WO2000047646A1 - Procede de preparation continue de resine de polyacetal - Google Patents

Procede de preparation continue de resine de polyacetal Download PDF

Info

Publication number
WO2000047646A1
WO2000047646A1 PCT/JP2000/000750 JP0000750W WO0047646A1 WO 2000047646 A1 WO2000047646 A1 WO 2000047646A1 JP 0000750 W JP0000750 W JP 0000750W WO 0047646 A1 WO0047646 A1 WO 0047646A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyacetal resin
polymerization
trioxane
silane compound
weight
Prior art date
Application number
PCT/JP2000/000750
Other languages
English (en)
Japanese (ja)
Inventor
Noriyuki Sugiyama
Original Assignee
Polyplastics Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Publication of WO2000047646A1 publication Critical patent/WO2000047646A1/fr

Links

Classifications

    • 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
    • C08G2/10—Polymerisation of cyclic oligomers of formaldehyde

Definitions

  • the present invention relates to a continuous production method of a polyacetal resin by cationic polymerization, and more particularly, to a method for industrially and continuously producing a polyacetal resin of a copolymer having a small number of unstable molecular terminals in a high yield in an industrially stable manner.
  • Polyacetal resin has excellent balance among mechanical properties, chemical resistance, slidability, etc., and is easy to mold, making it a typical engineering plastic material. It is widely used mainly in various other mechanical parts.
  • JP-A-2-6529, JP-A-4-165412, JP-A-4-65413 and JP-B-8-30103 disclose a cyclic ether and a polymerization catalyst in advance when producing a polyacetal resin. And a method of continuously adding the contacted mixture to trioxane.
  • JP-A-59-227916, JP-A-60-1216 and JP-A-53-111087 disclose in order to obtain a high quality polyacetal resin
  • a method has been proposed in which a sterically hindered phenolic antioxidant is added together with the monomer, and a method in which an organic trivalent phosphorus compound is added and mixed in advance to a monomer to be subjected to polymerization.
  • the quality of each method tends to deteriorate under high yielding production conditions, and no method has yet been proposed to satisfy both performances in a balanced manner.
  • Japanese Patent Application Laid-Open No. 641-11117 discloses a technique of introducing a silicone oil having a reactive epoxy group into a polymerization system at the time of producing a polyacetal resin, and synthesizing a copolymer of polyacetal and silicone oil. Proposed. Since the silicone oil used in this proposal has very few functional groups that react with water and formic acid, there is room for improvement in improving the quality of polyacetyl resins. In view of such circumstances, the present invention enables continuous production of a high-quality polyacetal resin, in particular, a copolymer polyether resin, by a cationic polymerization method with high yield and industrially stable for a long period of time. It is intended to provide a method. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, a method of adding a specific silane compound together with these monomers at the time of copolymerization of a specific main monomer and a comonomer, or a method in which the above monomer to be subjected to polymerization is prepared in advance. If the method of adding and mixing a specific silane compound is used, the specific silane compound can reduce the amount of formic acid and water, which are factors that reduce the catalytic activity at the time of polymerization. A high-concentration catalyst amount enables high-yield polymerization, and the silane compound has reactivity with the hydroxy terminal of a polymer generated by a side reaction of the catalyst, thereby enabling high quality. The inventors have found that the present invention can be solved, and have completed the present invention.
  • the present invention provides a method for continuously producing a copolymer polyacetal resin by adding and supplying a cyclic ether and / or cyclic formal as a comonomer to trioxane as a main monomer and performing cationic polymerization.
  • Polyacetal tree coexisting with at least one selected from the group of silane compounds represented by (IV) To provide a continuous method for producing fats,
  • R 1 , R 5 , R 6 , R 9 , R 10 , R ", R 13 , R 14 , R ' 5 and R 16 are a hydrogen atom and a hydrocarbon residue having 1 to 6 carbon atoms.
  • R 2 , R 3 , R 4 , R 7 , R 8 and R ′ 2 are a hydrogen atom, a hydrocarbon residue having 1 to 22 carbon atoms, An atom independently selected from the group consisting of hydrocarbon residues having a functional group containing one or more atoms each independently selected from the group consisting of fluorine, oxygen, nitrogen, iodide and phosphorus; or Indicates a residue.
  • At least one selected from the group of the silane compounds represented by the above general formulas (I) to (IV) is added and mixed in advance with at least one of trioxane, cyclic ether and / or cyclic formal.
  • An object of the present invention is to provide a method for continuously producing a polyacetyl resin.
  • the polyacetal resin according to the present invention is obtained by adding a cyclic ether and / or cyclic formal as a comonomer to trioxane as a main monomer and cationically copolymerizing the same.
  • a specific silane compound for removing a trace amount of formic acid / water component contained as an impurity in the copolymerization monomer is blended as a scavenger, and Brenstead acid and / or Lewis acid is used as a polymerization catalyst, and cationic polymerization is performed.
  • This is a method for producing a copolymer polyacetal resin.
  • trioxane is used as a main monomer
  • a cyclic ether and / or cyclic formal is used as a comonomer.
  • Examples of the cyclic ether include ethylene oxide and oxetane.
  • Examples of the cyclic formal include glycidyl ether compounds such as 1,4-butanediol diglycidyl ether, butyl glycidyl ether, and octyldaricidyl ether; 1,3-dioxolan; 1,3,5-trioxepane; , 3-Dioxane, 4-Methyl_1,3-Dioxolane, 6-Methyl-1,3,5-Trioxepane, 1,4-Butanediolformal, 4-Ethyl-1,3-Dioxolane, 6-Ethyru-1 , 3,5-trioxepane, 4-methyl-1,3-dioxane, 5-methyl-1,3-dioxane, 1,5-pentenediolformal, 4-propyl_1,3-dioxolan, 6- Propyl
  • the amount of these comonomers to be used is preferably 20% by weight or less, particularly 0.1 to 15 times, based on the trioxane of the main monomer, in consideration of the rigidity and chemical resistance of the molded article. % Is preferred.
  • the specific silane compound used in the production method according to the present invention at least one selected from the group of silane compounds represented by the general formulas (I) to (IV) is used.
  • Examples of the silane compound represented by the general formula (I) include monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane, and are represented by the general formula (II).
  • Examples of the silane compound include dialkoxysilanes such as dimethyldimethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, and dimethylethylethoxysilane.
  • Examples of the silane compound represented by the general formula (III) include triethoxysilane, trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane.
  • Saturated alkyltrialkoxysilanes such as sicilan, octyltriethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, propyltriethoxysilane, hexyltriethoxysilane, pentyltriethoxysilane, etc.
  • silane compound represented by the general formula (IV) tetramethoxysilane, tetraaryloxysilane, tetraethoxysilane, Single tetraalkoxysilanes such as tetrabutoxysilane, tetrakis (2-methoxyethoxy) silane, and tetraphenoxysilane, as well as methoxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane, and hexyloxytrimethoxysilane And the like.
  • silane compounds used in the present invention are not limited to those exemplified above, but among those exemplified above, dimethyldimethoxysilane, dimethylmethylethoxysilane, getyldimethoxysilane, dimethylethylmethoxysilane, Kutadecyltriethoxysilane, octadecyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-daricyloxypropyltrimethoxysilane, tris (2-methoxyethoxy) vinylsilane, tetraethoxysilane, tetrapropoxysilane Tetrabutoxysilane and tetrakis (2-methoxyethoxy) silane are particularly preferred.
  • the method of adding the silane compound according to the present invention is not particularly limited, and the silane compound may be supplied to the polymerization machine simultaneously with the main monomer trioxane, the comonomer cyclic ether or cyclic formal, or may be supplied in advance to the main monomer and / or The silane compound may be added to a comonomer and mixed, and then subjected to copolymerization.
  • the addition of the silane compound is preferably performed before the addition of the polymerization catalyst.
  • a method of maintaining the temperature at 0 ° C for 1 second or more is particularly preferable.
  • the amount of the silane compound used in the present invention is preferably from 1 to 500 ppm by weight, more preferably from 10 to 200 ppm by weight, based on trioxane as the main monomer. It is 50 to 1000 weight ppm. If the amount of the silane compound is too small, as in the case where the amount is less than 1 ppm by weight, it may not be possible to capture the formic acid / water, which is an impurity in the monomer, and it is said that a sufficient effect is obtained. can not cut.
  • the silane compound vaporizes and evaporates from the polyacetal resin in a later step in the production of the polyacetal resin, and the silane compound is concentrated following the adhesion to the piping.
  • problems such as contamination of the piping into the product bellet may occur.
  • a general cation-active catalyst is used as a polymerization catalyst used in the present invention.
  • the cation-active catalyst will be described by way of example.
  • Lewis acids in particular, halides such as boron, tin, titanium, phosphorus, arsenic, and antimony are suitable.
  • halides such as boron, tin, titanium, phosphorus, arsenic, and antimony are suitable.
  • Specific examples include boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentachloride, and pentafluoride. Examples thereof include phosphorus, arsenic pentafluoride, and antimony pentafluoride.
  • compounds such as complex compounds thereof for example, coordination compounds with organic compounds such as ether compounds
  • salts thereof can also be used.
  • Protonic acid specific examples include trifluoromethanesulfonic acid, perchloric acid and the like.
  • esters of protonic acid in particular, esters of perchloric acid and lower aliphatic alcohols can be used. Specific examples thereof include tertiary butyl perchlorate.
  • Protic acid anhydrides in particular, mixed anhydrides of perchloric acid and lower aliphatic carboxylic acids can be used, and specific examples thereof include acetyl chloride.
  • isopolyacid for example, phosphomolybdic acid
  • heteropolyacid for example, phosphomolybdic acid
  • triethyloxenoxahexafluorophosphato triphenylmethylhexafluoroarsenate
  • acetylhexafluoroborate acetylhexafluoroborate
  • boron trifluoride or a coordination compound of the boron trifluoride and an organic compound is the most common, and It is.
  • the boron trifluoride may be used by mixing with an inert gas such as nitrogen, and the boron trifluoride coordination compound may be used after being diluted once with an organic solvent or the like.
  • the basic molecular structure of the polyacetal resin obtained by the production method according to the present invention is not particularly limited, and includes those having a branched structure or a crosslinked structure, those having a block component introduced, and the like.
  • the molecular weight or melt viscosity is not limited as long as it can be melt-molded, but the melt index (MI) is 0.:! ⁇ lOO gZl Omin (ASTM D 1238-57T E) Are preferred.
  • MI melt index
  • ASTM D 1238-57T E melt index
  • a chain transfer agent that does not form an unstable molecular terminal portion that is, a compound having an alkoxy group such as methylal, methoxymethylal, dimethoxymethylal, trimethoxymethylal, and oxymethylenedi-n-butyl ether is used. Is exemplified.
  • components used when it is necessary to form a branched or crosslinked structure in the polyacetal resin according to the present invention include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,4-butanediol diglycol. Sidyl ether, hexamethylene glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene dalicol diglycidyl ether, polybutylene glycol diglycidyl ether, glycerin and its Inducers, pen-erythritol and its derivatives, and the like.
  • the amount of the component for adjusting the molecular weight is preferably 0.5% by weight or less, particularly preferably 0.4% by weight or less, based on the trioxane.
  • the amount of the component for forming the branched or crosslinked structure is preferably at most 0.3% by weight, particularly preferably at most 0.2% by weight, based on the trioxane.
  • a mixing means such as a screw, a paddle, a disk, a pin, and a blade is directly connected to two rotary drive shafts provided in a barrel.
  • a mixing means such as a screw, a paddle, a disk, a pin, and a blade is directly connected to two rotary drive shafts provided in a barrel.
  • Examples include a kneader and a co-kneader type polymerization machine.
  • the polymerization temperature is preferably in the range of 65 to 135 ° C.
  • the deactivation of the polymerization catalyst remaining in the resin after the polymerization of the polyacetal resin is performed by adding a basic compound or an aqueous solution thereof to the reaction product discharged from the polymerization machine after the polymerization reaction or the reaction product still in the polymerization machine. In addition it can be done. This inactivation is usually due to neutralization.
  • amines such as triethylamine, triptylamine, triethanolamine, and triethanolamine, or hydroxides of alkali metals and alkaline earth metals, Other known catalyst deactivators are used.
  • the polymerization product is further subjected to washing, separation and recovery of unreacted monomers, drying and the like, if necessary, by a conventionally known method. Further, if necessary, a stabilization treatment such as decomposition removal of terminal portions of unstable molecules or sealing is performed by a known method such as blending of various stabilizers.
  • a stabilization treatment such as decomposition removal of terminal portions of unstable molecules or sealing is performed by a known method such as blending of various stabilizers.
  • the stabilizer used herein include one or more of a hindered phenolic compound, a nitrogen-containing compound, an alkali or alkaline earth metal hydroxide, an inorganic acid, and a carboxylate. Those used in combination can be mentioned.
  • the polyacetal resin according to the present invention may contain, if necessary, a general additive to the thermoplastic resin, for example, coloring of a dye, a pigment or the like, as long as the properties of the resin are not impaired.
  • a general additive to the thermoplastic resin for example, coloring of a dye, a pigment or the like, as long as the properties of the resin are not impaired.
  • the present invention will be described specifically, but the present invention is not limited to these examples.
  • the trioxane mixture that is, the specific silane compound shown in Table 1 in advance at the ratio shown in Table 1 (% by weight of trioxane) was supplied from one end of the supply port.
  • the mixture was kept at 80 ° C for 30 minutes, and 4.0 mol 1% (based on trioxane) of a specific cyclic formal shown in Table 1 as a comonomer and 0.08 wt. % (Vs. trioxane) of the trioxane mixture was continuously fed.
  • cationic / bulk polymerization was continuously performed while continuously supplying boron trifluoride (30 weight parts per million (based on trioxane)) to the polymerization machine from the supply port.
  • the catalyst was deactivated for the polyatal resin collected within a certain period of time, the washed sample was dried at 50 ° C for 24 hr, weighed, and the obtained value was taken as the above-mentioned collection time. It was divided by the total weight of the feedstock added to the polymerization machine within the same time and expressed as a percentage.
  • the weight loss value obtained after holding at 200 ° CZ for 1 hour was divided by the weight loss value shown after holding at 450 ° CZ for 30 min to obtain a thermal weight loss rate.
  • a high-quality polyacetal resin having a small number of unstable molecular terminals can be obtained in a high yield and industrially for a long period of time.
  • the polyacetal resin obtained by the present invention is particularly excellent in molding processability, and also excellent in balance of mechanical properties, chemical resistance, slidability, etc. like ordinary polyacetal resin, so that injection molding is performed.
  • it is useful in various fields such as extrusion molded products, professional molded products, and foam molded products.

Landscapes

  • 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)

Abstract

Procédé de préparation continue de résine de polyacétal consistant à ajouter un comonomère à trioxane afin d'effectuer une polymérisation cationique en présence d'un composé spécifique de silane. Ce procédé permet de préparer en continu sur le plan industriel une résine de polyacétal de qualité élevée, de façon stable et hautement productive.
PCT/JP2000/000750 1999-02-10 2000-02-10 Procede de preparation continue de resine de polyacetal WO2000047646A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/33526 1999-02-10
JP11033526A JP2000230026A (ja) 1999-02-10 1999-02-10 ポリアセタール樹脂の連続製造方法

Publications (1)

Publication Number Publication Date
WO2000047646A1 true WO2000047646A1 (fr) 2000-08-17

Family

ID=12389003

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/000750 WO2000047646A1 (fr) 1999-02-10 2000-02-10 Procede de preparation continue de resine de polyacetal

Country Status (2)

Country Link
JP (1) JP2000230026A (fr)
WO (1) WO2000047646A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020255543A1 (fr) * 2019-06-21 2020-12-24 ポリプラスチックス株式会社 Copolymère de polyacétal et son procédé de production
WO2020261712A1 (fr) * 2019-06-27 2020-12-30 ポリプラスチックス株式会社 Composition de résine de polyacétal et procédé de production d'une composition de résine de polyacétal
CN113906098A (zh) * 2019-08-30 2022-01-07 宝理塑料株式会社 聚缩醛树脂组合物及其制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8816015B2 (en) 2012-06-05 2014-08-26 Ticona, Llc Low emission polyoxymethylene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5145199A (ja) * 1974-10-16 1976-04-17 Shinetsu Chemical Co Netsuanteiseihoriokishimechirenno seizohoho
JPS58174412A (ja) * 1982-04-08 1983-10-13 Asahi Chem Ind Co Ltd 新規アセタ−ル重合体及びその製法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5145199A (ja) * 1974-10-16 1976-04-17 Shinetsu Chemical Co Netsuanteiseihoriokishimechirenno seizohoho
JPS58174412A (ja) * 1982-04-08 1983-10-13 Asahi Chem Ind Co Ltd 新規アセタ−ル重合体及びその製法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020255543A1 (fr) * 2019-06-21 2020-12-24 ポリプラスチックス株式会社 Copolymère de polyacétal et son procédé de production
JP2021001264A (ja) * 2019-06-21 2021-01-07 ポリプラスチックス株式会社 ポリアセタール共重合体およびその製造方法
CN113677725A (zh) * 2019-06-21 2021-11-19 宝理塑料株式会社 聚缩醛共聚物和其制造方法
CN113677725B (zh) * 2019-06-21 2023-12-29 宝理塑料株式会社 聚缩醛共聚物和其制造方法
WO2020261712A1 (fr) * 2019-06-27 2020-12-30 ポリプラスチックス株式会社 Composition de résine de polyacétal et procédé de production d'une composition de résine de polyacétal
JP2021006597A (ja) * 2019-06-27 2021-01-21 ポリプラスチックス株式会社 ポリアセタール樹脂組成物およびポリアセタール樹脂組成物の製造方法
CN113677726A (zh) * 2019-06-27 2021-11-19 宝理塑料株式会社 聚缩醛树脂组合物和聚缩醛树脂组合物的制造方法
JP7356828B2 (ja) 2019-06-27 2023-10-05 ポリプラスチックス株式会社 ポリアセタール樹脂組成物およびポリアセタール樹脂組成物の製造方法
CN113677726B (zh) * 2019-06-27 2023-11-10 宝理塑料株式会社 聚缩醛树脂组合物和聚缩醛树脂组合物的制造方法
CN113906098A (zh) * 2019-08-30 2022-01-07 宝理塑料株式会社 聚缩醛树脂组合物及其制造方法
CN113906098B (zh) * 2019-08-30 2023-11-10 宝理塑料株式会社 聚缩醛树脂组合物及其制造方法

Also Published As

Publication number Publication date
JP2000230026A (ja) 2000-08-22

Similar Documents

Publication Publication Date Title
WO1992006126A1 (fr) Copolymere polyoxymethylenique et production de ce polymere
JP2001011143A (ja) ポリオキシメチレン共重合体、その製造方法及び分析方法
EP1630198A1 (fr) Composition de resine polyacetal
CN113166345B (zh) 氧亚甲基聚合物的制造方法和氧亚甲基聚合物树脂组合物
WO2000047646A1 (fr) Procede de preparation continue de resine de polyacetal
JP2000119357A (ja) ポリオキシメチレン共重合体の製造方法及びポリオキシメチレン共重合体組成物
WO2001042326A1 (fr) Copolymere polyacetalique
KR100529457B1 (ko) 폴리아세탈 공중합체
JP3208351B2 (ja) ポリアセタール樹脂の製造方法
JP4937436B2 (ja) ポリアセタール共重合体及びその製造方法
EP1167409B1 (fr) Copolymere de polyacetale et procede pour sa preparation
JP3998806B2 (ja) ポリアセタール樹脂の製造方法
JP3208353B2 (ja) ポリアセタール樹脂の製造方法
JP7179046B2 (ja) ポリアセタール共重合体及びその製造方法
JP4169868B2 (ja) ポリオキシメチレン共重合体及びその製造方法
WO2023276481A1 (fr) Engrenage en résine de polyacétal et procédé permettant d'améliorer la résistance à la fatigue d'un engrenage en résine de polyacétal
JP3926512B2 (ja) ポリアセタール共重合体
WO2022064924A1 (fr) Copolymère de polyacétal et son procédé de production
JP2000169668A (ja) ポリアセタール樹脂組成物ならびにそれからなる成形品
JP2001002886A (ja) 分岐ポリアセタール樹脂組成物
JP4429536B2 (ja) ポリアセタール共重合体及びその製造方法
JP4204876B2 (ja) バックル用樹脂材料及びその成形品
JP2001002887A (ja) 分岐ポリアセタール樹脂組成物
JP3883750B2 (ja) ポリアセタール共重合体
JP3926484B2 (ja) ポリアセタール共重合体

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase