WO2022137859A1 - ポリアセタール共重合体及びその製造方法 - Google Patents

ポリアセタール共重合体及びその製造方法 Download PDF

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Publication number
WO2022137859A1
WO2022137859A1 PCT/JP2021/041320 JP2021041320W WO2022137859A1 WO 2022137859 A1 WO2022137859 A1 WO 2022137859A1 JP 2021041320 W JP2021041320 W JP 2021041320W WO 2022137859 A1 WO2022137859 A1 WO 2022137859A1
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Prior art keywords
mass
compound
polyacetal copolymer
parts
glycidyl ether
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PCT/JP2021/041320
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English (en)
French (fr)
Japanese (ja)
Inventor
直裕 菅澤
智宏 門間
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 CN202180086260.3A priority Critical patent/CN116635441A/zh
Publication of WO2022137859A1 publication Critical patent/WO2022137859A1/ja

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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
    • 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
    • C08G2/24—Copolymerisation of aldehydes or ketones with acetals

Definitions

  • the present invention relates to a polyacetal copolymer and a method for producing the same.
  • Polyacetal resin has an excellent balance of mechanical properties, chemical resistance, slidability, etc., and because it is easy to process, it is mainly used as engineering plastics for electrical / electronic parts, automobile parts, and other various mechanical parts. It is widely used as. However, with the expansion of the range of use in recent years, there is a tendency that more advanced characteristics are gradually required. For example, when a polyacetal resin is used for thin-walled parts or the like, rigidity, creep resistance, etc. are required while maintaining the fluidity, moldability, thermal stability, and slidability inherent in the polyacetal resin. There are many.
  • the polyacetal copolymer obtained by the above method is basically good in terms of thermal stability.
  • the operation of the polymerization step, the terminal stabilizing step, the melt-kneading step with the compound such as the stabilizer, etc. becomes unstable in its production, or the heat of the obtained copolymer becomes unstable.
  • the stability may be inferior. Since such a copolymer is inferior in thermal stability, there is a problem that, for example, the color of the copolymer is discolored when it is melt-retained in the molding machine. In addition, some mechanical properties, especially impact resistance, may not provide satisfactory values. Elucidation and improvement of the cause has been an important issue in putting the polyacetal copolymer by these methods into practical use.
  • the present invention has been made in view of the above-mentioned conventional problems, and the present invention has excellent rigidity and excellent impact resistance, and also has thermal stability, particularly low discoloration during melt retention in the molding machine. It is an object of the present invention to provide a polyacetal copolymer and a stable production method thereof.
  • the present inventor has found that the sodium content in a specific aliphatic glycidyl ether compound used for forming a branched / crosslinked structure in the polymer skeleton of a polyacetal copolymer is found.
  • a suitable range of the degree of polymerization of the polyacetal copolymer and a control means thereof have completed the present invention.
  • trioxane (A) 100 parts by mass of trioxane (A), 0.05 to 5 parts by mass of a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring, trimethylolpropane triglycidyl ether, and glycerol triglycidyl.
  • a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring
  • trimethylolpropane triglycidyl ether trimethylolpropane triglycidyl ether
  • glycerol triglycidyl glycerol triglycidyl.
  • the total mass (g) of the (A), (B) and (C) is included in a
  • the number of moles of the (D) is included in b
  • the (A), (B) and (C) are included.
  • a method for producing a polyacetal copolymer, which is set so as to satisfy (b + c + d) / a 4.5 to 9 ⁇ mol / g, where c and d are the total number of moles of water and methanol, respectively.
  • a polyacetal copolymer having excellent rigidity, impact resistance, etc., and also having thermal stability, particularly low discoloration during melt retention in a molding machine, and a stable production method thereof. can.
  • the method for producing a polyacetal copolymer of the present embodiment comprises 100 parts by mass of trimethylol (A) and 0.05 to 5 parts by mass of a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in the ring.
  • An aliphatic glycidyl ether compound (C) which is one or more selected from the group consisting of trimethylolpropane triglycidyl ether, glycerol triglycidyl ether and pentaerythritol tetraglycidyl ether and has a sodium content of 0.1 to 100 mass ppm.
  • each component used in the production method of the present embodiment will be described below.
  • Trioxane (A) 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 by purifying it by a method such as distillation.
  • the trioxane (A) used for the polymerization is preferably one in which impurities such as water and methanol are reduced as much as possible.
  • Cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in the ring is a cyclic acetal compound capable of copolymerizing with trioxane (A) (hereinafter, also referred to as “cyclic acetal compound (B)”).
  • 1,3-dioxolane propanediolformal, diethyleneglycolformal, triethyleneglycolformal, 1,4-butanediolformal, 1,5-pentanediolformal, 1,6-hexanediolformal and the like.
  • 1,3-dioxolane is preferable.
  • the copolymerization amount of the cyclic acetal compound (B) is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of trioxane (A). .5 parts by mass.
  • the copolymerization ratio of the cyclic acetal compound (B) is less than 0.05 parts by mass, the difficulty of controlling the polymerization reaction increases and the thermal stability of the produced polyacetal copolymer becomes inferior.
  • the copolymerization ratio of the cyclic acetal compound (B) exceeds 5 parts by mass, the mechanical properties such as strength and rigidity are lowered.
  • the aliphatic glycidyl ether compound (C) is one or more selected from trimethylolpropane triglycidyl ether, glycerol triglycidyl ether and pentaerythritol tetraglycidyl ether, and has 3 to 4 glycidyloxy groups in one molecule. Further, the aliphatic glycidyl ether compound (C) has a structure capable of forming a branched or crosslinked structure in the polymer skeleton by copolymerization with trioxane. In this respect, it is distinguished from the cyclic acetal compound (B). Further, in the present embodiment, the aliphatic glycidyl ether compound (C) has a sodium content of 0.1 to 100 mass ppm.
  • the copolymerization amount of the aliphatic glycidyl ether compound (C) is 0.001 to 0.5 parts by mass, preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the trioxane of the component (A). Particularly preferably, it is 0.1 to 0.5 parts by mass. If the copolymerization amount of the component (C) is less than 0.001 part by mass, the effect of improving the rigidity may not be obtained. On the contrary, if it exceeds 0.5 parts by mass, a problem of poor moldability due to a decrease in fluidity may occur, and further, the mechanical properties of the obtained copolymer may decrease.
  • the present embodiment is characterized in that the aliphatic glycidyl ether compound (C) having a sodium content of 0.1 to 100% by mass is used. This makes it possible to stably produce a polyacetal copolymer having particularly excellent thermal stability. If the sodium content of the aliphatic glycidyl ether compound (C) to be used exceeds 100% by mass, the operation of the polymerization step, the terminal stabilizing step, the commercialization step by blending a stabilizer, etc. becomes unstable, and the operation becomes unstable. The thermal stability of the obtained polyacetal copolymer is also inferior.
  • the content is set to 0.1 mass ppm from the viewpoint of economic efficiency in the production of the aliphatic glycidyl ether compound (C).
  • the sodium content is preferably 0.1 to 30 mass ppm, more preferably 0.2 to 5 mass ppm.
  • Aliphatic glycidyl ether compounds are generally produced by the reaction of alcohol with epichlorohydrin.
  • a method of ring-opening and adding epichlorohydrin to an alcohol in the presence of an acidic catalyst and then ring-closing the molecule with an alkaline aqueous solution to obtain a glycidyl ether compound for example, Japanese Patent Application Laid-Open No. 61-178974 is known.
  • a method of reacting alcohol and epichlorohydrin in the presence of a solid alkali metal compound to produce a glycidyl ether compound in the presence of a solid alkali metal hydroxide pulverized in a reaction mixture is also disclosed. Due to such differences in the synthesis method and the purification step, aliphatic glycidyl ether compounds having different sodium contents are produced.
  • the polyacetal copolymer is basically a cation polymerization catalyst by adding a trioxane (A), a cyclic acetal compound (B) and an aliphatic glycidyl ether compound (C) in an appropriate amount of a molecular weight modifier. It can be obtained by a method such as bulk polymerization using.
  • Linear formal compound (D) As the molecular weight adjusting agent used in this embodiment, a linear formal compound is used.
  • the linear formal compound include methylal, etylal, dibutoxymethane, bis (methoxymethyl) ether, bis (ethoxymethyl) ether, bis (butoxymethyl) ether and the like. These may be used alone or in combination of two or more. Among them, one or more selected from the group consisting of methylal, etilal and dibutoxymethane is preferable.
  • the cyclic acetal compound (B) and the aliphatic compound in the molecular chain of the polyacetal copolymer It is preferable that the structural units derived from the glycidyl ether compound (C) are uniformly dispersed.
  • the cyclic acetal compound (B) and the catalyst are uniformly mixed in the production of the polyacetal copolymer by polymerization, and the aliphatic glycidyl ether compound (C) and the trioxane (C) and the trioxane (which are separately uniformly mixed in advance) are used.
  • a method of adding it to the uniform mixed solution of A) and supplying it to a polymerization machine for polymerization is effective.
  • the dispersed state of the branched structure derived from the aliphatic glycidyl ether compound becomes good, the mechanical properties are improved, and the thermal stability is also excellent.
  • the polymerization apparatus is not particularly limited, and a known apparatus is used, and any method such as a batch type or a continuous type can be used. Is. Further, it is preferable to keep the polymerization temperature at 65 to 115 ° C. Deactivation after polymerization is carried out by adding a basic compound or an aqueous solution thereof to the reaction product discharged from the polymerization machine or the reaction product in the polymerization machine after the polymerization reaction.
  • the cationic polymerization catalyst used in this embodiment includes lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimon trifluoride, phosphorus pentafluoride, antimon trifluoride, and trifluoride.
  • Inorganic and organic acids such as position compounds, perchloric acid, acetylparklorate, t-butylparklorate, hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid, toethyloxonium tetrafluoroborate, triphenylmethyl
  • complex salt compounds such as hexafluoroantimonate, allyldiazonium hexafluorophosphate and allyldiazonium tetrafluoroborate, alkyl metal salts such as diethylzinc, triethylaluminum and diethylaluminum chloride, heteropolyacids and isopolyacids.
  • boron trifluoride especially three such as boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetic anhydrate, and boron trifluoride triethylamine complex compound.
  • Boron trifluoride coordination compounds are preferred. These catalysts can also be used after being diluted in advance with an organic solvent or the like.
  • Examples of the basic compound for neutralizing and inactivating the polymerization catalyst include ammonia, amines such as triethylamine, tributylamine, triethanolamine, and tributanolamine, or alkali metals and alkaline earth metals. Hydroxide salts and other known catalytic deactivating agents are used. Further, after the polymerization reaction, it is preferable to quickly add these aqueous solutions to the product to inactivate it. After the polymerization method and the deactivation method, if necessary, further washing, separation and recovery of unreacted monomers, drying and the like are carried out by conventionally known methods.
  • stabilization treatment is performed by a known method as necessary, such as decomposition and removal of the unstable end portion or sealing of the unstable end with a stable substance, and various necessary stabilizers are blended.
  • the stabilizer used here include one or more of hindered phenolic compounds, nitrogen-containing compounds, hydroxides of alkaline or alkaline earth metals, inorganic salts, carboxylates and the like. can.
  • general additives to the polyacetal resin such as dyes, colorants such as pigments, lubricants, nucleating agents, mold release agents, and charging are required.
  • One or more kinds of inhibitors, surfactants, organic polymer materials, inorganic or organic fibrous, powdery, plate-like fillers and the like can be added.
  • the total mass (g) of the trioxane (A), the cyclic acetal compound (B), and the aliphatic glycidyl ether compound (C) is a, and the linear formal compound (D).
  • (b + c + d) / a 4.5 to 9 ⁇ mol / g is satisfied, rigidity and impact resistance can be improved while maintaining moldability.
  • the water and methanol contained in the above (A), (B) and (C) are derived from the respective impurities.
  • the polyacetal copolymer of the present embodiment is obtained by the above-mentioned method for producing a polyacetal copolymer of the present embodiment. Therefore, the polyacetal copolymer of the present embodiment has excellent rigidity and impact resistance, and also has thermal stability, particularly low discoloration during melt retention in the molding machine.
  • Examples 1 to 10 Two jackets with paddles, using a continuous mixing reactor consisting of a barrel with a cross-sectional shape in which two circles partially overlap and a rotating shaft with paddles, equipped with a jacket that allows heat (cold) media to pass through on the outside.
  • the trioxane (A), the cyclic acetal compound (B), and the aliphatic glycidyl ether compound (C) were added in the proportions and amounts shown in Table 1 while rotating the rotation shafts at 150 rpm.
  • the linear formal compound (D) shown in Table 1 is continuously supplied as a molecular weight modifier at the ratio and amount shown in Table 1, and the catalyst boron trifluoride gas is 0 with respect to the trioxane in terms of boron trifluoride.
  • a homogeneous mixture mixed so as to have a molecular weight of .005% by mass was continuously added and supplied to carry out bulk polymerization.
  • the reaction product discharged from the polymerizer was rapidly passed through the crusher and added to an aqueous solution at 80 ° C. containing 0.1% by mass of triethylamine to inactivate the catalyst. Further, after separation, washing and drying, a crude polyacetal copolymer was obtained.
  • Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was further added to 100 parts by mass of the branched or crosslinked polyacetal copolymer obtained by the above method as a stabilizer. .3 parts by mass and 0.15 parts by mass of melamine were added and melt-kneaded at 210 ° C. using a twin-screw extruder to obtain a pellet-shaped branched polyacetal copolymer. Table 1 shows the results of evaluation by the method described later.
  • the sodium content of the aliphatic glycidyl ether compound was measured by the following method. 1 g of the measurement sample was weighed in a platinum crucible and heated with an electric stove to decompose and volatilize the organic components in the crucible, and then heated at 600 ° C. for 1 hour in an electric furnace. After cooling, the inside of the crucible was washed with 3.5% by mass hydrochloric acid, and the cleaning solution diluted to 25 mL with 3.5% by mass hydrochloric acid was used as a sample for inductively coupled plasma emission spectroscopic analysis using CIROSC CD-120 manufactured by Spectro. , The amount of sodium was quantified, and the amount of sodium in the measurement sample was determined.
  • Total amount of water in component (A), component (B), and component (C) The water content of the mixed solution of the component (A), the component (B), and the component (C) was measured by the curl fisher method.
  • Total amount of methanol in component (A), component (B), and component (C) The amount of methanol in the mixed solution of the component (A), the component (B), and the component (C) was measured by a gas chromatography method.
  • the hue (L, a, b) of the molded product was measured with a Z-300A color sensor manufactured by Nippon Denshoku Kogyo Co., Ltd., and the deviation ( ⁇ E) from the initial hue was calculated by the following formula.
  • ⁇ E [(L 1 ⁇ L 0 ) 2 + (a 1 ⁇ a 0 ) 2 + (b 1 ⁇ b 0 ) 2 ] 1/2
  • L, a, and b are color values measured by a color difference meter, respectively, the subscript 1 of L, a, and b means the hue after staying for 2 hours, and 0 means the hue in the normal cycle. do.
  • the examples 1 to 10 have sufficient rigidity (flexural modulus of 2800 MPa or more), excellent impact resistance (charpy impact strength of 9 kJ / m 2 or more), and thermal stability (sharpy impact strength of 9 kJ / m 2 or more). It was shown that a polyacetal copolymer having a low melt retention discoloration degree (2.5 or less) can be produced. On the other hand, in Comparative Examples 1 to 4, although the rigidity was comparable to that of Examples, it was inferior in at least one of impact resistance and thermal stability.

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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)
PCT/JP2021/041320 2020-12-21 2021-11-10 ポリアセタール共重合体及びその製造方法 WO2022137859A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0482880A (ja) * 1990-07-25 1992-03-16 New Japan Chem Co Ltd グリシジル化合物の製造方法
JP2002234922A (ja) * 2001-02-09 2002-08-23 Polyplastics Co ポリアセタール共重合体及びその製造方法
WO2008078570A1 (ja) * 2006-12-25 2008-07-03 Polyplastics Co., Ltd. ポリアセタール樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0482880A (ja) * 1990-07-25 1992-03-16 New Japan Chem Co Ltd グリシジル化合物の製造方法
JP2002234922A (ja) * 2001-02-09 2002-08-23 Polyplastics Co ポリアセタール共重合体及びその製造方法
WO2008078570A1 (ja) * 2006-12-25 2008-07-03 Polyplastics Co., Ltd. ポリアセタール樹脂組成物

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