JP2005320394A - Polyacetal carbonate copolymer and process for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel copolymer which has sufficient mechanical properties and the like when used as a molded body and has excellent decomposability and can be easily discarded and decomposed and recovered.
SOLUTION: Trioxane (A) and at least one cyclic carbonate compound (B) selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one and their alkyl substituents A polyacetal carbonate copolymer obtained by copolymerization.
[Selection figure] None

Description

  The present invention relates to a novel polyacetal carbonate copolymer. More specifically, the present invention relates to a novel polyacetal carbonate copolymer that has sufficient mechanical properties and the like when used as a molded body and is excellent in decomposability and is easy to dispose and disassemble and recover. Since the copolymer of the present invention has such properties, it is suitable for applications such as film materials, civil engineering materials, and medical materials in packaging materials, horticulture, agriculture, dairy farming, fishing, and the like.

  Polyacetal resin has excellent balance of mechanical properties, chemical resistance, slidability, etc. and is easy to process, so it can be used as a representative engineering plastic for electrical / electronic parts, automobile parts and other various mechanical parts. Widely used as a center. In recent years, with the expansion of the range of use, for example, it is expected as a material suitable for use as a film material, civil engineering material, or medical material in packaging materials, horticulture, agriculture, dairy farming, fishery, and the like. In these fields, it may be required to have excellent decomposability from the viewpoint of facilitating disposal processing and decomposition / recovery processing. However, the conventional polyacetal resin has a chemical structure of only a formal site or an ether site, and tends to be inferior in degradability.

On the other hand, non-patent literature 1 reports that polycarbonate, which is a ring-opening polymer of a cyclic carbonate compound, exhibits biodegradability, but an insufficient tendency was observed in mechanical properties and the like.
Polym.Prepr.Jpn.46,320 (1997)

  In view of the actual situation, the present invention has an object to provide a novel copolymer that has sufficient mechanical properties and the like when used as a molded body, and is easy to dispose and disassemble and recover due to excellent decomposability. And

  As a result of intensive studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by a specific copolymer, and have completed the present invention.

  That is, the present invention relates to trioxane (A), at least one cyclic carbonate compound (B) selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one, and alkyl-substituted products thereof. The present invention relates to a polyacetal carbonate copolymer obtained by copolymerization of

  The polyacetal carbonate copolymer of the present invention has a formal part, a carbonate part and an ether part as its chemical structure, has sufficient mechanical properties when used as a molded article, and is excellent in decomposability, and therefore is a packaging material. It is expected to be used as film material, civil engineering material, and medical material in horticulture, agriculture, dairy farming, and fishery.

  The trioxane (A) used in the present invention is a cyclic trimer of formaldehyde, and is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst. Used after purification by the method.

  At least one cyclic carbonate compound (B) selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one and alkyl-substituted products thereof used in the present invention is Macromolecules Chem. Phys. 199,97 (1998), Journal of Polymer Science Part A Polym. Chem. 31,581 (1993) and the like, and further purified by recrystallization or the like.

  The polyacetal carbonate copolymer of the present invention comprises at least one cyclic compound selected from trioxane (A), 1,3-dioxepan-2-one, 1,3-dioxan-2-one, and alkyl-substituted products thereof. It is obtained by ring-opening copolymerization with a carbonate compound (B).

  A preferred use ratio of the trioxane (A) and the cyclic carbonate compound (B) is (A) / (B) = 99.9-10 mol% / 0.1-90 mol%. When the amount of trioxane (A) used exceeds 99.9 mol%, at least one cyclic carbonate compound selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one, and alkyl-substituted products thereof If the amount of trioxane (A) used is less than 10 mol%, the proportion of polyacetal skeleton generated by ring-opening polymerization of trioxane (A) is low. Since it becomes less, it becomes difficult to maintain the mechanical strength, which is not preferable.

Ring-opening copolymerization of trioxane (A) with at least one cyclic carbonate compound (B) selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one and alkyl-substituted products thereof In the production of the polyacetal carbonate copolymer of the present invention, the polymerization initiator used is perfluoroalkylsulfonic acid and its anhydride, perchloric acid, acetyl perchlorate, t-butyl perchlorate, hydroxyacetic acid. , Inorganic and organic acids such as trichloroacetic acid, trifluoroacetic acid and p-toluenesulfonic acid, complex salts such as triethyloxonium tetrafluoroborate, triphenylmethylhexafluoroantimonate, allyldiazonium hexafluorophosphate, allyldiazonium tetrafluoroborate Compound, die Alkyl metal salts such as ruzinc, triethylaluminum, diethylaluminum chloride, heteropolyacid, isopolyacid, lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trichloride, pentafluoride Phosphorus fluoride, antimony pentafluoride, boron trifluoride, boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetate anhydrate, boron trifluoride triethylamine 1 type, or 2 or more types, such as boron trifluoride coordination compounds, such as a complex compound, are mentioned. In particular, perfluoroalkylsulfonic acid, its anhydride, and its derivatives are preferably used. Specific examples of perfluoroalkylsulfonic acid include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, Nonafluorobutanesulfonic acid, undecanefluoropentanesulfonic acid, perfluoroheptanesulfonic acid and the like can be mentioned. Specific examples of the perfluoroalkylsulfonic acid anhydride include trifluoromethanesulfonic acid anhydride, pentafluoroethanesulfonic acid anhydride, heptafluoropropanesulfonic acid anhydride, and the like. Specific examples of the perfluoromethanesulfonic acid derivative include methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl pentafluoroethanesulfonate, methyl heptafluoropropanesulfonate, and the like.

  In producing the polyacetal carbonate copolymer of the present invention, as a polymerization method, a conventionally known method such as a bulk polymerization method using the monomer directly, a solution polymerization method using a solvent, and a suspension polymerization method is applied. can do. As the solvent in the polymerization method using a solvent, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethylene chloride, trichloroethylene, halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene, sulfur-containing compounds such as dimethyl sulfoxide, nitrobenzene, etc. Examples thereof include nitrogen-containing compounds, ether compounds such as diethyl ether, dibutyl ether, and tetrahydrofuran. Moreover, the apparatus used for superposition | polymerization is not specifically limited, Both a batch type, a continuous type, etc. are possible. Further, the molecular weight or melt viscosity of the copolymer of the present invention is not limited at all.

  The polyacetal carbonate copolymer of the present invention obtained as described above has a chemical structure of the copolymer, such as a formal site, a carbonate site, and an ether site (where the carbonate site is opened), as described in detail in Examples below. Decomposability can be improved by having a carbonic acid moiety, which is generated by decarboxylation during the ring.

  The polyacetal carbonate copolymer of the present invention is obtained by ring-opening copolymerization of trioxane (A) and the cyclic carbonate compound (B) as described above. In addition to these main components, a cyclic ether and It is also possible to use conventionally known reaction components such as cyclic formal, glycidyl ether compounds, and components for adjusting the molecular weight.

  Examples of cyclic ethers and / or cyclic formals that can be used in the present invention include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, styrene oxide, oxetane, and 3,3-bis (chloromethyl) oxetane. , Tetrahydrofuran, trioxepane, 1,3-dioxolane, ethylene glycol formal, propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1,4-butanediol formal, 1,5-pentanediol formal, 1,6-hexanediol formal Among them, ethylene oxide, 1,3-dioxolane, diethylene glycol formal, and 1,4-butanediol formal are preferable. Moreover, the addition amount or addition method of these cyclic ethers and / or cyclic formals is not limited at all as long as the effects of the present invention are not impaired.

  Examples of glycidyl ether compounds that can be used in the present invention include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, stearyl glycidyl ether, Ethoxybutyl glycidyl ether, 1-allyloxy-2,3-epoxypropane, 1- (1 ′, 1′-dimethylpropargyloxy) -2,3-epoxypropane, phenyl glycidyl ether, cresyl glycidyl ether, butylphenyl glycidyl ether , Naphthyl glycidyl ether, phenylphenol glycidyl ether, benzyl alcohol glycidyl ether, ethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether And polybutylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether and the like. Moreover, the addition amount of these glycidyl ether compounds or the addition method will not be limited at all, if it is a range which does not impair the effect of this invention.

  Examples of the component for adjusting the molecular weight (molecular weight regulator) usable in the present invention include a low molecular weight acetal compound having an alkoxy group, alcohols such as methanol, ethanol, butanol, ethylene glycol and polyalkylene glycol, water, and ester compounds. Illustrated. Among them, a low molecular weight acetal compound having an alkoxy group is preferable, and specific compound names include methylal, methoxymethylal, dimethoxymethylal, trimethoxymethylal, oxymethylene di-n-butyl ether and the like. Moreover, the addition amount of these molecular weight modifiers or the addition method will not be limited at all, if it is a range which does not impair the effect of this invention.

  About the copolymer superposed | polymerized as mentioned above, the deactivation process of an initiator is further performed as needed. Regarding the method of catalyst deactivation, a method using a large amount of a basic solution, a method of adding and mixing a basic compound or a small amount of a solution containing a basic compound, a method of contacting a product with a basic gas, etc. Conventionally known methods can be used. As the deactivator to be used, any known basic substance is effective. For example, ammonia, various amine compounds, alkali or alkaline earth metal oxides, hydroxides, organic acid salts or inorganic acid salts. And trivalent phosphorus compounds. Amine compounds include primary, secondary and tertiary aliphatic amines and aromatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine and the corresponding alcohols. Examples include amines (such as triethanolamine), aniline, diphenylamine, heterocyclic amines, hindered amines (various piperidine derivatives), and the like. Examples of the alkali or alkaline earth metal compound include inorganic weak acid salts such as alkali metal or alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, phosphates, borates, and silicates. , Acetate, oxalate, formate, benzoate, terephthalate, isophthalate, phthalate, fatty acid salt and other organic acid salts, methoxide, ethoxide, n-butoxide, sec-butoxide, tert-butoxide And alkoxides such as phenoxide. A combination of two or more of these is also a preferred method.

  After the polymerization method and the deactivation method, if necessary, further separation of solvent, washing, separation and recovery of unreacted monomers, drying, and the like are performed by a conventionally known method. In addition, the obtained crude polymer is further subjected to terminal stabilization treatment such as decomposition removal of unstable terminals or sealing of unstable terminals with a stable substance, if necessary, and various stabilizers and additions depending on the purpose. Agents and reinforcing materials can also be blended.

  As the known stabilizer, one or more of hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, carboxylates and the like can be mentioned. . Furthermore, as long as the purpose and effect of the present invention are not impaired, general additives for thermoplastic resins, for example, colorants such as dyes and pigments, lubricants, mold release agents, antistatic agents, surfactants, if necessary. Alternatively, one or more organic polymer materials, inorganic or organic fibrous, powdery, and plate-like fillers can be added.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, the method used for characteristic evaluation in the Example is as follows.
(1) Identification of cyclic carbonate compound and determination of copolymer composition NMR measurement was performed using a nuclear magnetic resonance apparatus, JEOL JNM-LA-270.
(2) Determination of the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the copolymer
Using Tosoh DP-8020 (pump) and Viscotek TDA300 (RI detector), GPC measurement was performed with eluent THF (tetrahydrofuran) at a flow rate of 1.0 ml / min and 40 ° C. The molecular weight was calculated using a calibration curve with polystyrene as a standard.
(3) Measurement of melting point of cyclic carbonate compound and copolymer It was measured using Seiko TG / DTA-220.
Reference Example 1 (Synthesis of 1,3-dioxepan-2-one)
It was synthesized according to Macromolecules Chem. Phys. 199, 97 (1998), recrystallized with diethyl ether / hexane and purified. The yield was 23% and the melting point was 75.5-76.5 ° C.

Measured by ¹ H-NMR (solvent: deuterated chloroform), peaks of 1.89-2.01 ppm and 4.15-4.27 ppm, and measured by ¹³ C-NMR (solvent: deuterated chloroform), 27.7 ppm The obtained compound was confirmed to be 1,3-dioxepan-2-one by peaks at 70.8 ppm and 155.4 ppm.
Reference Example 2 (Synthesis of 1,3-dioxan-2-one)
It was synthesized according to Journal of Polymer Science Part A Polym. Chem. 31,581 (1993), recrystallized with diethyl ether / THF and purified. The yield was 52% and the melting point was 45 ° C.

21.6 ppm measured by ¹ H-NMR (solvent: deuterated chloroform), 2.1-2.2 ppm and 4.4-4.5 ppm peaks, and ¹³ C-NMR (solvent: deuterated chloroform) From the peaks at 67.9 ppm and 148.5 ppm, it was confirmed that the obtained compound was 1,3-dioxan-2-one.
Example 1
A glass container equipped with a nitrogen flow tube was charged with trioxane (2.04 g, 22.6 mmol), 1,3-dioxepan-2-one (2.62 g, 22.6 mmol) and a nitrobenzene solution (45.2 ml) at 30 ° C. Then, trifluoromethanesulfonic acid (40 μl) was added as an initiator, and polymerization was carried out with stirring at the same temperature for 3 hours. Then, triethylamine (10 ml) was added as a quencher to stop the reaction. The reaction mixture was added dropwise to diethyl ether, and the resulting precipitate was filtered and dried under reduced pressure to obtain a copolymer in a yield of 56%.

The copolymer was identified by ¹ H-NMR (solvent: deuterated hexafluoroisopropanol). Polyacetal-derived peaks were around 4.99 ppm, polycarbonate-derived peaks were around 1.74 ppm and 4.20 ppm, Moreover, when carbonate was opened, peaks decarboxylated to become polyether appeared at 1.74 ppm and 3.17 ppm, confirming the formation of a copolymer. Further, by calculating these integral ratios, the composition of acetal site: carbonate site: ether site = 71: 17: 12 was calculated. The obtained copolymer had a number average molecular weight of 19,000 and a molecular weight distribution (Mw / Mn) of 1.52.
Example 2
The reaction and purification were carried out in the same manner as in Example 1 except that trioxane (36.2 mmol) and 1,3-dioxepan-2-one (9.0 mmol) were used as the charge composition of trioxane and 1,3-dioxepan-2-one. The copolymer was obtained with a yield of 33%.

The copolymer is identified by ¹ H-NMR (solvent: deuterated hexafluoroisopropanol), and by calculating the integral ratio of these, an acetal site: carbonate site: ether site = 84: 5: 11 The composition was calculated.
Example 3
The reaction and purification were conducted in the same manner as in Example 1 except that trioxane 1,3-dioxepan-2-one was charged with trioxane (9.0 mmol) and 1,3-dioxepan-2-one (36.2 mmol). The polymer was obtained in 66% yield.

The copolymer was identified by ¹ H-NMR (solvent: deuterated hexafluoroisopropanol), and by calculating the integral ratio of these, the acetal part: carbonate part: ether part = 2: 91: 7 The composition was calculated. The obtained copolymer had a number average molecular weight of 23,000 and a molecular weight distribution (Mw / Mn) of 1.81.
Example 4
A glass container equipped with a nitrogen flow tube was charged with trioxane (2.04 g, 22.6 mmol), 1,3-dioxan-2-one (2.31 g, 22.6 mmol), and a nitrobenzene solution (45.2 ml) at 30 ° C. Then, trifluoromethanesulfonic acid (40 μl) was added as an initiator and polymerization was carried out while stirring at the same temperature for 24 hours, and then triethylamine (10 ml) was added as a quencher to stop the reaction. The reaction mixture was added dropwise to diethyl ether, and the resulting precipitate was filtered and dried under reduced pressure to obtain a copolymer in a yield of 17%.

The copolymer was identified by ¹ H-NMR (solvent: deuterated hexafluoroisopropanol). Polyacetal-derived peaks were around 4.76 ppm and 4.96 ppm, and polycarbonate-derived peaks were 2.00 ppm and 4.27 ppm. In the vicinity, peaks where carbonate was decarboxylated to form a polyether during ring opening appeared at 2.00 ppm and 4.75 ppm, confirming the formation of a copolymer. Further, by calculating these integral ratios, the composition of acetal part: carbonate part: ether part = 95: 3: 2 was calculated.

  As described above, the polyacetal carbonate copolymer of the present invention obtained in Examples 1 to 4 has a formal site, a carbonate site, and an ether site as its chemical structure.

  This copolymer is considered to have sufficient mechanical properties, etc. when used as a molded product mainly from the presence and ratio of the formal site, and is mainly decomposable from the presence and proportion of the carbonate site. It is considered excellent, and is expected to be used as a film material, civil engineering material, and medical material in packaging materials, horticulture, agriculture, dairy farming, fishery, and the like.

Claims (4)

Trioxane (A) is copolymerized with at least one cyclic carbonate compound (B) selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one, and alkyl-substituted products thereof. A polyacetal carbonate copolymer. The polyacetal carbonate copolymer according to claim 1, wherein the use ratio of trioxane (A) to the cyclic carbonate compound (B) is (A) / (B) = 99.9 to 10 mol% / 0.1 to 90 mol%. A perfluoroalkyl comprising trioxane (A) and at least one cyclic carbonate compound (B) selected from 1,3-dioxepan-2-one, 1,3-dioxan-2-one, and alkyl-substituted products thereof. A method for producing a polyacetal carbonate copolymer comprising copolymerizing at least one compound selected from a sulfonic acid, an anhydride thereof and a derivative thereof as an initiator. The method for producing a polyacetal carbonate copolymer according to claim 3, wherein the use ratio of the trioxane (A) and the cyclic carbonate compound (B) is (A) / (B) = 99.9-10 mol% / 0.1-90 mol%. .