ppm of methylal, and three catalysts were used as catalysts. Polymerization was performed by adding 20 ppm (as boron trifluoride) of boron dibutyl etherate (dibutyl ether solution). The polymer discharged from the discharge port of the polymerization machine was immediately added with an aqueous solution containing 1000 ppm of triethylamine, pulverized and stirred to deactivate the catalyst. Then, the polymer was recovered by centrifugation and dried to obtain a polyacetal resin (A).
  • the polyacetal copolymer (B) was prepared as follows. 300 g of trioxane was placed in a closed autoclave having a jacket through which a heat medium can pass and a stirring blade, and further, the compounds shown in Table 1 as the component (b) and optionally 1,3-dioxolane (DO) as the component (c). ) Or butanediol formal (BDF) was added so that the proportions of the parts by mass shown in Table 1 were respectively obtained. After stirring the contents and passing hot water of 80° C.
  • the catalyst solution (phosphotungstic acid (PWA) is a solution of methyl formate, boron trifluoride dibutyl etherate (BF 3 OBu).
  • PWA phosphotungstic acid
  • boron trifluoride dibutyl etherate boron trifluoride dibutyl etherate
  • a dibutyl ether solution was added so that the catalyst concentration (relative to all monomers) shown in Table 1 was added to initiate polymerization.
  • the catalyst concentration was the concentration of boron trifluoride.
  • the component (b) used in the examples is the following (b-1).
  • Me represents a methyl group.
  • Examples and Comparative Examples> The various components shown in Table 1 were added and mixed in the proportions shown in Table 1, and melt-kneaded with a vented twin-screw extruder to prepare pelletized compositions.
  • ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-) was added to 100 parts by weight of the total amount of the components (A) and (B).
  • Hydroxy-m-tolyl)propionate] IRGANOX245 manufactured by BASF Japan Ltd.
  • 0.08 parts by weight of melamine were added.
  • ⁇ Evaluation> The characteristic evaluation items and evaluation methods in the examples are as follows. ⁇ Tensile strength> The tensile strength of the ISO Type 1A test piece was measured according to ISO527-1, 2. The measurement chamber maintained an atmosphere of 23° C. and 50% RH. ⁇ Bending strength and flexural modulus> The flexural modulus was measured according to ISO178. The measurement chamber maintained an atmosphere of 23° C. and 50% RH.
  • composition of the present invention is excellent in mechanical properties (tensile strength, flexural modulus).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour objet de fournir une composition de résine polyacétal qui présente un niveau de propriétés mécaniques amélioré.　À cet effet, l'invention concerne une composition de résine polyacétal qui est obtenue par mélange pour 100 parties en masse d'une résine polyacétal (A), de 0,1 à 100 parties en masse d'un copolymère de polyacétal (B) obtenu par copolymérisation au moins avec un trioxane (a) et un composé siloxane (b) représenté par la formule (1).　(Dans la formule (1), Ｒ１ représente un groupe hydrocarbure aliphatique monovalent de 1 à 6 atomes de carbone ou un groupe hydrocarbure aromatique de 1 à 10 atomes de carbone, et X représentent chacun Ｒ１ ou un groupe organique possédant un groupe époxy. Parmi les X présents en pluralité, deux ou plus représentent un groupe organique possédant un groupe époxy. Les Ｒ１ présents en pluralité et les X peuvent chacun être identiques ou différents.)
PCT/JP2019/047575 2018-12-26 2019-12-05 Composition de résine polyacétal, et procédé de fabrication de celle-ci WO2020137414A1 (fr)

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Cited By (1)

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WO2021039003A1 (fr) * 2019-08-30 2021-03-04 ポリプラスチックス株式会社 Composition de résine de polyacétal et son procédé de production

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JP2005232404A (ja) * 2004-02-23 2005-09-02 Mitsubishi Gas Chem Co Inc ポリアセタール樹脂組成物
JP2010059356A (ja) * 2008-09-05 2010-03-18 Mitsubishi Gas Chemical Co Inc 分岐・架橋ポリアセタール共重合体
JP2010150306A (ja) * 2008-12-24 2010-07-08 Polyplastics Co ポリアセタール樹脂組成物
JP2011084702A (ja) * 2009-10-19 2011-04-28 Mitsubishi Gas Chemical Co Inc ポリアセタール共重合体
WO2012049926A1 (fr) * 2010-10-15 2012-04-19 ポリプラスチックス株式会社 Composition de résine polyacétal et son procédé de production
JP2016204288A (ja) * 2015-04-20 2016-12-08 信越化学工業株式会社 エポキシ基含有環状オルガノシロキサン

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JPH01146958A (ja) * 1987-12-04 1989-06-08 Polyplastics Co 熱可塑性樹脂組成物
JP2002234923A (ja) * 2001-02-09 2002-08-23 Polyplastics Co ポリアセタール共重合体及び樹脂組成物
JP2005232404A (ja) * 2004-02-23 2005-09-02 Mitsubishi Gas Chem Co Inc ポリアセタール樹脂組成物
JP2010059356A (ja) * 2008-09-05 2010-03-18 Mitsubishi Gas Chemical Co Inc 分岐・架橋ポリアセタール共重合体
JP2010150306A (ja) * 2008-12-24 2010-07-08 Polyplastics Co ポリアセタール樹脂組成物
JP2011084702A (ja) * 2009-10-19 2011-04-28 Mitsubishi Gas Chemical Co Inc ポリアセタール共重合体
WO2012049926A1 (fr) * 2010-10-15 2012-04-19 ポリプラスチックス株式会社 Composition de résine polyacétal et son procédé de production
JP2016204288A (ja) * 2015-04-20 2016-12-08 信越化学工業株式会社 エポキシ基含有環状オルガノシロキサン

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021039003A1 (fr) * 2019-08-30 2021-03-04 ポリプラスチックス株式会社 Composition de résine de polyacétal et son procédé de production

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